Matte article and method for producing the same

Abstract

To provide a matte article having excellent visibility and texture of the matte effect and various surface properties according to requirements, a matte article used for shaping that can meet diversifying demands, and a method for producing the matte article. [Solution] A method for producing a matte article that contains a predetermined amount of a wrinkle formation stabilizer, has an uneven shape composed of irregular wrinkles, and employs a matte layer with a 60° gloss value of 5.0 or less, or has a layer made of a resin composition cured under specific irradiation conditions.

Description

[Technical Field]

[0001] MATTE ARTICLES AND METHODS FOR MAKING MATTE ARTICLES FIELD OF THE INVENTION The present invention relates to matte articles and methods for making matte articles. [Background technology]

[0002] Conventionally, so-called decorative materials and decorative sheets have been used as articles for decorating and protecting the surfaces of, for example, interior building components such as walls, ceilings, and floors; exterior building components such as exterior walls, eaves ceilings, roofs, fences, and fences; fittings or fixtures such as window frames, doors, door frames, handrails, baseboards, moldings, and other building components; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various furniture and components used in wet areas such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels for cabinets and other components of home appliances and office automation equipment; interior or exterior vehicle components, etc. Such decorative materials and decorative sheets have, for example, a surface layer with desired functions, and are required to have various properties, mainly surface properties such as scratch resistance, stain resistance, and weather resistance, as well as processability.

[0003] For decorative materials and decorative sheets used in these applications, a method of improving texture by using a matte effect (matt effect) to enhance their design is commonly used. For example, Patent Document 1 proposes a decorative sheet using a matte effect, which has a pattern layer and a concealing layer on one side of a base sheet and a gloss-adjusting layer (matt layer, gloss layer) on the other side. The decorative sheet of Patent Document 1 achieves a design effect by highlighting the pattern layer and the concealing layer due to the difference in gloss between the matte layer and the gloss layer of the gloss-adjusting layer. In the examples, the matte layer applied over the entire surface uses a matte ink containing 50 parts by weight of matting agents, namely, 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of resin.

[0004] Furthermore, Patent Document 2 proposes a decorative material having a printed layer and a transparent resin layer in this order on a substrate, with an embossed pattern on the outermost surface of the transparent resin layer.

[0005] In order to impart surface properties such as weather resistance to articles such as decorative materials and decorative sheets used in the above applications, a curable resin is used to form a surface layer, and the cured resin is used as a layer (see, for example, Patent Documents 3 to 5). Patent Document 3 describes a decorative sheet in which a surface layer (top coat layer) is formed by irradiating an electron beam-curable resin composition with an electron beam to cure it, and Patent Document 4 describes a surface layer (gloss-adjusting resin layer) formed from a crosslinked, cured product of an ionizing radiation-curable resin composition containing matte silica. Patent Document 5 also describes the use of an ultraviolet-curable resin layer as a surface protective layer.

[0006] Among the above-mentioned applications, exterior components such as exterior walls, soffits, roofs, fences, and railings are used outdoors, and problems such as color change and resin deterioration occur due to the effects of wind, rain, and even ultraviolet rays from sunlight. A common method for improving the light resistance of decorative sheets used in such applications is to add an ultraviolet absorber as a weather resistance agent to the surface protective layer of the decorative material. Furthermore, even for applications such as interior components that are basically intended for indoor use, if they are exposed to sunlight near a window, for example, light resistance similar to that of exterior components may be required.

[0007] However, there is a problem in that the UV absorber tends to bleed out from the surface protective layer over time. When the UV absorber bleeds out, the surface appearance of the decorative sheet is impaired by issues such as stickiness, and the bled-out UV absorber is gradually lost due to washout by rain, etc., resulting in a decrease in the concentration of the UV absorber in the surface protective layer over time, resulting in problems such as a decrease in weather resistance. Under these circumstances, to solve the problem of UV absorber bleed-out, decorative sheets have been proposed that have a cured layer of a resin whose main component is an electron beam-curable resin containing an electron beam-reactive UV absorber selected from specific benzotriazole-based compounds, for example (see, for example, Patent Document 1). The decorative sheet described in Patent Document 1 can solve the problem of UV absorber bleed-out.

[0008] In recent years, with the increasing trend in customers' preference for luxury goods, there has been a demand for decorative materials and decorative sheets used for the above-mentioned purposes that have a luxurious feel. A commonly used method for imparting a luxurious feel is to impart a textured surface to enhance its texture. Specifically, examples include embossing using a mold-transfer sheet or embossing plate, or using a transfer sheet with a textured layer to transfer a textured layer onto the surface to impart a textured texture, thereby achieving a matte effect. For example, Patent Document 6 proposes a mold-transfer sheet that has a textured layer made of an ionizing radiation-curable resin on the surface of a substrate sheet, and a polyester decorative board that reproduces a desired pattern by imparting a crosslinking density that prevents the textured pattern from cracking when peeled off, as well as a polyester decorative board that uses the mold-transfer sheet. Patent Document 2 also proposes a decorative sheet that has a printed layer and a transparent resin layer, in that order, on a substrate, and an embossed pattern on the outermost surface of the transparent resin layer.

[0009] Furthermore, decorative materials and sheets having a matte effect (matt effect) are sometimes used as writing sheets that form the surfaces of various writing boards such as blackboards and whiteboards, and as reflective screens. When installed indoors, such as in a lecture room or conference room, the matte coating-formed sheets used for these purposes are required to reduce reflections from room lights and the like and to suppress gloss, thereby improving the visibility of letters and the like displayed on the writing board or projection screen.

[0010] For example, Patent Documents 7 and 8 propose whiteboard sheets having a whiteboard writing layer. Conventional products, including the whiteboard sheets of Patent Documents 7 and 8, have matting agents such as silica and calcium carbonate, as well as other pigments, added to the surface coating film to reduce reflections from room lights and the like by scattering light, reduce gloss, and improve the visibility of letters and the like displayed on writing boards, projection screens, etc. In other words, conventional products reduce reflections from room lights and gloss by the matting effect of the matting agents, thereby improving visibility.

