Matting article

Abstract

Provided is a matte article having excellent visibility and texture of a matte effect, and excellent dry smoothness of touch, the matte article having a surface shape in which the Ssk (skewness) defined in ISO 25178-2:2012 is 0.00 or higher and the Sku (kurtosis) is 3.50 or lower in at least a part of a surface.

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 (exterior walls, eaves, roofs, fences, etc.); window and door fixtures or decorative components (window frames, doors, door frames, handrails, crossbeams, perimeter edges, trim strips, etc.); general furniture (wardrobes, shelves, tables, etc.); kitchen furniture (dining tables, sinks, etc.); surface decorative panels for the housings of home appliances, office equipment, etc.; and interior or exterior components of vehicles. Furthermore, decorative materials, for example, those with a surface layer possessing the desired function, are used.

[0003] For decorative materials used in these applications, it is common practice to enhance texture by utilizing a matte effect (also known as a "glossy effect") 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-adjusting layer such as a matte layer and a 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-adjusting layer achieves a design effect that highlights the pattern layer and the masking layer. In its embodiment, the matte layer, which is applied to the entire surface, uses a matte ink containing a total of 50 parts by weight of a matting agent, with 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate added per 100 parts by weight of resin component.

[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 finish, the main examples include the use of a matting agent (also known as a "matting agent") as described in Patent Document 1 above, which achieves a matte finish 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. But as the amount increases, surface properties tend to decrease due to several reasons: the matting agent peels off the coating, damaging it and reducing scratch resistance; damage becomes more noticeable due to gloss changes caused by the absence of matting agent; and contaminants 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, creating a contradictory relationship between surface properties and matting effect. 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 a visually matte finish as described above, but also a tactile feel. For example, when using a matting agent like that in Patent Document 1, increasing the amount used causes the outline of the matting agent to be exposed on the surface of the decorative sheet, sometimes resulting in a slightly rough feel. Furthermore, when using embossing as in Patent Document 2, a tactile feel is sometimes achieved due to the uneven shape of the surface formed by the embossing plate. However, in both cases, tactile feel is not adequately considered, resulting in a situation where a sufficient level of tactile quality cannot be achieved. In other words, conventional decorative sheets and materials cannot be said to simultaneously achieve excellent matte finish and tactile feel. In this invention, a "dry and smooth" tactile feel is particularly emphasized.

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

[0015] Methods for solving problems

[0016] To address the aforementioned issues, the present invention provides a matte article having at least a portion of its surface having a surface shape as specified in ISO 25178-2:2012, with a Sk (skearing) of 0.00 or more and a Sku (kurtosis) of 3.50 or less.

[0017] Invention Effects

[0018] According to the present invention, matte articles with excellent visibility and texture and excellent dry and smooth feel can be provided. Attached Figure Description

[0019] Figure 1 This is a schematic diagram illustrating the surface shape of the matte article of the present invention.

[0020] Figure 2 This is a schematic diagram illustrating the surface shape of the matte article of the present invention.

[0021] Figure 3 This is a cross-sectional view showing one embodiment of the matte article of the present invention.

[0022] Figure 4 This is a cross-sectional view showing one embodiment of the matte article of the present invention.

[0023] Figure 5 This is a cross-sectional view showing one embodiment of the matte article of the present invention.

[0024] Figure 6 This is a top view schematic diagram illustrating one embodiment of the matte article of the present invention.

[0025] Figure 7 This is an optical microscope image of the surface of the matte article obtained in Example 1.

[0026] Figure 8 This is an optical microscope image of the surface of the matte article obtained in Example 2.

[0027] Figure 9 This is an optical microscope image of the surface of the matte article obtained in Example 3.

[0028] Figure 10 This is an optical microscope image of the surface of the matte article obtained in Example 4.

[0029] Figure 11 This is an optical microscope image of the surface of the matte article obtained in Example 5.

[0030] Figure 12 This is an optical microscope image of the surface of the matte article obtained in Example 6.

[0031] Figure 13These are optical microscope images of the surface of the item obtained in Comparative Example 1.

[0032] Figure 14 This is an optical microscope image of the surface of the item obtained in Comparative Example 2. Detailed Implementation

[0033] Matte finish items

[0034] The matte article of the present invention will now be described. It should be noted that, in this specification, the values ​​referred to by "above", "below", and "~" related to the description of numerical ranges are values ​​that can be arbitrarily combined, and the values ​​in the embodiments are values ​​that can be used as the upper and lower limits of the numerical range.

[0035] The matte article of the present invention is characterized in that at least a portion of its surface has a surface shape with a Sk (skism) of 0.00 or more and a Sku (ku) of 3.50 or less as specified in ISO 25178-2:2012.

[0036] [Regarding surface shape]

[0037] The description will be based 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 the present invention.

[0038] The surface shape requires a Sk (skewness) of 0.00 or higher and a Sku (ku) of 3.50 or lower, as specified in ISO 25178-2:2012. By having such a surface shape, the matte articles of the present invention exhibit excellent visibility and texture of the matte effect, and as a tactile experience, they exhibit a particularly "dry and smooth" feel. Hereinafter, the "visibility and texture of the matte effect" will sometimes be simply referred to as the "matte effect."

[0039] The sensation of "dry and smooth" is a sensory experience, but in this instruction manual, "dry and smooth" generally encompasses all sensations of a "dry and smooth" feel. Specifically, it refers to the sensation felt when touching a smooth surface without moisture with the fingertips.

[0040] The "dry and smooth" feel of an item can vary depending on its surface finish. Furthermore, for fabrics (described later), the feel can vary depending on their weaving method, so generalizations are not possible. Examples include high-quality paper without a coated surface, Oxford cloth made with fine yarns (around 60-120 count), and even baby skin. Additionally, fabrics made from natural fibers such as silk and Tencel (also known as "Lyser"), and metals like brass, gold, silver, copper, aluminum, steel, and stainless steel, especially those with various surface finishes such as hairline finishing, sprue finishing, and sandblasting, can also be listed as items with a "dry and smooth" feel. It should be noted that regarding surface finishes like hairline finishing and sandblasting on metals, depending on the degree of processing, there are cases where the feel is not "dry and smooth," but this excludes cases where such finishes have been applied. In addition, regarding other fabrics, depending on the thickness of the yarn used and the weaving method, there are cases where the feel is not "dry and smooth," but of course, this does not include such cases.

[0041] Therefore, the matte articles of the present invention are preferably used for applications where it is desired to showcase the designs of fabrics, metals, etc. In this case, the matte articles of the present invention preferably have a decorative layer having a pattern on the surface of various materials such as fabrics and metals, in order to showcase the desired design. Details regarding the decorative layers that the matte articles of the present invention can have will be described later.

[0042] Skewness (Ssk) is one of the three-dimensional surface property parameters specified by ISO, and it is an indicator of the degree of deviation in the distribution of height from the mean plane. When Ssk is 0, the surface shape is symmetrical with respect to the mean plane. If Ssk exceeds 0, the surface shape deviates from the mean plane on the lower side, i.e., the side with lower height. It is a measure that can be understood as a tendency for convex parts to taper sharply near the top. Here, "symmetrical with respect to the mean plane" can also be referred to as "normal distribution".

[0043] On the other hand, if Ssk is less than 0, the surface shape is biased upwards relative to the average surface, i.e., the side with higher height. This can be measured as a tendency for the top of the convex part to become blunter and coarser. Figure 1 The trend of the shape exhibited by the surface shape represented by Ssk (skex) is explained.

[0044] Figure 1This is a schematic diagram showing when Ssk (skexia) exceeds 0 (1-1) and is less than 0 (1-2). A surface shape in this invention with an Ssk (skexia) of 0.00 or higher indicates a tendency towards having the shape shown in (1-1). That is, since the surface shape deviates from the average surface on the lower side, the surface shape, which is the surface side above the average surface (i.e., the matte shape of this invention), can be said to have the following shape: it has more convex portions with a narrow width relative to its height, a high aspect ratio, and an elongated cross-sectional shape, distributed at a certain distance. Here, in Figure 1 and Figure 2 In this context, the "mean surface" is the average level surface, equivalent to a horizontal line. "Relative to the lower side of the mean surface" refers to... Figure 1 and Figure 2 The middle is also the bottom side, or the outer surface side of a matte item.

[0045] Based on its relationship with Sku (ku) described later, Ssk (skewness) is preferably 0.03 or higher, more preferably 0.05 or higher, and as an upper limit, preferably 1.50 or lower, more preferably 1.00 or lower, more preferably 0.75 or lower, and even more preferably 0.50 or lower. If Ssk (skewness) is within the above range, the matting effect and the dry, smooth feel are improved.

[0046] Ssk (skewness) is measured using a shape analysis laser microscope on a rectangular area (1024 μm × 768 μm) of any part of the surface shape of the matte article. The measurement conditions can be adjusted appropriately, for example, the conditions described in the examples can be used. In addition, Sku (kurtosis), as well as RSm (average length of curve element), Rz (maximum height), and Ra (arithmetic mean roughness) related to the profile curve, can also be measured in the same way.

[0047] Kurtosis (Sku) is one of the three-dimensional surface characteristics parameters defined by ISO, and it is an indicator of the sharpness of the distribution of height relative to the mean surface. When Sku is 3, the surface shape is symmetrical with respect to the mean surface (normal distribution). If Sku exceeds 3, it tends to have a sharply distributed shape; if Sku is less than 3, it tends to have a flattened shape. Sku is a measurement that captures these characteristics. Figure 2 This section describes the trend of the shape represented by the surface shape, expressed by Sku (kurtosis). Figure 2These are schematic diagrams showing Sku (kurtosis) values ​​less than 3.000 (2-1) and greater than 3.00 (2-2). In this invention, a surface shape with a Sku (kurtosis) value of 3.50 or less indicates a tendency for the surface shape to exhibit a sharp height distribution as shown in (2-2), a shape with a gradually tapering height distribution, a shape exceeding 3.00 but less than 3.50, and a shape with a flattened height distribution as shown in (2-1). In other words, the surface shape can be described as having a rounded shape or a gradually tapering shape near the top of the convex portion on the upper side relative to the average surface, and the shape near the lowest surface of the concave portion on the lower side also exhibits a rounded shape or a gradually tapering shape, similar to the convex portion. Here, "relative to the upper side of the average surface" refers to... Figure 1 and Figure 2 The middle is also the upper side, or the outer surface side of a matte item.