[0011] In particular, writing sheets for whiteboards and the like are required to be able to write on and erase with a marker, and therefore, they are required to have a balance between appropriate surface wettability and easy cleaning properties, and to have good writing and erasing properties with a marker. To achieve this, the surface needs to be as smooth as possible. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] Japanese Patent Application Laid-Open No. 2000-062081 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-073207 [Patent Document 3] Japanese Patent Application Laid-Open No. 2000-117905 [Patent Document 4] Japanese Patent Application Laid-Open No. 2004-148632 [Patent Document 5] Japanese Patent Application Laid-Open No. 2000-103019 [Patent Document 6] Japanese Patent Application Publication No. 2-235744 [Patent Document 7] Special Publication No. 7-64155 [Patent Document 8] Japanese Patent Application Publication No. 11-28892 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0013] Examples of methods for improving texture by a matte effect include a method in which a matting agent (also referred to as a "matting agent") is used to obtain a matte effect by the light diffusion effect of the agent itself, as in Patent Document 1, and a method in which an embossing process is performed to form an uneven shape on the outermost surface, as in Patent Document 2. However, when a matting agent is used as in Patent Document 1, the amount used must be increased to improve the matting effect. However, as the amount used increases, the surface properties tend to deteriorate because the matting agent falls off the coating film and scratches the coating film, reducing scratch resistance. On the other hand, if the amount used is reduced to prevent the deterioration of surface properties, the matting effect tends to deteriorate, and surface properties and matting effect are in a trade-off relationship. Therefore, there is a limit to the matte effect achieved using a matting agent. Furthermore, when embossing is used as in Patent Document 2, it is not easy to create an embossing plate, which requires a great deal of time and effort, and it is also necessary to create a plate for each desired pattern. Therefore, it cannot be said that this method is easy to fully respond to the diversity of customer demands.

[0014] The decrease in scratch resistance due to the matting agent falling off from the coating film and damaging the coating film is particularly noticeable, for example, in applications such as flooring materials among interior building components, frequently used building materials such as window frames, doors, door frames, and handrails, and whiteboard sheets that are repeatedly subjected to friction from blackboard erasers (or whiteboard erasers) and markers.

[0015] Furthermore, in recent years, decorative sheets for outdoor use have been used under more severe solar radiation conditions due to the rise in average temperatures caused by global warming, and conventional decorative materials are no longer able to cope with this, with the rate at which they deteriorate is accelerating year by year. Therefore, while the design concept of suppressing the bleed-out of UV absorbers is still valid, it is necessary to reconsider the means of achieving this.

[0016] Furthermore, while there is a demand for decorative sheets that have excellent surface properties, particularly easy decontamination properties (also referred to as "erasability") that allow for the easy decontamination of dirt adhering to the surface, and that also have an excellent matte effect and texture, for example, in fields such as building flooring, which is prone to staining, and whiteboards, where writing with a marker is repeatedly performed and then erased, there is currently no decorative sheet that can adequately meet these demands.

[0017] Thus, in addition to the matte effect, there is a demand for further desired surface properties, but currently there are no decorative materials, decorative sheets or other articles that can fully meet this demand.

[0018] As described in Patent Documents 3 to 5, ionizing radiation-curable resins, particularly electron beam-curable resins and ultraviolet-curable resins, are used as the curable resin for forming the surface layer. When using an ultraviolet-curable resin that can be cured using ultraviolet light, a photopolymerization initiator is typically used, as disclosed in Patent Document 5. Because ultraviolet light has significantly lower energy than other ionizing radiations such as electron beams, the addition of a photopolymerization initiator does not promote curing by functional groups, such as ethylenically unsaturated groups, which exhibit curability when exposed to ionizing radiation, and therefore the desired surface properties cannot be obtained. Thus, while the composition of the resin composition forming the surface layer must be adjusted depending on the curing method of the resin composition, it is desirable to form a layer with excellent surface properties regardless of the resin composition used. Furthermore, a matte effect may be required to improve design. Under these circumstances, there has been a demand for a method for forming a surface layer made of an ionizing radiation-curable resin that can provide excellent surface properties and a visible matte effect without adding a photopolymerization initiator when curing the surface layer.

[0019] Furthermore, with customers increasingly turning to luxury goods, there is a demand for higher quality textures. However, the textured shape of the pattern-transfer film described in Patent Document 3 is formed by forming a predetermined pattern with a liquid-repellent resin, then applying a two-component curing resin composition containing an inorganic filler, and then repelling only the two-component curing resin composition on the pattern due to the liquid-repellent effect of the liquid-repellent resin. Therefore, there are limitations to forming a delicate textured shape, and it is not possible to impart an excellent matte effect, and there are cases where the desired demands cannot be fully met. Furthermore, in the case of the method of forming a concave-convex shape on the outermost surface by embossing as in Patent Document 2, the production of the embossing plate is a laborious and not easy task, and furthermore, a plate must be produced for each desired pattern. Therefore, it cannot be said that this method is easy to fully respond to the diversity of customer demands.

[0020] When using matting agents, pigments, etc., as described above, to achieve excellent visibility through a matte effect in products used in whiteboard sheets having the above-mentioned whiteboard writing layer, markers tend to seep between these particles and the coating resin. Once soaked, the markers cannot be erased even by wiping them off (reduced marker erasability). Furthermore, to achieve a matte effect using particles such as matting agents or pigments to reduce glare and gloss from room lights and improve visibility, a large amount of particles is required, making the problem of ink inerasability even more pronounced. Furthermore, using a large amount of particles makes the shape corresponding to the shape of the matting agent, pigment, etc. particles more apparent, resulting in a loss of smoothness and reduced marker erasability. Thus, there is a trade-off between reducing glare and gloss from room lights and improving visibility through the matte effect using matting agents, pigments, etc., and, in particular, marker erasability. Therefore, the whiteboard sheets described in Patent Documents 1 and 2 are insufficient in terms of both visibility due to the matte effect and marker erasability, and further improvements are required.