[0048] In relation to the previously described Sk (skewness), Sku (ku) is preferably 2.95 or less, with a lower limit being 1.00 or more, more preferably 1.50 or more, further preferably 2.00 or more, and even more preferably 2.30 or more. If the Sku (ku) is within the above range, the matting effect and the dry, smooth feel are improved.

[0049] As described above, the surface shape of the matte article of the present invention has specific Ssk (skearing) and Sku (kurtosis), and has the following characteristics: more convex parts with a narrow width relative to the height based on Ssk (skearing), a higher aspect ratio, and an elongated cross-sectional shape that are distributed at a certain distance, and the shape near the top of the convex parts based on Sku (kurtosis) is rounded.

[0050] Regarding the surface shape of the matte article of the present invention, the rounded shape near the top of the protrusions and the abundance of elongated protrusions allow for a rounded tip shape to be felt at a moderate frequency when touched with the fingertip. This sensation is believed to result in a smooth, dry feel, i.e., a "dry and smooth" feel. Furthermore, the presence of these protrusions, coupled with the relative concave areas, also contributes to the matte effect. Details regarding the performance of the matte effect will be described later.

[0051] The surface shape of the matte article of the present invention preferably has the shape described later. Figure 6The diagram shows minute wrinkles visible when viewed from above. Regarding the surface shape of the matte article of the present invention, Ssk (skearing) and Sku (kurtosis), preferably RSm (average length of the curve element), Rz (maximum height), and Ra (arithmetic mean roughness), which are described later, are easily within specific numerical ranges due to the presence of minute wrinkles. On the other hand, minute wrinkles are easily formed by having Ssk (skearing) and Sku (kurtosis) within specific numerical ranges, and preferably having RSm (average length of the curve element), Rz (maximum height), and Ra (arithmetic mean roughness) within specific numerical ranges. Thus, it can be said that Ssk (skearing) and Sku (kurtosis), etc., are consistent with the minute wrinkles. Furthermore, by having such a surface shape, the matte effect is improved while enhancing the dry and smooth feel.

[0052] In the surface shape of matte articles, in order to set Ssk (skearing) and Sku (kurtosis) within the specific numerical range mentioned above, it is preferable to set them as RSm (average length of curve element), Rz (maximum height), and Ra (arithmetic mean roughness) as described later. As mentioned above, it is preferable that:

[0053] (1) A micro-wrinkled structure is formed on the surface of the matte layer. Preferably:

[0054] (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 agents when wrinkle-forming stabilizers are used.

[0055] (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.

[0056] (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 Ssk (skearing) and Sku (kurtosis) within the specific numerical range mentioned above for the surface shape of the matte article of the present invention, and preferably make RSm (average length of curve element), Rz (maximum height) and Ra (arithmetic mean roughness) within the specified numerical range described later.

[0057] In this invention, as the surface shape, the lateral parameter RSm (average length of the curve element) of the profile curve specified in JIS B0601:2013 is preferably 100.00 μm or less.

[0058] RSm (average length of curve elements) is a lateral parameter of the profile curve, representing the average length of the profile curve elements within a reference length. A smaller RSm value indicates a narrower width of the convex portion, becoming an indicator of a surface shape with a tendency towards narrower convex portions. Therefore, in surface shapes satisfying the aforementioned Ssk (skearing) and Sku (kurtosis), if RSm (average length of curve elements) is 100.00 μm or less, the width of the convex portion of the surface shape becomes narrower, and its leading edge is rounded. Thus, the rounded leading edge shape of the convex portion, as specified by Sku (kurtosis), is emphasized, improving the dry and smooth feel. Furthermore, the matting effect is also improved.

[0059] The average length of the curve element (RSm) is preferably 90.00 μm or less, more preferably 75.00 μm or less, even more preferably 60.00 μm or less, and even more preferably 40.00 μm or less. As a lower limit, it is preferably 15.00 μm or more, more preferably 17.50 μm or more, and even more preferably 20.00 μm or more. If the average length of the curve element (RSm) is within the above range, the matting effect and the dry, smooth feel are improved.

[0060] It should be noted that when measuring RSm (average length of curve element) in this specification, the cutoff value is 0.8 mm.

[0061] In this invention, as a surface shape, the lateral parameter Rz (maximum height) of the profile curve specified in JIS B0601:2013 is preferably 3.00 μm or more.

[0062] Rz (maximum height) is one of the peak and height parameters of the profile curve. It is the sum of the height of the highest peak and the depth of the deepest valley in the profile curve over a reference length. The larger the value of Rz (maximum height), the more prominent (tall) convexities are when viewed from the valley, making it an indicator of a tendency for such convexities to be abundant. Therefore, in surface shapes that satisfy the above-mentioned Ssk (skewness) and Sku (ku), if Rz (maximum height) is 3.00 μm or higher, the rounded front end shape of the convexities specified based on the above-mentioned Sku (ku) is emphasized, improving the dry and smooth feel. In addition, the matting effect is also improved.

[0063] The maximum height (Rz) is preferably 3.25 μm or more, more preferably 3.50 μm or more, and even more preferably 4.00 μm or more. As an upper limit, it is preferably 12.50 μm or less, more preferably 11.50 μm or less, and even more preferably 10.50 μm or less. If the maximum height (Rz) is within the above range, the matte finish and the dry, smooth feel are improved.

[0064] It should be noted that when measuring Rz (maximum height) in this instruction manual, the cutoff value is 0.8 mm.

[0065] In this invention, as a 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.

[0066] 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 convexities and corresponding concave areas in the surface shape become, indicating a tendency to become a smoother and more uniform shape. Therefore, in surface shapes that satisfy the above-mentioned Ssk (skearing) and Sku (kurtosis), if Ra (arithmetic mean roughness) is below 2.00 μm, there is a greater presence of more uniform and gentler convex shapes in the surface shape, thus suppressing abnormal tactile sensations, especially improving the dry and smooth feel. In addition, the matting effect is also improved.

[0067] 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. If the Ra (arithmetic mean roughness) is within the above range, the matting effect and the dry, smooth feel are improved.

[0068] It should be noted that when measuring Ra (arithmetic mean roughness) in this specification, the cutoff value is 0.8 mm.

[0069] [Regarding layer composition]

[0070] The matte article of the present invention does not have any particular limitation on the layer composition as long as it has the shape specified by the above parameters as the surface shape, and any layer structure can be adopted.

[0071] For example, the simplest layer structure of the matte article of the present invention can be exemplified by, for instance, Figure 3 The structure of a single layer is shown. As... Figure 3 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 formed by embossing or other processing on the surface of a resin molded article, and other articles consisting of a single layer.

[0072] 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 4 and Figure 5 An article consisting of multiple layers stacked as shown, for example, an article consisting of a laminate having a substrate and having a cured layer of a resin composition having the aforementioned surface shape in at least a portion thereof as a matting layer.

[0073] Hereinafter, regarding the layers constituting the matte article of the present invention, for an article constituting a laminate as one of the preferred embodiments, 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 will be described.

[0074] [Substrate]

[0075] The morphology (or shape) of the substrate forming the matte article of the present invention is not particularly limited, and various shapes such as film, sheet or plate, polyhedron, polygonal prism, cylinder, sphere, and ellipsoid of revolution are preferred. Here, film, sheet, and plate are referred to as film, sheet, and plate because of their relatively thin thickness, but in this specification, there is no particularly strict distinction between these three terms, and the interpretation of the claims of the present 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.

[0076] In the case where the matte article of the present invention 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, for example, thus improving post-processing adaptability.

[0077] 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 together allows for the complementary functions of each layer.

[0078] 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:

[0079] (1) Resin / wood-based materials

[0080] (2) Resin / metal

[0081] (3) Resin / fibrous materials,

[0082] (4) Resin / Non-metallic inorganic materials

[0083] (5) Resin 1 / Resin 2 (for example, the case where there are multiple layers composed of different resins such as "olefin resin / acrylic resin")

[0084] (6) Metal / wood-based materials

[0085] (7) Metallic / non-metallic inorganic materials

[0086] (8) Metal / fibrous materials

[0087] (9) Metal 1 / Metal 2 (e.g., the case of having multiple layers composed of different metals such as "copper / chromium")

[0088] (10) Non-metallic inorganic materials / fibrous materials, etc.

[0089] 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).

[0090] 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.

[0091] 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.

[0092] Natural resins such as natural rubber, rosin, and amber are preferred examples.

[0093] 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.

[0094] Examples of metals suitable for use as substrates include aluminum or aluminum alloys such as aluminum and duralumin; iron or iron alloys such as iron, carbon steel, and stainless steel; copper or copper alloys such as copper, brass, and bronze; and 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.

[0095] Non-metallic inorganic materials that can be used as substrates include, for example, cement, ALC (lightweight aerated concrete), gypsum, calcium silicate, wood chip cement and other non-ceramic kiln materials; ceramic kiln materials such as ceramics, pottery, glass, enamel and other ceramic kiln materials; and natural stones such as limestone (including marble), granite, and andesite.