[0021] An object of the present invention is to provide a matte article that has excellent visibility and texture of the matte effect and has various desired surface properties, and a method for producing the matte article. [Means for solving the problem]

[0022] In order to solve the above problems, the present invention has discovered that by incorporating a predetermined amount of a wrinkle formation stabilizer and employing a matte layer having an uneven shape composed of irregular wrinkles, it is possible to obtain a matte article that has excellent visibility and texture of the matte effect, and that has various surface properties as desired, and that can be used for shaping and can meet diverse needs. Furthermore, with regard to a method for manufacturing an article, the inventors have found that (i) by subjecting a resin composition containing a predetermined amount of a wrinkle formation stabilizer to a specific irradiation treatment to form a matte layer, the matte layer has an uneven shape composed of irregular wrinkles, and the matte effect is excellent in visibility and texture, and matte articles having various desired surface properties can be easily obtained; and further, (ii) even if a resin composition does not contain a photopolymerization initiator, by subjecting the resin composition to a specific irradiation treatment to form a surface wrinkle layer, the surface wrinkle layer will have wrinkles, and matte articles having desired surface properties and which can also have the visibility of the matte effect can be easily obtained. [Effects of the Invention]

[0023] According to the present invention, it is possible to provide a matte article which has excellent visibility and texture of the matte effect and has various surface properties as desired, a matte article which can be used for shaping and which can meet diversifying needs, and a method for producing a matte article. [Brief explanation of the drawings]

[0024] [Figure 1] 1 is a schematic plan view showing one embodiment of a matte article of the present invention. [Figure 2] 1 is a cross-sectional view showing one embodiment of the matte layer of a matte article of the present invention. [Figure 3] 1 is a cross-sectional view showing one embodiment of the matte article of the present invention. [Figure 4] 1 is a cross-sectional view showing one embodiment of the matte article of the present invention. [Figure 5] 1 is an optical microscope image of the surface of the matte article obtained in Example 1A. [Figure 6] 1 is an optical microscope image of the surface of the matte article obtained in Example 2A. [Figure 7] 1 is an optical microscope image of the surface of the matte article obtained in Example 3A. [Figure 8] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1A. [Figure 9] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2A. [Figure 10] 1 is an optical microscope image of the surface of the matte article obtained in Example 1B. [Figure 11] 1 is an optical microscope image of the surface of the matte article obtained in Example 2B. [Figure 12] 1 is an optical microscope image of the surface of the matte article obtained in Example 3B. [Figure 13] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1B. [Figure 14] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2B. [Figure 15] 1 is an optical microscope image of the surface of the matte article obtained in Example 1C. [Figure 16] 1 is an optical microscope image of the surface of the matte article obtained in Example 2C. [Figure 17] 1 is an optical microscope image of the surface of the matte article obtained in Example 3C. [Figure 18] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1C. [Figure 19] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2C. [Figure 20] 1 is an optical microscope image of the surface of the matte article obtained in Example 1D. [Figure 21] 1 is an optical microscope image of the surface of the matte article obtained in Example 2D. [Figure 22] 1 is an optical microscope image of the surface of the matte article obtained in Example 3D. [Figure 23] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1D. [Figure 24] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2D. [Figure 25] 1 is an optical microscope image of the surface of the matte article obtained in Example 1E. [Figure 26] 1 is an optical microscope image of the surface of the matte article obtained in Example 2E. [Figure 27] 1 is an optical microscope image of the surface of the matte article obtained in Example 3E. [Figure 28]1 is an optical microscope image of the surface of the article obtained in Comparative Example 1E. [Figure 29] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2E. [Figure 30] 1 is an optical microscope image of the surface of the matte article obtained in Example 1F. [Figure 31] 1 is an optical microscope image of the surface of the matte article obtained in Example 2F. [Figure 32] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1F. [Figure 33] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2F. [Figure 34] FIG. 1 is a cross-sectional view showing one embodiment of a matte article G of the present invention. [Figure 35] FIG. 1 is a cross-sectional view showing one embodiment of a matte article G of the present invention. [Figure 36] 1 is an optical microscope image of the surface of the matte article obtained in Example 1G. [Figure 37] 1 is an optical microscope image of the surface of the matte article obtained in Example 2G. [Figure 38] 1 is an optical microscope image of the surface of the matte article obtained in Example 3G. [Figure 39] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1G. [Figure 40] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2G. [Figure 41] 1 is a cross-sectional view showing one embodiment of a matte article H of the present invention. [Figure 42] 1 is a cross-sectional view showing one embodiment of a matte article H of the present invention. [Figure 43] 1 is an optical microscope image of the surface of the matte article obtained in Example 1H. [Figure 44] 1 is an optical microscope image of the surface of the matte article obtained in Example 2H. [Figure 45] 1 is an optical microscope image of the surface of the matte article obtained in Example 3H. [Figure 46] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1H. [Figure 47] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2H. [Figure 48] 1 is an optical microscope image of the surface of the matte article obtained in Example 1I. [Figure 49] 1 is an optical microscope image of the surface of the matte article obtained in Example 2I. [Figure 50] 1 is an optical microscope image of the surface of the matte article obtained in Example 3I. [Figure 51] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 1I. [Figure 52] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2I. [Figure 53] 1 is an optical microscope image of the surface of the matte article obtained in Example 1J. [Figure 54] 1 is an optical microscope image of the surface of the matte article obtained in Example 2J. [Figure 55] 1 is an optical microscope image of the surface of the matte article obtained in Example 3J. [Figure 56] 1 is an optical microscope image of the surface of the article obtained in Comparative Example 2J. DETAILED DESCRIPTION OF THE INVENTION

[0025] Hereinafter, an embodiment of the present invention (hereinafter, sometimes referred to as "the present embodiment") will be described. In this specification, the numerical values ​​associated with "greater than or equal to," "less than or equal to," and "to" in describing a numerical range can be arbitrarily combined, and the numerical values ​​in the examples are numerical values ​​that can be used as the upper and lower limits of the numerical range.

[0026] [Matte article A] The matte article of this embodiment is a matte article having a matte layer, the matte layer being composed of a cured product of a resin composition containing 0.5 to 6.0 parts by mass of a wrinkle formation stabilizer per 100 parts by mass of resin, at least one surface of the matte layer having an irregular shape composed of irregular wrinkles, and the 60° gloss value of the matte layer being 5.0 or less (hereinafter simply referred to as "matte article A"). By having such a configuration, matte article A has excellent surface properties, particularly scratch resistance, and also excellent visibility and texture of the matte effect.

[0027] [Matte layer] The matte layer in the matte article A is a layer formed of a cured product of a resin composition (hereinafter sometimes referred to as a "matte layer-forming resin composition.") containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin. That is, in this embodiment, the matte layer is a layer containing the wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin that forms the matte layer.

[0028] (Wrinkle formation stabilizer) The wrinkle formation stabilizer stabilizes wrinkle formation on at least one surface of the matte layer, thereby achieving a stable visibility of the matte effect across the entire surface of the matte article A and reducing localized unevenness in gloss (hereinafter, the term "stable visibility of the matte effect" or equivalent expressions may be used). The wrinkle formation stabilizer also has the function of imparting uniformity to the surface condition (also referred to as "texture") due to the stable formation of wrinkles across the entire surface of the matte article A. In other words, even if the so-called "matting agent" in the prior art and the "wrinkle formation stabilizer" in this embodiment have the same constituent substances and average particle diameter, they differ in the mechanism (action) of matting, the structure for achieving matting, and the relationship between the amount used and the level of surface gloss (gloss value). The wrinkle formation stabilizer's ability to "stabilize wrinkle formation" means, more specifically, that the shape of the "wrinkles" and their geometric characteristic values ​​(individual protrusions in the uneven shape of the wrinkles (length, width, and ratio of these protrusions) as well as statistical indicators such as Rz (maximum height), Rsm (average length of curved elements), Ra (arithmetic mean roughness), Ssk (skewness), and Sku (kurtosis) as well as these characteristic values ​​or indicators, and various numerical values ​​and indicators resulting from these, such as the in-plane distribution (variance σ) of 60° gloss values ​​on the surface of the matte surface layer, converge when the "wrinkle formation stabilizer" is used compared to when it is not used.

[0029] In general, when the surface of a resin layer containing particles such as matting agents comes into contact with and is rubbed against another object, the particles near the surface tend to fall off. Therefore, if the gloss of the layer surface is reduced solely by adding matting agents, the falling off of such particles will cause a change in gloss when the layer comes into contact with or rubs against another object. The change in gloss due to this mechanism becomes more pronounced the higher the content of matting agents is, the lower the gloss specification becomes. In particular, the 60° gloss value G 60 When a matting agent is added to achieve a surface with a gloss of 10 or less, it is necessary to add approximately 50 parts by mass or more of the matting agent per 100 parts by mass of resin (although this depends on the dispersion form of the resin and the type of matting agent), and this results in a significant change in gloss due to the matting agent falling off when it comes into contact with or rubs against other objects. In the matte layer of the matte article A, as will be demonstrated in the examples and comparative examples described later, the 60° gloss value G 60 Even when a surface having a 60° gloss value G of 5.0 or less is realized by adding a matting agent, the content of the wrinkle formation stabilizer per 100 parts by mass of resin can be about 10 parts by mass or less, more specifically, 6.0 parts by mass or less. For example, in the examples of the present invention, when the total content of the wrinkle formation stabilizer is a maximum of 6 parts by mass, the 60° gloss value G 60 In this specification, a 60° gloss value of 5.0 or less is considered to be "matte," as will be described later. Therefore, in the case of the matte article A, as will be demonstrated in the examples and comparative examples described later, when the same low gloss surface is realized, the 60° gloss value G 60 When a value of 10 or less, or even 5.0 or less is achieved, the particle content is significantly reduced compared to conventional matte articles, and therefore, there is little change in gloss due to the matting agent falling off when the article comes into contact with or rubs against other objects.

[0030] In the prior art such as Patent Document 1, matting agents used to achieve a matte finish themselves exhibit a matte finish due to a light diffusion effect resulting from their physical shape and inherent refractive index. Specifically, what is generally referred to as a matting agent generally has a refractive index difference between the matting agent particles and the surrounding resin and air, and the matte finish is visible due to a light diffusion effect at the interface where light is reflected and refracted corresponding to the particle's contour. In contrast, in the matte article of the present embodiment, the wrinkle formation stabilizer does not exhibit the visibility of the matte finish due to light diffusion caused by the reflection and refraction of light by the particles themselves, but stabilizes the formation of wrinkles on the surface of the matte layer, thereby imparting a stable texture to the matte article along with the visibility of the matte finish due to the light diffusion effect at the interface where the refractive index difference between the surface and air exists. Therefore, the wrinkle formation stabilizer used in this embodiment is different from a matting agent that itself exhibits a visible matting effect in terms of the matting mechanism (action) and structure for exhibiting the matting effect (even if the constituent substances and average particle diameters of both are the same). Furthermore, the relationship between the content of "wrinkle formation stabilizers" and "matt agents" is also different in terms of the surface gloss (gloss value). When the same substance A is used as a wrinkle formation initiator AW (W: an abbreviation for wrinkles), and a specific amount C is added to form wrinkles on the surface, the 60° gloss value G of the surface is 60° AW (C) is the 60° gloss value G of the surface when the substance A is used simply as a matting agent AM (M: abbreviation for matte) and is contained in the specified amount C, but no wrinkles are formed on the surface. 60° AM (C) is clearly lower than (C). In other words, the following relationship holds: G60° AW (C) <G 60° AM (C)

[0031] The matte layer may contain a conventional matting agent. However, considering the characteristic effect of the present invention, namely, the stable provision of excellent visibility and texture of the matte effect, which cannot be achieved even with the use of a matting agent, it is preferable to not contain a matting agent. Thus, it can be said that the matte article A has excellent visibility and texture of the matte effect, even without substantially containing the matting agents conventionally used to achieve the visibility of the matte effect. Therefore, when a matting agent is included (added), it is sufficient to reinforce the matte effect due to wrinkles on the surface of the matte layer. Here, "not containing a matting agent" means not only that the matting agent is not included at all, but also that even if it is included, the visibility of the matte effect due to the action and effect of the matting agent itself is not achieved. Specifically, the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, and more preferably 3.0 parts by mass or less, per 100 parts by mass of the resin. In this specification, the term "matting agent" refers to particles having an average particle size whose lower limit is the smaller of more than 100% of the thickness of the layer in which the matting agent can be contained, i.e., more than 30 μm, or more than the thickness of the matting layer, from the viewpoint of realizing the visibility of the matting effect by the light diffusion effect due to the refractive interface and the reflection of light rays corresponding to the outline shape of the particles, as described above.