[0096] Examples of fibrous materials suitable for use as substrates include, for instance, thin paper, kraft paper, premium paper, Japanese paper, titanium dioxide paper, cotton linter paper, tracing paper, paraffin paper, parchment paper, cellophane, wallpaper liner paper, cardboard, and gypsum board base paper; and woven or nonwoven fabrics made from polyester resin fibers, acrylic resin fibers, natural fibers such as silk, kapok, and hemp (protein or cellulose-based), glass fibers, and carbon fibers. In order to improve the inter-fiber strength of paper substrates made of paper, or the interlayer strength of other substrates used in combination with washi paper substrates, and to prevent pilling, various resins such as acrylic resins, styrene-butadiene rubber, melamine resin, and urethane resin can be further added (these resins are impregnated after papermaking or filled during papermaking). Examples of paper with added resin include inter-paper reinforced paper and resin impregnated paper.

[0097] In addition, as a laminate made by stacking layers of fibrous materials and layers of resin, wallpaper raw materials commonly used in the building materials field can be preferably made by stacking layers of various resins such as vinyl chloride resin, olefin resin, and acrylic resin on the surface of wallpaper backing paper.

[0098] Wood-based materials that can be used as substrates include, for example, veneers, plywood, engineered wood, particleboard, and medium-density fiberboard (MDF) made of various woods such as cedar, cypress, pine, beech, oak, oak, walnut, lauan, teak, and rubber tree.

[0099] As a substrate, any substrate made of the aforementioned materials can be used without limitation; furthermore, it can be appropriately selected according to the desired properties, etc. From the viewpoint of improving the matte effect and the dry, smooth feel, a substrate made of resin is preferred, a substrate made of fibrous material is preferred, and a substrate made of resin is more preferred.

[0100] 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 the dry, smooth feel is easily improved.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] 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.

[0105] The substrate can be colored or not (it can be transparent). If it is colored, there are no particular restrictions on the way it is colored. It can be transparent or opaque (masking color). They can be chosen arbitrarily.

[0106] 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 containing flake-like foils of aluminum, brass, etc.; and pearlescent (pearlescent) pigments containing flake-like foils of titanium dioxide coated with mica, basic lead carbonate, etc. For example, when the surface tone of the bonded material, such as a resin molded product of a laminated matte article, is uneven, and it is desired to mask the surface tone and improve the tone stability of the decorative layer to be applied as required, inorganic pigments such as white pigments can be used.

[0107] 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 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.

[0108] 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 or adding to the substrate, or a combination thereof.

[0109] Additives can be incorporated into the substrate as needed. When the main component is resin, examples of additives 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.

[0110] From the viewpoint of improving the weather resistance of the matte articles of the present invention, weather-resistant agents such as ultraviolet absorbers and light stabilizers are preferably used among the above-mentioned additives.

[0111] 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.

[0112] These UV absorbers, light stabilizers, and other weather-resistant agents, as well as various other additives, can be used alone or in combination.

[0113] In this invention, the aforementioned substrates can be used alone or in combination. The substrate can be a combination of multiple paper substrates, or a combination of paper substrates and fiber substrates, paper substrates and resin substrates, fiber substrates and resin substrates, or paper substrates, fiber substrates and resin substrates. Furthermore, the resin substrate can be a single layer of the aforementioned resin substrate, or a multilayer formed from the same or different types of resin.

[0114] 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, serviceability, post-processing adaptability, mechanical strength, and economy, 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.

[0115] For the same reason, when the substrate is paper, the weight per unit area is typically preferred to be 20–150 g / m². 2 More preferably 30-100 g / m 2 .

[0116] [Matte Layer]

[0117] The matte layer in the matte article of the present invention is a layer provided on at least a portion of the aforementioned substrate and having the aforementioned surface shape, i.e., a surface shape with Ssk (skexity) of 0.00 or more and Sku (kurtosis) of 3.50 or less. Additionally, as... Figure 4 As shown, the layer is provided such that the surface with the surface shape is the opposite side to the substrate side.

[0118] Therefore, the matte article of the present invention preferably has the following structure: it has a matte layer, the surface shape of which is formed by the surface of the matte layer; in addition, considering mechanical strength, manufacturing adaptability, etc., the matte layer is preferably a layer composed of a cured resin composition, and more preferably a cured resin composition containing a cured resin.

[0119] As for the resin composition used to form the matte layer, considering the need to obtain a matte article with excellent matte effect and a smooth, dry feel, a resin composition comprising a resin and a wrinkle-forming stabilizer (hereinafter, sometimes referred to as "resin composition for forming a matte layer") is preferred. That is, in the present invention, the matte layer is preferably a layer comprising a resin and a wrinkle-forming stabilizer.

[0120] (Wrinkle formation stabilizer)

[0121] The wrinkle-forming stabilizer functions as follows: by stabilizing wrinkle formation 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 forming the matte article, reducing local gloss unevenness, imparting stable visibility of the matte effect, and imparting surface uniformity by stably forming wrinkles across the entire surface of the matte layer. Furthermore, the wrinkles formed in the matte layer greatly contribute to expressing a dry, smooth feel. In this specification, the phrase "stable visibility of the matte effect" is sometimes used hereinafter, and is based thereon. Additionally, "uniformity of surface state" is sometimes referred to as "texture."

[0122] Therefore, even if the so-called "matting agent" in the prior art and the "wrinkle-forming stabilizer" in this invention have the same 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 "matting agents" in that they exhibit a dry and smooth feel by forming wrinkles.

[0123] In the prior art, such as Patent Document 1, the matting agent used for matting effects 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 the present invention, 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 and textured matting effect to the matting article through the light diffusion effect at the interface of the refractive index difference between the surface and air. Therefore, compared with the matting agent that exhibits a visible matting effect on its own, the wrinkle-forming stabilizer used in the present invention differs in its matting mechanism and function, and the structure used to exhibit matting, even if the constituent materials and average particle size are the same.

[0124] 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 a specific amount of C but does not form wrinkles on the surface. 60° AM (C). That is, the following relation holds.

[0125] G 60° AW (C) < G 60° AM (C)

[0126] The matte layer in the matte article of the present invention may contain reagents conventionally used as matting agents. However, considering the characteristics of the effect of the present invention—namely, consistently achieving an extremely superior matte effect that cannot be obtained even with the use of matting agents, and obtaining a dry and smooth feel—it is preferable that it does not contain matting agents. Thus, it can be said that the matte article of the present invention, even without substantially containing matting agents conventionally used to achieve visibility of the matte effect, possesses extremely superior visibility and texture of the matte effect. Here, "free of matting agents" means that, apart from being completely free of matting agents, even if it contains them, it does not have the visibility of the matting effect based on the matting agent's own action. 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.

[0127] 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.

[0128] In this invention, 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.

[0129] Considering the improvement of matte finish and a dry, smooth feel, for wrinkle-forming stabilizers with an upper limit of the smaller of 100% or less of the thickness of the matte layer and 30 μm or less, it is preferable to use at least one of two wrinkle-forming stabilizers distinguished by their average particle size. Specifically, the two wrinkle-forming stabilizers are wrinkle-forming stabilizer 1 with an average particle size of 1 μm or more and an upper limit of the smaller of 100% or less of the thickness of the matte layer and 30 μm or less, and wrinkle-forming stabilizer 2 with an average particle size of less than 1 μm.

[0130] In this invention, if at least one of the two wrinkle-forming stabilizers is used, wrinkle formation is stable, resulting in a consistently excellent matting effect and a dry, smooth feel. In this invention, wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 can be used alone, or they can be used in combination. More preferably, wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 can be used in combination. By using them in combination, both the matting effect and the dry, smooth feel are improved.

[0131] As a wrinkle-forming stabilizer, organic particles or inorganic particles can be used, for example.

[0132] 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.

[0133] 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.

[0134] There are no particular limitations on the shape of the wrinkle-forming stabilizer; for example, spherical, polyhedral, scaly, and amorphous shapes are possible.

[0135] The average particle size of the wrinkle-forming stabilizer 1 is 1 μm or more, with the upper limit being the smaller of 100% or less of the thickness of the matte layer and 30 μm or less. Considering the need to stably improve the matte effect and enhance the dry, smooth feel, the average particle size of the wrinkle-forming stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.8 μm or more. As an upper limit, relative to the thickness of the matte layer, it is preferably 90% or less, more preferably 80% or less, and even more preferably 70% or less. 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 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 upper limit can be the smaller of 90% or less of the thickness of the matte layer and 20 μm or less, or the smaller of 90% or less of the thickness of the matte layer and 10 μm or less. It should be noted that the thickness of the matte layer will be explained later.

[0136] The average particle size of the wrinkle-forming stabilizer 2 is less than 1 μm. Considering the need to stabilize wrinkle formation, consistently improve the matting effect, and enhance the dry, smooth feel, the average particle size of the wrinkle-forming stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more. As an upper limit, it is preferably 900 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less.

[0137] In this specification, the average particle size of the wrinkle-forming stabilizer is determined as the mass average value d50 in a particle size distribution determination based on laser diffraction.

[0138] If we consider the stable formation of wrinkles, the stable improvement of matte effect, and the improvement of dry and smooth feel through the wrinkle-forming stabilizer, then 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. On the other hand, as an upper limit, 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. Regarding the upper limit, there is no particular limitation on the improvement of stable matte effect and the improvement of dry and smooth feel, but if the upper limit is within the above range, the productivity of decorative materials, such as the coatability of the resin composition for forming the matte layer, as well as the visibility and texture of the matte effect are efficiently improved.

[0139] When wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 are used in combination, there are no particular restrictions on the content of each wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 as long as the total content is within the above-mentioned range. The content of wrinkle-forming stabilizer 2 relative to 100 parts by weight of resin is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, even more preferably 1.0 parts by weight or more, and as an upper limit, preferably 10.0 parts by weight or less, more preferably 7.5 parts by weight or less, even more preferably 5.0 parts by weight or less, and even more preferably 3.5 parts by weight or less. Furthermore, regarding the mixing ratio of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2, based on the amount of wrinkle-forming stabilizer 1 when their total amount is set to 100 parts by weight, it is preferably 0.05 to 0.95 parts by weight, more preferably 0.10 to 0.90 parts by weight, even more preferably 0.20 to 0.80 parts by weight, and even more preferably 0.30 to 0.70 parts by weight.

[0140] 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, consisting of 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate. However, in the present invention, as described above, even at a small amount—that is, even at a amount less than that required to achieve visible matting effects through light diffusion caused by their physical shape—an extremely superior matting effect is obtained compared to the effect obtained by using matting agents, and a dry, smooth feel is also achieved.

[0141] Therefore, it can be said that although the matte article of the present invention does not actually contain matting agents, it achieves a more stable and superior matting effect in terms of visibility compared to the case where matting agents are used, by stably forming wrinkles on the surface, while also obtaining a texture and a dry and smooth feel.

[0142] (Surface shape of the matte layer)

[0143] The matte layer in the matte article of the present invention 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 dry and smooth tactile feel. Figure 6 This is a top view schematic diagram illustrating one embodiment of the matte article of the present invention, and is a schematic diagram illustrating the surface of the matte article obtained in the embodiment. Figure 6 The image shows that the matte article of the present invention has wrinkles formed on its surface, i.e., on the surface of the matte layer. Here, "top view" refers to... Figures 3-6 In the XYZ coordinate system shown, the surface of the matte object is viewed from the positive Z-axis direction.

[0144] There are no particular restrictions on the wrinkles exhibited on at least one surface of the matte layer, as long as they present the aforementioned surface shape, i.e., have Ssk (skearing) and Sku (kurtosis) within the aforementioned specific numerical range, and preferably also have RSm (average length of curve element), Rz (maximum height), and Ra (arithmetic mean roughness) within the aforementioned specific numerical range. Because of the appearance of wrinkles, the surface shape is stabilized by wrinkle formation stabilizer, stably exhibiting a matte effect, and also exhibiting a dry and smooth feel.

[0145] Regarding wrinkles, from the viewpoint of exhibiting the aforementioned surface shape, improving the matte effect, and enhancing the dry and smooth feel, at least one surface of the matte layer preferably has an uneven shape composed of irregular wrinkles. The irregular wrinkles preferably consist of multiple protrusions and recesses, 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 raised portions. In this specification, a "linear raised portion" (hereinafter also referred to as a "linear raised portion") refers to a raised portion 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 the length and width is described below.

[0146] In this invention, more preferably, the irregular folds are composed of multiple protrusions and concave portions, wherein the multiple protrusions are formed by multiple line protrusions, and the concave portions are formed by being surrounded by multiple line protrusions.

[0147] As a way related to these folds, for example, can be cited as Figure 6 As shown. In Figure 6 The invention also shows an article with 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 3 formed by multiple curved line protrusions and recesses 2 formed by being surrounded by the multiple protrusions (multiple protrusions 3). Furthermore, at least a portion of each of the multiple curved protrusions 3 is formed by meandering line protrusions, forming meandering recesses 2 such that they are surrounded by the meandering line protrusions. The matte article of the present invention... Figure 6 The stable formation of the folds results in a consistent matte finish and a dry, smooth feel.

[0148] Here, "curve" refers to a portion in which the extension direction of a continuous line's protrusion 3, 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 shapes with inflection points when approximating a continuous curve, neglecting the width of the line's protrusion 3 in its top view (assuming the width of the top view shape is 0). Furthermore, when approximating a straight line while neglecting the width of the line's protrusion 3 in its top view, examples include V-shaped broken lines or portions approximating a triangle with two sides containing one vertex.

[0149] Furthermore, "winding" refers to a portion where the extension direction of a protrusion 3, which has at least two continuous lines when viewed from above, reverses from one side to the other (hereinafter also referred to as "reversed portion"). And when the protrusion 3 of the line extends along its extension direction, portions where the extension direction of the protrusion 3 of the line alternately reverses in two adjacent locations. For example, if the width of the top-view shape of the protrusion 3 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 3 of the line is ignored and approximated as a straight line, a shape approximating the Roman letter "W" can be given.

[0150] In this specification, "irregular" refers to a shape that cannot be described as having a fixed rule or a pattern that is not arranged according to a fixed rule. Typical examples of non-irregular shapes, i.e., regular shapes, include, for instance, a so-called "lenticular lens," which is formed by arranging multiple cylindrical unit lenses adjacent to each other in a direction orthogonal to their length direction, or a shape arranged in a certain periodicity in a specific direction. Therefore, the irregular wrinkles in this invention include the following: the shape of a protrusion itself is not formed according to a fixed rule 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 rule but are irregular; and furthermore, the shape of the concave portion surrounded by such multiple protrusions is also irregular.

[0151] In the matte article of the present invention, if any of the following is irregular: the shape of a protrusion (a raised portion), the shape and arrangement of the plurality of protrusions (a plurality of raised portions), or the shape of the recess surrounded by the plurality of protrusions, a matte effect resulting from irregular wrinkles and a dry, smooth feel can be obtained; however, it is preferable that all of them are irregular. The matte article of the present invention, by having irregular wrinkles, improves the visibility and texture of its matte effect, consistently exhibits an extremely excellent matte effect, and provides a dry, smooth feel.

[0152] As described above, the matte layer has wrinkles, i.e., an uneven shape, on at least one surface. Regarding the convex and concave portions of the uneven shape, for example, by utilizing the brightness difference of the surface image of the decorative material of the present invention, the darkest part of the concentration distribution image is set to grayscale 255, and the lightest part is set to grayscale 0. For grayscale values ​​0 to 255, grayscale values ​​0 to 127 are designated as concave portions, and grayscale values ​​128 to 255 as convex portions, and binarization processing is performed to distinguish them.

[0153] The surface of the matte article of the present invention preferably has irregular wrinkles formed in at least a portion thereof, and more preferably irregular wrinkles 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, i.e., on the pattern itself. As long as the wrinkles are on at least a portion of the surface, the matte effect and dry, smooth 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, such as on the pattern itself, the pattern is visually perceived as a more matte area compared to its surroundings, thus enabling an improvement in design.

[0154] In addition, as Figure 6 As shown, it is preferable to have multiple convex portions formed by multiple irregular protrusions with a certain degree of homogeneity, and concave portions surrounded by the convex portions. Therefore, in a single convex portion (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 the visibility and texture of the matte effect, nor can it be considered a preferred method in terms of achieving a dry and smooth feel. Regarding the shape of the convex portions (protrusions) and concave portions that form irregular wrinkles, the following will explain specific ways that can be advantageous in terms of consistently improving the matte effect and improving the dry and smooth feel. By having the following shape for the wrinkles, the aforementioned surface shape is easily achieved, thereby improving the matte effect and the dry and smooth feel.

[0155] 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 dry, smooth feel is enhanced.

[0156] Here, the aforementioned dimensions of the protrusions are the average of any 10 protrusions (raised portions) from any 10 locations (100μm square areas × 10 locations) in the matte article of the present invention, i.e., a total of 100 protrusions. Additionally, as... Figure 6 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).

[0157] 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 dry, smooth feel is enhanced.

[0158] Here, the dimensions of the concave portion are determined in the same way as the dimensions of the convex portion described above.

[0159] The distance from the top of the convex portion to the bottom of the concave portion, i.e., 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 the distance is within the above range, the above-mentioned surface shape is easily achieved, the matting effect is stably improved, and the dry and smooth touch is enhanced.

[0160] Here, the dimensions of the concave portion are determined in the same way as the dimensions of the convex portion described above.

[0161] The proportion of the protrusions 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 protrusions 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 protrusions, the matting effect is stably improved, and the dry and smooth touch is improved.

[0162] 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 the present invention.

[0163] The convex and concave portions can have approximately the same direction and approximately the same width, but a shorter length is preferred to improve the matte finish and the dry, smooth feel. 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 the length is within the above range, the wrinkles become more irregular, thus the matte finish is consistently improved, and the dry, smooth feel is enhanced.

[0164] Here, regarding any 10 locations (10 square areas of 100 μm × 10 locations) of the matte article of the present invention, it is preferable that at least 80% of the 10 protrusions and recesses (i.e., a total of 100 protrusions and recesses) satisfy the above conditions, more preferably at least 85%, further preferably at least 90%, and even more preferably at least 95%. Furthermore, in this specification, "approximately the same" means roughly the same, without branching; in the case of direction, it means a difference within ±3°, and in the case of width, it means a difference within ±5%.

[0165] 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 dry and smooth touch is improved.

[0166] The number of protrusions is the average number of protrusions in 10 locations (100μm square area × 10 locations) of the matte article of the present invention.

[0167] Figure 3 This is a cross-sectional view showing one embodiment of the matte article of the present invention, obtained by cutting the matte article 1 with a plane parallel to its thickness direction. The thickness direction of the matte article 1 is... Figure 3 The Z direction in the equation.

[0168] As the shape of the concave portion, for example, it can be like Figure 3 It can be acute-angled like 2a, or semi-circular or semi-elliptical like 2b, or a combination of both. Alternatively, it can be a convex part with a concave part. Figure 3 It has a shape like 2c.

[0169] On the other hand, as a shape of the convex part, although... Figure 3 Like 3a and 3b, it has a width that varies, but it is in the shape of a semicircle or a semi-ellipse.

[0170] The thickness of the matte layer is not particularly limited as long as it can form the aforementioned wrinkles to a degree that stably exhibits a matte effect and provides a dry and smooth feel. However, considering ease of fabrication, it is typically 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.

[0171] 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.

[0172] The matte layer is a layer that presents the aforementioned surface shape on its entire surface. Since the matte article of the present invention has a surface shape on at least a portion of its surface, it is sufficient to provide it 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 the present invention has the aforementioned substrate and matte layer, it is sufficient to provide it on at least a portion of the surface of the substrate, or it can be provided on its entire surface.

[0173] 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 dry, smooth feel, can be achieved.

[0174] Furthermore, when the substrate is in the form of a film, sheet, or plate, the matte layer only needs to be applied to the parts of the matte article that the user visually identifies and touches. It only needs to be applied to at least a portion of one surface, or it can be applied to the entire surface. From the viewpoint of improving the matte effect and the dry, smooth feel, such as... Figures 4-6 As shown, it is preferred to set it on the entire surface of a face.