[0032] The wrinkle formation stabilizer is not a matting agent as described above, but rather has an average particle size of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller, and various particles such as organic particles, inorganic particles, etc. In the present embodiment, if a wrinkle formation stabilizer is not used, wrinkle formation becomes unstable, and as a whole, the visibility and texture of the excellent matte effect due to wrinkle formation cannot be stably obtained.

[0033] The wrinkle formation stabilizer used in the matte article A is not particularly limited as long as it is a particle that is not a matte agent and has an average particle size of 100% or less of the thickness of the matte layer. Among these, it is preferable to use wrinkle formation stabilizer 1, which has 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 or 30 μm or less, or wrinkle formation stabilizer 2, which has an average particle size of less than 1 μm. In this embodiment, as the wrinkle formation stabilizer, one or more types of wrinkle formation stabilizer 1 may be used, or one or more types of wrinkle formation stabilizer 2 may be used, or one or more types of wrinkle formation stabilizer 1 may be used in combination with one or more types of wrinkle formation stabilizer 2. In this embodiment, it is preferable to use two types of wrinkle formation stabilizers, wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, from the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect.

[0034] As the wrinkle formation stabilizer, for example, organic particles or inorganic particles can be used. Examples of organic materials that can be used to form organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin, and polyester-based resin. Examples of inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate, and among these, silica is preferred because of its excellent transparency.

[0035] The shape of the wrinkle formation stabilizer is not particularly limited, but examples thereof include spherical, polyhedral, scaly, and amorphous shapes.

[0036] From the viewpoint of stabilizing wrinkle formation and improving the visibility and texture of the matte effect, the upper limit of the average particle diameter of the wrinkle formation stabilizer is preferably 90% or less of the matte layer thickness, more preferably 80% or less of the matte layer thickness, and even more preferably 70% or less of the matte layer thickness. The absolute value 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. The upper limit may be the smaller of any combination of the upper limit relative to the matte layer thickness and the upper limit of the absolute value. For example, the upper limit may be the smaller of either 90% or less of the matte layer thickness or 20 μm or less, or the smaller of either 90% or less of the matte layer thickness or 10 μm or less. The thickness of the matte layer will be described later. The lower limit is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more.

[0037] When wrinkle formation stabilizers 1 and 2 are used separately as described above, the average particle diameter of wrinkle formation 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, from the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, with the upper limit being as described above. From the same viewpoint, the average particle diameter of the wrinkle formation stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, and even more preferably 5 nm or more, with the upper limit being preferably 900 nm or less, more preferably 700 nm or less, and even more preferably 500 nm or less. In this specification, the average particle size of the wrinkle formation stabilizer is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method.

[0038] The content of the wrinkle formation stabilizer, or the total content when wrinkle formation stabilizers 1 and 2 are used in combination as wrinkle formation stabilizers, is 0.5 to 6.0 parts by mass per 100 parts by mass of the resin forming the matte layer. If the content is less than 0.5 parts by mass, the effect of using the wrinkle formation stabilizer cannot be obtained, and wrinkle formation is unstable, resulting in the inability to consistently obtain the visibility and texture of the matte effect. On the other hand, if the content exceeds 6.0 parts by mass, the wrinkle formation stabilization effect becomes saturated, and as described in the "Background Art and Its Problems" section, the impact of deterioration of surface properties such as scratch resistance, contamination resistance, and ease of decontamination (erasability) tends to increase. Furthermore, if the content exceeds 6.0 parts by mass, depending on the type of wrinkle formation stabilizer and resin and the conditions for forming the matte layer (or surface wrinkle layer), it may become difficult to stabilize wrinkle formation, making it difficult to consistently obtain the visibility and texture of the matte effect, and surface properties may also be deteriorated.

[0039] From the viewpoint of stabilizing the formation of wrinkles by the wrinkle formation stabilizer and stably improving the visibility and texture of the matte effect, the total content of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 is preferably 0.75 parts by mass or more, more preferably 1.0 part by mass or more, and even more preferably 1.2 parts by mass or more, per 100 parts by mass of the resin that forms the matte layer, and there is no particular upper limit as long as it is 6.0 parts by mass or less, from the viewpoint of stably improving the visibility of the matte effect.

[0040] The content of wrinkle formation stabilizer 2 is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and even more preferably 1.0 part by mass or more, relative to 100 parts by mass of the resin, with the upper limit being 6.0 parts by mass or less, preferably 5.0 parts by mass or less, more preferably 3.5 parts by mass or less, and even more preferably 3.0 parts by mass or less. The blending ratio of wrinkle formation stabilizer 1 to wrinkle formation stabilizer 2 (wrinkle formation stabilizer 1 / wrinkle formation stabilizer 2) is preferably 0.05 to 0.95, more preferably 0.10 to 0.90, even more preferably 0.20 to 0.80, and still more preferably 0.30 to 0.70.

[0041] As described above, organic particles and inorganic particles can be used as wrinkle formation stabilizers, but these particle types themselves can also be said to include those conventionally used as matting agents. For example, matting agents such as spherical alumina and calcium carbonate are used in the matte layer of the decorative sheet described in Patent Document 1 above. In order for matting agents such as spherical alumina and calcium carbonate to exhibit the visibility of their matting effect by themselves due to the light diffusion effect caused by their physical shape, they need to be used in a total content of about 50 parts by weight, i.e., 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of resin, as described in Patent Document 1. However, in Matte Article A, as described above, even when a small amount is used, i.e., a content less than the content necessary to exhibit the visibility and texture of the matting effect by itself due to the light diffusion effect caused by the physical shape, extremely superior visibility and texture of the matting effect are obtained compared to the effects obtained by matting agents. Therefore, it can be said that although Matte Article A does not substantially contain a matting agent, wrinkles are stably formed on the surface, thereby consistently achieving a superior matting effect in visibility and texture compared to when a matting agent is used.