[0175] (resin)

[0176] 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 4-6As shown, the matte layer is a layer that can be provided on the outermost surface of the matte article of the present invention. Therefore, in addition to resins that are easy to form wrinkles using wrinkle-forming stabilizers, resins that easily exhibit surface properties such as processing characteristics, stain resistance, scratch resistance, and weather resistance are preferred in order to improve the usability of the matte article. From these viewpoints, ionizing ray curable resins are preferred. Because the matte article of the present invention 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.

[0177] 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.

[0178] 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.

[0179] Examples of ionizing ray curable resins include electron beam curable resins and ultraviolet curable resins. If the formation of wrinkles is stabilized by a wrinkle-forming stabilizer, thus improving the matting effect and the smooth, dry feel, then an ultraviolet curable resin is preferred.

[0180] 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.

[0181] 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".

[0182] 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.

[0183] Considering the need to stabilize wrinkle formation, consistently improve matte finish, enhance the smooth feel after drying, and further improve 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 smooth feel after drying is easily improved.

[0184] These multifunctional (meth)acrylates can be used alone or in combination.

[0185] 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.

[0186] 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.

[0187] These polymeric oligomers can be used alone or in combination.

[0188] Among the polymerizable oligomers mentioned above, 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. Using these polymerizable oligomers can stabilize wrinkle formation, steadily improve matte finish, enhance the smooth, dry feel, and consequently improve surface properties such as post-processing characteristics, scratch resistance, and weather resistance.

[0189] The number of functional groups in these polymeric oligomers is preferably 2 or more and 8 or less, with an upper limit, more preferably 6 or less, and even more preferably 4 or less. If the number of functional groups is within the above range, the formation of wrinkles can be stabilized, the matting effect can be steadily improved, the dry and smooth feel can be improved, and surface properties such as processing characteristics, scratch resistance and weather resistance can be improved.

[0190] Furthermore, for the same reason, the weight-average molecular weight of these polymeric oligomers is preferably 900 or more and 7,500 or less, more preferably 1,000 or more and 7,000 or less, and even more preferably 1,200 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.

[0191] In this invention, 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, and enhances the dry, smooth feel. It also improves surface properties such as processing characteristics, scratch resistance, and weather resistance.

[0192] When used in combination, for the same reason, 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.

[0193] (Resin Composition)

[0194] 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 invention may also contain other components depending on desired properties, etc.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] Since the matte layer is a layer that can be applied to the outermost surface of the matte article of the present invention, it is preferably a weather-resistant layer, for example, preferably containing various weather-resistant agents such as ultraviolet absorbers and light stabilizers.

[0200] 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.

[0201] These UV absorbers, light stabilizers, and other weather-resistant agents can be used alone or in combination.

[0202] [60° gloss value]

[0203] The matte articles of the present invention are articles with excellent visibility and texture due to their 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. For example, if the 60° gloss value is 20.0 or less, preferably about 10.0 or less, it is usually considered "matte".

[0204] To date, even in matte articles exhibiting black or other dark colors, excellent visibility with a 60° gloss value of 20.0 or less, preferably 10.0 or less, has been achieved, even when using matting agents. Here, "dark color" refers to low brightness, for example, an L* value (hereinafter sometimes simply referred to as "L* value") in the CIE (International Commission on Illumination) L*a-b* color system as measured according to JIS Z8781-4:2013, typically around 40 or less, preferably 30 or less.

[0205] However, due to the extensive use of matting agents, streaks and unevenness occur during layer formation, making manufacturing difficult and reducing surface properties. Furthermore, for example, regarding matte items exhibiting shades 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 items exhibiting black, it is not easy to obtain matte items with excellent surface properties, as well as excellent visibility and texture of the matte effect. This trend becomes more pronounced as the 60° gloss value decreases.

[0206] In the matte articles of the present invention, by using two wrinkle-forming stabilizers having a specified average particle size in combination and in a small amount as described above, not only is a consistently excellent matte effect in terms of visibility and texture obtained, but also a dry and smooth feel is achieved. Furthermore, by suppressing the amount of wrinkle-forming stabilizer used to an extremely 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.

[0207] As described above, the matte articles of the present invention vary depending on the hue, and therefore 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.

[0208] Furthermore, matte articles exhibiting hues other than black and other dark colors can also possess the aforementioned 60° gloss value. The 60° gloss value on the matte layer side of the matte article of the present invention 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 disposed on the surface side of the matte layer, the 60° gloss value refers to the 60° gloss value of the other layers; however, the specific 60° gloss value of the matte article of the present invention substantially depends on the composition of the matte layer.

[0209] 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.

[0210] Total transmittance

[0211] As described above, the matte articles of the present invention sometimes employ a substrate made of an opaque material, a decorative layer described later, etc., and can be used for exterior components, interior components, etc. Considering the use of the aforementioned substrate, the decorative layer described later, and its use for the aforementioned purposes, the total light transmittance of the matte articles of the present invention, 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.

[0212] In this specification, the total transmittance of the matte article is the total transmittance measured according to JIS K7361-1:1997, which is the average value of measurements taken at any 10 locations.

[0213] [Other layers]

[0214] In addition to the aforementioned matte layer and substrate, the matte article of the present invention may, as needed, include other layers such as a base coating layer, a transparent resin layer, a decorative layer, and an adhesive layer. A cross-sectional view illustrating an embodiment of the matte article of the present invention having these layers is shown below. Figure 4 and Figure 5 . Figure 4 and Figure 5 This is a cross-sectional view showing one embodiment of the matte article of the present invention, obtained by cutting the matte article 1 along a plane parallel to its thickness direction. Here, "thickness direction" refers to... Figure 4 and Figure 5 The Z direction in the equation.

[0215] Figure 4 The matte decorative material 1 shown has a substrate 5 and a matte layer 4 in sequence. Figure 5 The matte article 1 shown has, in sequence, a substrate 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a base coating layer 9, and a matte layer 4.

[0216] (Base coat)

[0217] In the case where the matte article of the present invention is composed of multiple layers, a base layer may be provided in order to improve the interlayer adhesion of the multiple layers.

[0218] In cases where the matte article of the present invention has a layer other than the matte layer, such as when it has a matte layer and a substrate, a base coating layer may be provided between the matte layer and the substrate in order to improve interlayer adhesion.

[0219] The base coating is mainly composed of adhesive resin and may contain additives such as UV absorbers and light stabilizers as needed.

[0220] 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.

[0221] 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.

[0222] The thickness of the base coating is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and even more preferably 2 μm or more and 6 μm or less.

[0223] The matte article of the present invention aims to improve the adhesion to bonded materials such as resin molded articles of laminated articles. 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.

[0224] (Transparent resin layer)

[0225] In order to improve the strength of the matte article of the present invention, 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.

[0226] 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.

[0227] The transparency of the resin layer is sufficient to allow visual identification of the substrate side relative to the transparent resin layer. Furthermore, in the case of a decorative layer, the transparency is sufficient to allow visual identification of the decorative layer; besides colorless transparency, it can also be colored transparency or translucent. That is, in this specification, "transparency" refers to colorless transparency, as well as colored transparency and translucentness.

[0228] The transparent resin layer may contain weather-resistant agents such as ultraviolet absorbers and light stabilizers, as well as additives such as colorants.

[0229] Taking into account the protection of the decorative layer and its adaptability to post-processing, 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.

[0230] (Decorative layer)

[0231] To improve design flexibility, the matte article of the present invention may have a decorative layer. The decorative layer may be disposed on the side opposite to at least one of the wrinkled sides of the matte layer. If a substrate is provided, the decorative layer may be disposed between the substrate and the matte layer. Alternatively, if a transparent resin layer is provided, the decorative layer, the transparent resin layer, and the matte layer may be disposed in that order.

[0232] Decorative layers can be, for example, a coloring layer covering the entire surface, or a pattern layer formed by printing various designs using ink and a printing press. Here, a "coloring layer covering the entire surface" is also referred to as a "solid coloring layer," which is composed of... Figure 5 The layer indicated by "6a" is the "pattern layer". Figure 5 The "6b" in the text indicates... Additionally, as... Figure 5 As shown, solid color layers and patterned layers can also be combined.

[0233] 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.

[0234] Alternatively, examples of patterns that provide a "dry and smooth" tactile feel include fabric textures, metal surfaces, patterns resembling baby skin, patterns on metal surfaces such as hair textures, and leather textures. By combining the "dry and smooth" tactile feel of the matte article of the present invention with patterns of objects that also possess a "dry and smooth" tactile feel, a more realistic design can be achieved.

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

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

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

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

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

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

[0241] (Adhesive)

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

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

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

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

[0246] In order to obtain the desired adhesive strength efficiently, the thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0247] [Manufacturing Method for Matte Finish Items]

[0248] The first method for manufacturing a matte article of the present invention is characterized by comprising a matte layer forming step, wherein a matte layer is formed by irradiating a layer of a resin composition for matte layer forming comprising the above-mentioned resin and a wrinkle forming stabilizer with light of a wavelength of at least 100 nm and less than 380 nm.

[0249] The first manufacturing method enables the manufacture of, for example... Figure 4 and Figure 5 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. For example, if the resin composition for forming the matte layer is coated onto a substrate, a layer of the resin composition is formed on the substrate, and a matte layer is formed by irradiation, a matte article having a substrate and a matte layer can be manufactured. By passing the matte article through the matte layer to obtain the aforementioned surface shape, the surface on the matte layer side can have the aforementioned surface shape. Therefore, the first manufacturing method is a suitable method for manufacturing matte articles having a matte effect with a 60° gloss value of 20.0 or less, 10.0 or less, or even less on the matte layer side, and having a dry and smooth feel.

[0250] The matte article of the present invention can be easily obtained by the manufacturing method of the present invention. Specifically, when forming the matte layer, by irradiating a resin composition for matte forming containing a wrinkle-forming stabilizer with low-wavelength ultraviolet light of at least 100 nm and less than 380 nm, wrinkles can be formed on at least one surface of the matte layer, thereby imparting a matte effect and a dry, smooth feel to the matte article (matte layer).

[0251] 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 low-wavelength ultraviolet light, thereby exhibiting a matte effect and a dry, smooth feel, are not yet clear, but it is speculated to be based on the following mechanism.

[0252] If a coating layer formed by applying a resin composition for matte layer formation to a specified thickness is irradiated with low-wavelength ultraviolet light, the energy of the ultraviolet light only penetrates to the surface portion and does not reach the underlying layer, thus only the surface portion of the resin composition begins to cure. Therefore, it is believed that only the surface undergoes curing shrinkage, forming wrinkles. Thus, it is considered that the wrinkles are formed in a state where curing occurs only in a certain thickness direction from the surface of the resin composition for matte layer formation through irradiation with low-wavelength ultraviolet light.

[0253] Furthermore, based on the comparison of the embodiments and comparative examples described later, without a wrinkle-forming stabilizer, wrinkle formation becomes unstable, the visibility and texture of the matte effect are not consistently and fully expressed across the entire surface of the matte layer, and the dry, smooth feel is not sufficiently achieved. Therefore, the stable expression of the matte effect and the dry, smooth feel cannot be explained solely by curing only the surface portion using low-wavelength ultraviolet light. In other words, in order for the matte article of the present invention to stably possess wrinkles and exhibit both a matte effect and a dry, smooth feel, the inclusion of a wrinkle-forming stabilizer is essential.

[0254] Considering that a stable matte finish and a dry, smooth feel resulting from wrinkle formation cannot be obtained without a wrinkle-forming stabilizer, the wrinkle-forming stabilizer functions like a core that triggers wrinkle formation. Around this core, resin on the surface portion of the resin composition aggregates to form the raised portion (protrusion) of the wrinkle, and simultaneously forms the recessed portion. As a result, wrinkle formation is considered stable, consistently exhibiting a matte finish and a dry, smooth feel.

[0255] The wrinkle-forming stabilizer used in the manufacturing method of the present invention and the resin composition for forming a matte layer containing the wrinkle-forming stabilizer are the same as those described as wrinkle-forming stabilizers and resin compositions for forming a matte layer that can be used in the matte decorative material of the present invention.

[0256] In the manufacturing method of the present invention, 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. Upon this irradiation, as described above, the energy of the ultraviolet light penetrates only to the surface portion and does not reach the underlying layers, thus only the surface portion of the resin composition begins to cure. Therefore, only the surface undergoes curing shrinkage, thereby stabilizing the formation of wrinkles, and 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 slow to the deeper portion in the depth direction, and the layer of the resin composition becomes a cured product, thereby curing over the entire thickness of the resin composition and exhibiting a light diffusion effect on the surface, forming a wrinkled matte layer with a dry, smooth feel. To promote curing to the deeper portions, 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.

[0257] "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 naturally emitted light or highly coherent (interferometric) lasers based on stimulated emission can be used, but naturally emitted light is usually sufficient. It should be noted that discharge lamps emitting ultraviolet light are also called "excimer lamps".

[0258] The excimer light has a single wavelength peak, and as a characteristic, its half-width at half-maximum (WWHM) is narrower than that of ordinary ultraviolet light (such as ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). By using such excimer light, wrinkle formation is stabilized, the matting effect is consistently improved, and the dry, smooth feel is also enhanced.

[0259] To stabilize the formation of wrinkles, consistently improve the matting effect, and enhance the dry, smooth feel, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, and even more preferably 155 nm or more. As an upper limit, it is preferably 320 nm or less, more preferably 300 nm or less, even more preferably 250 nm or less, even more preferably 200 nm or less, and most preferably 172 nm (Xe2). Thus, in this invention, to consistently improve the matting effect and enhance the dry, smooth feel, it is also preferable to use shorter wavelengths of 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.

[0260] In this invention, from the viewpoint of stabilizing the formation of wrinkles, consistently improving the matting effect, and enhancing the dry and smooth feel, the cumulative light intensity of the aforementioned wavelength is preferably 1 mJ / cm. 2 The above, more preferably 10 mJ / cm 2 The above is further optimized to 30 mJ / cm 2 The above is further optimized to 50 mJ / cm. 2 That's all. Furthermore, as an upper limit, there is no particular restriction, but considering factors such as reducing the number of lamps required for wavelength illumination and improving production efficiency, 1000 mJ / cm² is preferred. 2 Below, 500 mJ / cm is more preferred. 2 The following is a further preferred value: 300 mJ / cm 2 For the same reason, 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.

[0261] 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.

[0262] In the matte layer formation step of the method for manufacturing matte articles of the present invention, 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 be performed.

[0263] For example, to stabilize 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 to promote 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. Furthermore, after irradiation with light of a wavelength between 100 nm and 380 nm, post-curing is performed to further cure the resin composition. Regarding pre-curing and post-curing, their use can be determined appropriately based on the desired properties of the matte layer, such as processing characteristics and surface properties like 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.

[0264] In the manufacturing method of the present invention, the matte layer can be formed by irradiating the coating layer (uncured resin layer) with light of a wavelength of at least 100 nm and less than 380 nm. The coating layer (uncured resin layer) is obtained by coating the resin composition for forming the matte layer using known methods such as gravure printing, bar coating, roller coating, reverse roller coating, and comma coating.

[0265] Furthermore, the matte article obtained by the manufacturing method of the present invention may have a substrate as described above as a layer that can be used in the matte article of the present invention, and other layers such as a transparent resin layer.

[0266] 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, a resin film for forming the transparent resin layer can be formed by dry lamination or the like.

[0267] In the matte articles of the present invention, such as Figure 3 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.

[0268] The second manufacturing method is characterized by having: a step of forming a coating layer by coating a resin composition for forming matte articles, comprising a resin and a wrinkle-forming stabilizer, onto the release layer of a support sheet having a release 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.

[0269] 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, easy to handle, and economical.

[0270] 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 into a matte article. 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. Waxes can be mixed as needed.

[0271] 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.

[0272] The resin composition for forming matte articles, which includes resin and wrinkle-forming stabilizer, can be derived from resins and wrinkle-forming stabilizers that are 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.

[0273] 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.

[0274] 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.

[0275] 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.

[0276] 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 where curing is slow to the deeper portion that is farther away in the depth direction, and the resin composition is cured as a whole, thereby becoming a matte article with the aforementioned surface shape on at least a portion of the surface.

[0277] In addition, regarding irradiation, post-curing can be performed to promote curing to deeper parts, or pre-curing can be performed.

[0278] 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.

[0279] Furthermore, in the matte articles of the present invention, such as Figure 3 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.

[0280] 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 to impart the aforementioned surface shape.

[0281] Embossing plates and shaped sheets can be used without particular restrictions as long as they can impart the aforementioned surface shape. The surface shape of the embossing plates and shaped sheets is the opposite of the surface shape they shape. Specifically, it becomes a shape in which the Ssk (skewness) and Sku (kurtosis) are symmetrical to the Ssk (skewness) and Sku (kurtosis) of the shaped sheet, each exhibiting a normal distribution between 0 and 3. Therefore, in order to obtain the matte article of the present invention, the shaped sheet used can be any embossing plate or shaped sheet having a surface shape with a Ssk (skewness) of 0 or less and a Sku (kurtosis) of 3 or more. For example, if an embossing plate or shaped sheet with a Ssk (skewness) of -0.50 and a Sku (kurtosis) of 3.75 is used, a matte article with a surface shape having a Ssk (skewness) of 0.50 and a Sku (kurtosis) of 2.25 can be obtained. It should be noted that the values ​​related to the surface shape of shaped sheets and matte articles are only theoretical values ​​and will naturally have some errors.

[0282] Furthermore, examples of matte articles according to the present invention 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, phenolic resin decorative panels, and other thermosetting resin decorative panels. Thermosetting resin decorative panels are obtained as follows: A material, such as paper, woven fabric, or nonwoven fabric, which can be used as the substrate for the aforementioned matte article, is used as the substrate. This material is 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.

[0283] In this case, the thermosetting resin impregnated into the substrate may 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, sulfonamide resin, etc. are also preferred. Among these, melamine resin, melamine-urea resin, and phenolic resin are preferred, and melamine resin is particularly preferred.

[0284] (use)

[0285] As described below, the matte articles of the present invention can be used as decorative components.

[0286] Furthermore, the matte article of the present invention 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.

[0287] The surface shape of the object being shaped (an article composed of a single layer, a thermosetting resin decorative panel, etc.) is as described above, exhibiting a shape opposite to the surface shape of the shaped sheet material used as the matte article of the present invention. Therefore, the object, such as an article composed of a single layer or a thermosetting resin decorative panel, has a Sk (skex) of 0.00 or less and a Sku (ku) of 2.50 or more, exhibiting a moist feel and a matte effect.

[0288] [Decorative components]

[0289] The matte article of the present invention can be used directly as a decorative component, or it can be layered, composited, or combined with a bonded material to be used as a decorative part. Whichever method is chosen depends on the need. When using the matte article of the present invention as a decorative component, the matte article preferably has a decorative layer.

[0290] When an adhesive material is included, the decorative component comprises the adhesive material and the matte article of the present invention described above. Specifically, it is formed by laminating the surface of the adhesive material to be decorated and the opposite side of the matte article (which exhibits a matte effect and a dry, smooth feel by forming wrinkles with the matte layer) face to face. Furthermore, when an adhesive material is included, the matte article of the present invention preferably has a film or sheet form, taking into account ease of lamination.

[0291] On the other hand, the matte articles of the present invention are Figure 3 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 the present invention 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, household appliances, etc.

[0292] in addition, Figure 3 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.