[0042] (Matte layer surface shape) The matte layer is a layer composed of a cured product of a resin composition for forming a matte layer, which contains the specific wrinkle formation stabilizer at a specific content. As described above, the formation of wrinkles on the surface of the matte layer is stabilized, and the layer stably exhibits the visibility and texture of the matte effect due to the light diffusion effect caused by the shape of the wrinkles. Figure 1 is a schematic plan view of one embodiment of a matte article A of this embodiment, and is a schematic image of the surface of the matte article A obtained in the examples. Figure 1 shows that wrinkles are formed on the surface of the matte article A of this embodiment, i.e., on the surface of the matte layer.

[0043] In the matte article A, at least one surface of the matte layer has an uneven shape formed by irregular wrinkles. The uneven shape formed by such wrinkles is stabilized by the addition of a wrinkle formation stabilizer, resulting in a stable matte effect with visibility and texture. The irregular wrinkles are preferably formed by a plurality of protrusions and a recess formed by being surrounded by the plurality of protrusions, and the protrusions preferably have linear protrusions. In this specification, "linear protrusions" (hereinafter also referred to as "linear protrusions") means that the ratio of the length to the width of the protrusions (length / width) is 3 or more, preferably 5 or more, and more preferably 10 or more, and the method for determining the length and width is as described below. In this embodiment, more preferable irregular wrinkles are those constituted by a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions.

[0044] An example of the wrinkles is shown in Fig. 1. Fig. 1 shows that the surface of the matte article A, i.e., the surface of the matte layer, has irregular wrinkles in a planar view, and that the irregular wrinkles are configured to include a plurality of protrusions 3 formed by a plurality of curved filamentary protrusions and recesses 2 formed by being surrounded by the plurality of protrusions (a plurality of protrusions 3). It also shows that at least a portion of the curved protrusions 3 are formed by meandering filamentary protrusions in a planar view (observed from the z direction in Figs. 1 to 3), and that the meandering recesses 2 are formed so as to be surrounded by the meandering filamentary protrusions. The matte article A of this embodiment stably exhibits the visibility and texture of the matte effect due to the stable formation of wrinkles shown in Fig. 1.

[0045] Here, "curved" means that there is one or more portions where the extension direction of the continuous linear protrusions 3 reverses from one side to the other in a planar view. Examples of portions where the extension direction reverses from one side to the other include a form having an inflection point when the linear protrusions 3 are approximated by a continuous curve when the width of the planar view shape is ignored (when the width is considered to be 0). Further, examples include a form having a portion that is approximated by a V-shaped folded line or two sides of a triangle sandwiching one vertex when the linear protrusions 3 are approximated by a straight line when the width of the planar view shape is ignored. Furthermore, "meandering" means that there are at least two or more portions where the extension direction of the continuous linear protrusions 3 reverses from one side to the other in a planar view (hereinafter also referred to as "reversed portions"). When the linear protrusions 3 are followed in their extension direction, the extension direction of the linear protrusions 3 alternately reverses in opposite directions at two adjacent portions. For example, when the width of the planar view shape of the linear protrusions 3 is ignored and the linear protrusions 3 are approximated by a continuous curve, an example of such a shape is one having a portion that can be approximated by the Roman letter "S." Furthermore, when the width of the planar view shape of the linear protrusions 3 is ignored and the linear protrusions 3 are approximated by a straight line, an example of such a shape is one having a portion that can be approximated by the Roman letter "W."

[0046] In this specification, "irregular" means a shape that does not have a fixed rule or is not arranged according to a fixed rule, i.e., is not patterned. A typical example of a non-irregular shape (regular shape) is a shape that is arranged with a fixed periodicity in a specific direction, such as a so-called "lenticular lens," in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to their longitudinal direction. Therefore, the irregular wrinkles in this embodiment include a shape in which the shape of a single protrusion itself is irregular and not formed according to a fixed rule such as periodicity, a shape in which the shapes of multiple convex portions formed by multiple protrusions are irregular and not formed and arranged according to a fixed rule, and a shape in which a concave portion surrounded by such multiple protrusions is also irregular. In matte article A, if the shape of a single protrusion (a single convex portion), the shape and arrangement of each of a plurality of protrusions (a plurality of convex portions), or the shape of a recess surrounded by a plurality of protrusions is irregular, the visibility and texture of the matte effect due to the irregular wrinkles can be obtained, but it is preferable that all of them are irregular. By having irregular wrinkles, matte article A improves the visibility and texture of its matte effect, and stably exhibits extremely excellent visibility and texture of the matte effect.

[0047] As described above, the matte layer has wrinkles, i.e., an uneven shape, on at least one surface thereof. The convex and concave portions in the uneven shape can be classified by, for example, binarizing the image of the surface of the matte article A by using the brightness difference of the image of the surface of the matte article A, where the darkest portion of the density distribution image is set to gradation 255 and the lightest portion of the density distribution image is set to gradation 0, with gradations 0 to 127 representing concave portions and gradations 128 to 255 representing convex portions.

[0048] Preferably, irregular wrinkles are formed on at least a portion of the surface of the matte article A, and more preferably, irregular wrinkles are formed over the entire surface. The location where the wrinkles are formed is not particularly limited as long as it is on the surface of the matte article A, and is not limited to, for example, only locations corresponding to a pattern (on the pattern) described below. As long as the wrinkles are formed on at least a portion of the surface, the visibility and texture of the matte effect due to the formation of wrinkles will be realized. For example, in the case of a matte article having a pattern layer described below and having irregular wrinkles formed in a portion, if the wrinkles are formed in locations corresponding to the pattern of the pattern layer (for example, on the pattern), the pattern will be visually perceived as being more matte than the surrounding area, thereby improving the design. 1, it is preferable to have a plurality of convex portions formed by a plurality of protrusions that are irregular but have a certain degree of uniformity, and a concave portion surrounded by the convex portions. Therefore, a shape of one convex portion (protrusion) in which the width or height changes drastically is not considered to be a preferable embodiment for obtaining the visibility and texture of the matte effect. Specific embodiments of the shapes of convex portions (protrusions) and concave portions that form irregular wrinkles and that can be advantageous for stably improving the visibility and texture of the matte effect are described below.