[0293] (Materials to be bonded)

[0294] Examples of materials that can be bonded include flat or curved panels, cylindrical or polygonal prisms, and sheets (or films) made from various raw materials. For instance, examples include wooden components made from various types of wood such as fir, cypress, pine, and willow, used as wood veneers, plywood, engineered wood, particleboard, MDF (medium-density fiberboard), and other wood fiberboards, as well as three-dimensional objects; metal components made from metals such as iron, aluminum, copper, and alloys containing one or more of these metals, used as panels, three-dimensional objects, or sheets; ceramic components made from non-ceramic materials such as glass, ceramics, gypsum, cement, ALC (lightweight aerated concrete), and calcium silicate; and resin components made from resins such as acrylic resins, polyester resins, polystyrene resins, polyolefin resins such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer), 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.

[0295] 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.

[0296] 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.

[0297] (Adhesive layer)

[0298] To achieve excellent adhesion, the materials to be bonded and the matte articles are preferably bonded together by an adhesive layer.

[0299] There are no particular limitations on the adhesive used as the adhesive layer; any known adhesive can be used, selected appropriately according to the application. For example, moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), pressure-sensitive adhesives, and other adhesives are preferred.

[0300] 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.

[0301] 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.

[0302] There is no particular limitation on the thickness of the adhesive layer. In order to obtain 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.

[0303] Total transmittance

[0304] Regarding decorative components using the matte articles of the present invention, as described above, there are cases where the matte articles include a substrate and a decorative layer made of an opaque material, and there are also cases where an adhesive material made of an opaque material is used. Furthermore, they can be used for exterior components, interior components, and other applications. Considering the above, the total light transmittance of the decorative component using the matte articles of the present invention, 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.

[0305] (Manufacturing method of decorative components)

[0306] Decorative components can be manufactured by laminating the matte article of the present invention with the adhesive material.

[0307] This process involves laminating the adhesive material to be bonded with the matte article of the present invention. The surfaces of the adhesive material to be decorated and the matte article of the present invention (which exhibits a matte effect and a dry, smooth feel due to the wrinkles formed by the matte layer) are laminated together, facing each other. Alternatively, when the matte article of the present invention has a substrate, the surfaces of the adhesive material to be decorated are laminated together, facing the substrate side. Examples of methods for laminating the adhesive material and the matte article include lamination methods where the matte article is pressed onto a sheet-like adhesive material using a pressure roller with an adhesive layer.

[0308] When using a hot melt adhesive (also known as a "thermal adhesive"), the heating temperature is preferably 160°C or higher and 200°C or lower, depending on the type of resin constituting the adhesive. In the case of a reactive hot melt adhesive, 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.

[0309] 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 like walls, ceilings, and floors; exterior components for walls, eaves, roofs, fences, and other exterior decorations; window frames, doors, door frames, handrails, crossbeams, perimeter edges, inlays, and other door and window equipment or decorative components; additionally, they are suitable for use as general furniture such as wardrobes, shelves, and tables; kitchen furniture such as dining tables and sinks; surface decorative panels for the housings of home appliances and OA equipment; and interior or exterior components for vehicles.

[0310] 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 combination with other raw materials (adhesive materials) through layering, lamination, or assembly, for packaging materials, whiteboards or blackboards, credit cards, debit cards, phone cards, various cards such as 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 dry, smooth feel, on the outermost surface, but of course, other forms of use are also possible depending on the application and purpose.

[0311] Example

[0312] The invention will now be described in further detail through examples, but the invention is not limited by these examples.

[0313] (Measurement of surface shape)

[0314] Regarding the Ssk (skewness), Sku (kurtosis), RSm (average length of curve element), Rz (maximum height), and Ra (arithmetic mean roughness) of the articles obtained in the examples and comparative examples, for a rectangular part (1024μm × 768μm) of any part of the surface shape of the article, the measurements were performed 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: 658nm, measurement mode: surface shape mode, measurement interval: 0.13μm, and measurement quality: high-speed mode.

[0315] In addition, the cutoff values ​​for RSm (average length of curve feature), Rz (maximum height), and Ra (arithmetic mean roughness) are 0.8 mm.

[0316] (Evaluation method: 60° gloss value)

[0317] 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.

[0318] (Evaluation of texture (uniformity of surface condition))

[0319] 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.

[0320] A: More than 18 people rated it as having a uniform surface condition and high visibility of the matte effect.

[0321] B: Evaluations by 15 to 17 people indicate that the surface is uniform and the matte effect is highly visible.

[0322] C: Less than 14 people rated it as having a uniform surface condition and high visibility of the matte effect.

[0323] (Evaluation of the dry and smooth texture)

[0324] For the articles obtained in the examples and comparative examples, as a benchmark for the feel of a dry and smooth feel, 20 random adults evaluated the feel of the surface using Oxford cloth made of 80-count cotton yarn, according to the following benchmark.

[0325] A: The feel is close to the benchmark, described by more than 18 people as a dry and smooth feel.

[0326] B: The feel is close to the benchmark, with 15 to 17 people giving the evaluation. It is a dry and smooth feel.

[0327] C: Rated by fewer than 14 people, the feel is close to the benchmark, and is dry and smooth.

[0328] [Example 1]

[0329] A polypropylene sheet (thickness: 100 μm) treated with corona discharge was used as the substrate. A coloring layer (thickness: 3 μm) was formed by coating one side of the substrate with printing ink (adhesive resin: two-component curable acrylic-urethane resin) using a gravure method. A base layer (thickness: 2 μm) was formed by coating a resin composition containing acrylic resin and urethane resin as adhesive resin on the coloring layer. A coating (coating amount: 5 g / m²) was then applied on the base layer using a gravure method. 2 (When dry) The resin composition for forming the matte layer (polyfunctional urethane acrylate oligomer 1 (quadrifunctional, average molecular weight: 1800): 65 parts by weight, polyfunctional acrylate monomer (difunctional, molecular weight: 400): 35 parts by weight, wrinkle-forming stabilizer 1 (silica particles, average particle size: 3μm): 3.0 parts by weight, wrinkle-forming stabilizer 2 (silica particles, average particle size: 5nm): 3.0 parts by weight, photopolymerization initiator (benzophenone-based): 0.8 parts by weight) is then irradiated with ultraviolet light (wavelength: 395nm, UV dose: 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 having a substrate and a matte layer. The gloss value at 60° was measured from the matte layer side of the obtained matte article, and the result was 1.4. Furthermore, the surface shape, texture, and tactile feel were evaluated using the above method. These results are shown in Table 1.

[0330] [Examples 2-6]

[0331] In Example 1, the amount of wrinkle-forming stabilizer in the resin composition for forming the matte layer was set as shown in Table 1, and the resin composition for forming the matte layer and the substrate were used. Otherwise, the procedure was the same as in Example 1 to obtain a matte article. The polyfunctional urethane acrylate oligomer 2 used in Examples 5 and 6 is an oligomer with 3 functional groups. The 60° gloss value and texture evaluation of the matte layer side of the obtained matte article are shown in Table 1. Furthermore, the surface shape, texture, and tactile feel were measured using the methods described above. These results are shown in Table 1.

[0332] [Comparative Example 1]

[0333] In Example 1, the amount of wrinkle-forming stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, i.e., no wrinkle-forming stabilizer was used. Otherwise, the procedure was the same as in Example 1 to obtain an article. The 60° gloss value of the matte layer side of the obtained article was measured, and the surface shape, texture, and tactile feel were evaluated using the methods described above. These results are shown in Table 1.

[0334] [Comparative Example 2]

[0335] In Example 1, the amount of wrinkle-forming stabilizer in the resin composition used for forming the matte layer was set to 0 parts by mass, and instead, 15.0 parts by mass of matting agent (average particle size: 8.0 μm) was used. The article was obtained by irradiation with an electron beam (accelerating voltage: 75 kV, irradiation linear dose: 30 kGy (3 Mrad)). Otherwise, the procedure was the same as in Example 1. The 60° gloss value of the matte layer side of the obtained article was measured, and the surface shape, texture, and tactile feel were evaluated using the methods described above. These results are shown in Table 1.

[0336] [Comparative Example 3]

[0337] A polypropylene sheet (thickness: 100 μm) treated with corona discharge was used as the substrate. A coloring layer (thickness: 3 μm) was formed by coating one side of the substrate with printing ink (adhesive resin: two-component curable acrylic-urethane resin) using a gravure method. A base layer (thickness: 2 μm) was formed by coating a resin composition containing acrylic resin and urethane resin as adhesive resin on the coloring layer. A coating (coating amount: 5 g / m²) was then applied on the base layer using a gravure method. 2 (When dry) The resin composition for forming the matte layer (polyfunctional urethane acrylate oligomer (4-functional, average molecular weight: 1800): 65 parts by mass, polyfunctional acrylate monomer (2-functional, molecular weight: 400): 35 parts by mass, wrinkle-forming stabilizer 1 (silica particles, average particle size: 3μm): 3.0 parts by mass, wrinkle-forming stabilizer 2 (silica particles, average particle size: 5nm): 3.0 parts by mass, photopolymerization initiator (benzophenone-based): 0.8 parts by mass) is irradiated with ultraviolet light (wavelength: 172nm (Xe2), ultraviolet power density: 1W / cm, cumulative light intensity: 10~100mJ / cm) using an excimer light irradiation device. 2The 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 having a substrate and a matte layer. The gloss value at 60° was measured from the matte layer side of the obtained matte article, and the result was 1.6. Furthermore, the surface shape, texture, and tactile feel were evaluated using the above method. These results are shown in Table 2.

[0338] [Comparative Example 4]

[0339] In Comparative Example 3, a paper substrate (thickness: 30 μm) was used as the substrate, and the same procedure as in Comparative Example 3 was followed to obtain a matte article. The 60° gloss value and texture evaluation of the matte layer side of the obtained matte article are shown in Table 2. Furthermore, the surface shape, texture, and tactile feel were measured using the methods described above. These results are shown in Table 2.

[0340] [Comparative Example 5]

[0341] In Comparative Example 3, the resin composition used to form the matte layer used only a polyfunctional acrylate monomer (2-sensory). Otherwise, the procedure was the same as in Comparative Example 3 to obtain a matte article. The evaluation of the 60° gloss value and texture of the obtained matte article on the matte layer side is shown in Table 2. Furthermore, the surface shape, texture, and tactile feel were measured using the methods described above. These results are shown in Table 2.

[0342] [Comparative Example 6]

[0343] A PET sheet (thickness: 100μm) treated with corona discharge was used as the substrate. A coloring layer (thickness: 3μm) was formed by coating one side of the substrate with printing ink (adhesive resin: two-component curable acrylic-urethane resin) using a gravure method. A base layer (thickness: 2μm) was formed by coating a resin composition containing acrylic resin and urethane resin as adhesive resin on the coloring layer. A coating (coating amount: 5g / m²) was then applied on the base layer using a gravure method. 2 (During drying) The resin composition for forming the matte layer (polyfunctional urethane (meth)acrylate oligomer (4-functional, average molecular weight: 1800): 65 parts by weight, polyfunctional acrylate monomer (2-functional, molecular weight: 400): 35 parts by weight, wrinkle-forming stabilizer 1 (silica particles, average particle size: 3 μm): 3.0 parts by weight, wrinkle-forming stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by weight, photopolymerization initiator (benzophenone-based): 0.8 parts by weight) is then irradiated with ultraviolet light (wavelength: 395 nm, ultraviolet light dose: 6 W / cm²) using a UV irradiation device composed of LEDs. 2Then, 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 is subjected to a nitrogen atmosphere (oxygen concentration below 200 ppm), followed by irradiation with a high-pressure mercury lamp (ultraviolet power density: 200 W / cm²) to create a matting layer, resulting in a shaped sheet with a substrate and a matting layer.

[0344] Next, we will prepare phenol-impregnated kraft paper (manufactured by Ohta Sangyo Co., Ltd., with a unit area weight of 200g / m²). 2 It is obtained by impregnating 30% by mass of phenolic resin into kraft paper, and black titanium paper (80 g / m²) is used as a decorative layer. 2 Covering paper (with a unit area weight of 22g / m²) 2 The paper (manufactured by Mead) is impregnated with 300% by mass of hydroxymethyl melamine resin (manufactured by CYMEL). Phenolic resin-impregnated kraft paper, black titanium paper, and a cover paper are then sequentially overlapped. The cover paper is further overlapped with the surface of the aforementioned shaped sheet in contact with the surface of the sheet, and then clamped between mirror plates under a pressure of 7.8 MPa (80 kg / cm²). 2 Heating and processing at 145℃ for 30 minutes allows the resin to penetrate, cure, and integrate, resulting in a matte finish product, thus obtaining a thermosetting resin decorative panel (high-pressure melamine decorative panel).

[0345] For the obtained matte articles, the gloss value at 60° was measured from the matte layer side, and the result was 1.5. In addition, the surface shape, texture, and tactile feel were evaluated using the methods described above. These results are shown in Table 3.

[0346] [Comparative Example 7]

[0347] In Comparative Example 6, the resin composition used to form the matte layer contained 90 parts by weight of a polyfunctional urethane acrylate oligomer and 10 parts by weight of a single-sensory acrylate monomer. Otherwise, the procedure was the same as in Comparative Example 6 to obtain a shaped sheet. The obtained shaped sheet itself was used as the matte article of Comparative Example 7. For the obtained matte article, the gloss value at 60° was measured from the matte layer side, and the result was 1.6. Furthermore, the surface shape, texture, and tactile feel were measured using the methods described above. These results are shown in Table 3.

[0348] [Table 1]

[0349] Table 1

[0350]

[0351] Based on the results in Table 1, it can be confirmed that the matte article of the present invention has a 60° gloss value of 1.4 on the matte layer side, making it an article with extremely excellent visibility of the matte effect and excellent texture. In addition, it was also confirmed that it has an excellent dry and smooth feel.

[0352] On the other hand, the article of Comparative Example 1, which does not contain wrinkle-forming stabilizers, such as Figure 13 As shown, although some wrinkles were formed on the surface, the visibility of the matte effect could not be consistently obtained. Although there were parts with the same gloss value as the example, there were also parts with high gloss, and the surface condition was unstable (uneven), so the texture could not be said to be excellent. In addition, it was confirmed that even though the decorative material of Comparative Example 2 containing a matte agent contained 15.0 parts by weight, which was more than the amount of wrinkle-forming stabilizer in the example, wrinkles were not formed on the surface layer corresponding to the matte layer. Its 60° gloss value was 8.3, which was inferior to the gloss value of the matte article of the example, and the texture was also poor. In addition, the articles of Comparative Examples 1 and 2 lacked a dry and smooth feel, and instead had a rough or wet feel.

[0353] Figures 7-12 These are optical microscope images of the matte articles from Examples 1 to 6 (each image width is approximately 272.0 μm). Optical microscope images according to the examples (each...) Figures 7-12 It can be confirmed that the matte decorative materials of these embodiments have irregular wrinkles on their surface. On the other hand, according to the optical microscope image of Comparative Example 1 ( Figure 13 As can be seen from the above, several wrinkles were formed on its surface. Although there were localized areas with the same wrinkles as in the embodiment, the formation of the wrinkles was unstable (uneven) and mixed with areas without wrinkles. Furthermore, according to the optical microscope image of Comparative Example 2 (…),… Figure 14 The article did not confirm the presence of wrinkles like those found in the matte decorative material of the embodiment, but rather a convex shape corresponding to the outline of the matting agent. The surface condition was unstable (uneven), and the texture could not be considered excellent. Based on this result, it was confirmed that the matte article of the present invention exhibits a specific surface shape due to the wrinkles on its surface, and due to this surface shape, it possesses extremely excellent visibility and texture of matte effect, as well as an excellent dry and smooth touch.

[0354] [Table 2]

[0355] Table 2

[0356]

[0357] The items in Comparative Examples 3-5 had a 60° gloss value of 1.4-1.6 on the matte side, confirming that they were items with excellent visibility due to their matte effect, and also had excellent texture. However, they did not have a dry and smooth feel; instead, they had a rough feel.

[0358] [Table 3]

[0359] Table 3

[0360]

[0361] Comparative Examples 6 and 7 show gloss values ​​of 1.5 and 1.6 at 60° on the matte side, confirming that they are items with excellent visibility and texture due to their matte finish. However, they do not have a dry, smooth feel; instead, they feel moist.

[0362] Industrial availability

[0363] The matte articles of this invention have excellent visibility and texture with a matte effect, and a superior dry and smooth feel, making them suitable for various applications. For example, they are suitable for use as interior components for buildings such as walls, ceilings, and floors; exterior components for exterior walls, eaves, roofs, fences, and other exterior finishes; window frames, doors, door frames, handrails, crossbeams, perimeter edges, and trim strips; and also as decorative components for general furniture such as wardrobes, shelves, and tables; kitchen furniture such as dining tables and sinks; surface decorative panels for the housings of home appliances and OA equipment; and decorative components for various components such as interior or exterior finishes of vehicles.

[0364] In addition to decorative components used in the aforementioned buildings, the matte articles of the present invention can be used directly as individual items or in the form of layering, compounding, or combining matte articles with other raw materials (adhesive materials) as packaging materials, whiteboards or blackboards, credit cards, cash cards, phone cards, various cards such as various certificates, keyboards of various keyboards, transparent panels (window glass, etc.) for windows, doors, partitions, etc., artificial leather, etc.

[0365] Explanation of reference numerals in the attached figures

[0366] 1: Matte items

[0367] 2: concave part

[0368] 3: convex part (protruding part)

[0369] 4: Matte layer

[0370] 5: Substrate

[0371] 6: Decorative layer

[0372] 6a: Shading layer

[0373] 6b: Pattern layer

[0374] 7: Adhesive layer

[0375] 8: Transparent resin layer

[0376] 9: Primer coating

Claims

1. A matte article, which is laminated, compounded, or combined with an adhesive material and used as a decorative component of a building. The decorative components of the building are interior decoration components, exterior decoration components, door and window equipment, or finishing components. The matte finish material is in sheet form and comprises, in sequence, a substrate, a decorative layer, and a matte finish layer. The matte layer is composed of a cured resin composition comprising a resin and a wrinkle-forming stabilizer, wherein the matte layer contains 0.5 parts by weight or more of the wrinkle-forming stabilizer relative to 100 parts by weight of the resin. The matte layer has uneven surfaces that form the surface of the matte article. The concave and convex surfaces have a wrinkled shape. The uneven surface, as specified in ISO 25178-2:2012, has a skewness of Ssk (above 0.00) and a kurtosis of Sku (below 3.50). The gloss value at 60° of the uneven surface is below 10.

0.

2. The matte article according to claim 1, wherein, The average length of the curve element RSm, which is the lateral parameter of the contour curve specified in JIS B0601:2013, is less than 100.00 μm.

3. The matte article according to claim 1 or 2, wherein, The maximum height of the peak and height parameter Rz of the contour curve of the uneven surface, as specified in JIS B0601:2013, is 3.00 μm or more.

4. The matte article according to claim 1 or 2, wherein, The arithmetic mean roughness of the uneven surface, which is the parameter Ra of the height direction of the profile curve as specified in JIS B0601:2013, is less than 2.00 μm.

5. The matte article according to claim 1, wherein, The fold shape is composed of multiple protrusions and concave parts, the multiple protrusions are formed by multiple line protrusions, and the concave parts are formed by being surrounded by the multiple line protrusions.

6. 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.

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

8. The matte article according to claim 7, wherein, The matte layer is disposed on the entire surface of one side of the substrate.

9. The matte article according to claim 1 or 2, wherein, The total transmittance, as measured by JIS K7361-1:1997, is less than 20%.

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