[0049] Regarding the shape of the wrinkles formed on at least one surface of the matte layer, the height of the convex portions (height of the protrusions) 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 about 10 μm or less. Furthermore, the width of the convex portions 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 preferably 10 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less. When the height and width of the convex portions are within the above ranges, the visibility and texture of the matte effect are stably improved in relation to the concave portions. Here, the above dimensions of the convex portions are the average values ​​of 10 convex portions (projections) at 10 arbitrary locations (100 μm square areas × 10 locations) on the matte article of this embodiment, i.e., a total of 100 convex portions. Furthermore, as shown in FIG. 1, the width of each convex portion (projection) is not uniform but varies, so the width of each convex portion (projection) is the average value of the widths at five arbitrary locations on that single convex portion (projection). The same applies to the height of the convex portions (projections).

[0050] The depth of the recesses 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 about 10 μm or less. The width of the recesses 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 preferably 10 μm or less, more preferably 3 μm or less, and even more preferably 2 μm or less. When the depth and width of the recesses are within the above ranges, the visibility and texture of the matte effect are stably improved in relation to the protrusions. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0051] The distance from the top of the convex portion to the bottom of the concave portion (height difference between the convex portion and the concave portion) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 8 μm or less, and even more preferably 7 μm or less. When the distance is within the above range, the visibility and texture of the matte effect are stably improved. Here, the dimensions of the recessed portion are determined in the same manner as the dimensions of the protruding portion described above.

[0052] The proportion of the convex portions is preferably 15% or more, more preferably 20% or more, and even more preferably 30% or more, with the upper limit being preferably 80% or less, more preferably 70% or less, and even more preferably 60% or less. When the proportion of the convex portions is within the above range, the visibility and texture of the matte effect are stably improved in relation to the proportion of the concave portions surrounded by the convex portions. Here, the proportion of the convex portions is the average value of the proportion of the convex portions in 10 arbitrary locations on the matte article A (100 μm square area×10 locations).

[0053] The convex portions and concave portions may have portions of approximately the same direction and width, but from the viewpoint of stably improving the visibility and texture of the matte effect, it is preferable that the length be short. Specifically, the length of the convex portions and concave portions of approximately the same direction and width continuing is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, with the lower limit being preferably 5 μm or more, more preferably 10 μm or more, and even more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, thereby stably improving the visibility and texture of the matte effect. Here, of any 10 convex portions and concave portions (i.e., a total of 100 convex portions and concave portions) in any 10 locations (100 μm square areas × 10 locations) on matte article A, it is preferable that 80% or more of them satisfy the above conditions, more preferably 85% or more, even more preferably 90% or more, and even more preferably 95% or more. Furthermore, in this specification, the "substantially the same" in "substantially the same" means roughly the same, without branching, meaning a difference of within ±3° in the direction, and within ±5% in the width.

[0054] The number of convex portions (projections) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more, with the upper limit being preferably 200 or less, more preferably 100 or less, and even more preferably 70 or less. When the number of convex portions is within the above range, the visibility and texture of the matte effect are stably improved. The number of convex portions is the average value of the number of convex portions in 10 places on the matte article A (100 μm square area×10 places).

[0055] FIG. 2 is a cross-sectional view showing one embodiment of the matte article A, in which the matte article is cut along a plane parallel to its thickness direction (Z direction in the figure). The shape of the recess may be, for example, acute-angled as shown in 2a in Figure 2, semicircular or semi-elliptical as shown in 2b, or a combination of these.Furthermore, a shape such as 2c in Figure 2, in which one protrusion has a recess in a part thereof, may also be used. On the other hand, the shape of the convex portion is semicircular or semielliptical, although the width varies as shown in 3a and 3b in FIG.

[0056] The thickness of the matte layer is not particularly limited as long as it is thick enough to form the above-mentioned wrinkles to a degree that can stably express the visibility and texture of the matte effect. However, taking into consideration ease of production, the thickness is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, and still more preferably 5 μm or more, with the upper limit being preferably 300 μm or less, more preferably 200 μm or less, even more preferably 150 μm or less, and still more preferably 100 μm or less. In this specification, the thickness of the matte layer is determined by measuring the thickness at 20 points on an image of the cross section of the matte article taken using a scanning electron microscope (SEM), and averaging the values ​​at the 20 points. The accelerating voltage of the SEM is 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

[0057] The matte layer may be provided partially or entirely, but is preferably provided entirely from the viewpoint of improving the visibility and texture of the stable matte effect. When the matte layer is provided partially, the matte article A of this embodiment preferably has a substrate, which will be described later, as a layer substantially other than the matte layer.

[0058] (resin) The resin forming the matte layer may be any resin that forms a matte layer by forming a resin composition for forming the matte layer containing a predetermined amount of the wrinkle formation stabilizer and curing the composition to form a cured product. Examples of such resins include ionizing radiation curable resins. Since the matte layer is a layer that can be formed on the outermost surface of the matte article A, it is preferable that the resin be one that is easily wrinkled by the wrinkle formation stabilizer, and that, from the viewpoint of improving usability as a matte article, it is also preferable that the resin be one that is easily able to exhibit surface properties such as scratch resistance, contamination resistance, and weather resistance, as well as processability. From these viewpoints, ionizing radiation curable resins are preferred. Since the content of the wrinkle formation stabilizer in the matte layer of the matte article A is extremely low, the performance of the resin forming the matte layer is more directly exerted as its surface properties.

[0059] The ionizing radiation curable resin is a resin having an ionizing radiation curable functional group, which is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferred examples thereof include functional groups having an ethylenic double bond, such as a (meth)acryloyl group, a vinyl group, and an allyl group. In this specification, the term "(meth)acryloyl group" refers to an acryloyl group or a methcroyl group. In this specification, the term "(meth)acrylate" refers to an acrylate or a methacrylate. Furthermore, ionizing radiation refers to electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing and / or crosslinking molecules. Typically, ultraviolet (UV) rays or electron beams (EB) are used, but it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0060] Examples of the ionizing radiation curable resin include electron beam curable resins and ultraviolet curable resins, and ultraviolet curable resins are preferred from the viewpoint of stabilizing the formation of wrinkles by the wrinkle formation stabilizer and improving the visibility and texture of the matte effect. Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins.

[0061] As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferred, and among them, a polyfunctional (meth)acrylate monomer is preferred. Here, "(meth)acrylate" means "acrylate or methacrylate." Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group. The (meth)acrylate monomer is not particularly limited as long as it has a (meth)acryloyl group, but examples include di(meth)acrylates (functional group number: 2) such as diethylene glycol di(meth)acrylate and propylene glycol di(meth)acrylate; tri(meth)acrylates (functional group number: 3) such as trimethylolpropane tri(meth)acrylate; tetra(meth)acrylates (functional group number: 4) such as trimethylolpropane tetra(meth)acrylate and dipentaerythritol tetra(meth)acrylate; and (meth)acrylates (functional group number: 5 or more) having five or more (meth)acryloyl groups, such as dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0062] From the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, and further from the viewpoint of improving surface properties such as scratch resistance and weather resistance, as well as processing properties, the number of functional groups in the polyfunctional (meth)acrylate monomer is preferably from 2 to 8, more preferably from 2 to 6, even more preferably from 2 to 4, and even more preferably from 2 to 3. These polyfunctional (meth)acrylates may be used alone or in combination of two or more.

[0063] Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least a (meth)acryloyl group as the functional group, such as 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. Other polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain, aminoplast resin (meth)acrylate oligomers obtained by modifying aminoplast resins having many reactive groups in a small molecule, and oligomers having cationically polymerizable functional groups in the molecule, such as novolac epoxy resins, bisphenol epoxy resins, aliphatic vinyl ethers, and aromatic vinyl ethers.

[0064] These polymerizable oligomers may be used alone or in combination of two or more kinds. From the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, and further from the viewpoint of improving surface properties such as scratch resistance and weather resistance, as well as processing properties, 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, with urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers being more preferred, and urethane (meth)acrylate oligomers being even more preferred.

[0065] The number of functional groups of these polymerizable oligomers is preferably 2 or more and 8 or less, from the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, and further from the viewpoint of improving surface properties such as scratch resistance and weather resistance, as well as processing properties, and the upper limit is more preferably 6 or less, even more preferably 4 or less, and even more preferably 3 or less. From the same viewpoint, the weight-average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, and even more preferably 3,500 or more and 6,000 or less. Here, the weight-average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

[0066] In the matte article A, the resin forming the matte layer is preferably a combination of the polymerizable oligomer and polymerizable monomer. In this case, the content of the polymerizable oligomer relative to 100 parts by mass of the total of the polymerizable oligomer and polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, even more preferably 55 parts by mass or more, and even more preferably 60 parts by mass or more, with the upper limit being 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. When the content of the polymerizable oligomer is within the above range, wrinkle formation can be stabilized, and the visibility and texture of the matte effect can be stably improved, and further surface properties such as scratch resistance and weather resistance, as well as processing properties, can be improved.

[0067] (Resin composition) The matte layer is composed of a cured product of a resin composition containing the above-mentioned wrinkle formation stabilizer at a predetermined content, and the resin composition specifically contains the above-mentioned resin and the above-mentioned wrinkle formation stabilizer at a predetermined content. The resin composition used in this embodiment may contain other components in addition to the above-mentioned wrinkle formation stabilizer and resin, depending on the desired performance, etc. The resin composition for forming the matte layer may contain a monofunctional (meth)acrylate, for example, for the purpose of reducing its viscosity, etc. These monofunctional (meth)acrylates may be used alone or in combination of two or more kinds.

[0068] Furthermore, when the resin is an ultraviolet-curable resin that is cured by ultraviolet light, it preferably contains additives such as a photopolymerization initiator, a photopolymerization accelerator, etc. By including these additives, wrinkle formation is promoted and the visibility and texture of the matte effect are improved. The photopolymerization initiator may be one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing rate, and examples thereof include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc.

[0069] Since the matte layer is a layer that can be provided on the outermost surface of the matte article A, it is preferably a weather-resistant layer, and preferably contains various weather-resistant agents such as an ultraviolet absorber and a light stabilizer. The ultraviolet absorber can be any ultraviolet absorber commonly used in decorative sheets, without any particular limitations, including, for example, benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, and hydroxyphenyltriazine-based ultraviolet absorbers. The light stabilizer can also be any ultraviolet absorber commonly used in decorative sheets, without any particular limitations, including, for example, hindered amine-based light stabilizers such as piperidinyl sebacate-based light stabilizers. These ultraviolet absorbers and light stabilizers may also have a reactive functional group with an ethylenic double bond in the molecule, such as a (meth)acryloyl group, a vinyl group, or an allyl group. These weathering agents such as ultraviolet absorbers and light stabilizers may be used alone or in combination of two or more kinds.

[0070] [60° gloss value] Matte Article A is an article that has excellent matte effect visibility and texture, and has a 60° gloss value of 5.0 or less. In this specification, "matte" means that the gloss is difficult to visually recognize, and although it cannot be generalized because it varies depending on the color tone, pattern, etc. of the article, for example, an article with a 60° gloss value of 5.0 or less will be considered "matte." Until now, for example, black and other dark colors ("dark colors" means colors with low brightness, for example, CIE (International Commission on Illumination) L * a * b * L in color space * value (hereinafter simply referred to as "L *This is sometimes referred to as the "60° gloss value." ) usually means that the 60° gloss value is about 40 or less, preferably 30 or less. For matte articles exhibiting a 60° gloss value of 20.0 or less, preferably 10.0 or less, even when a matting agent is used, it is possible to achieve excellent visibility of the matte effect. However, the use of a large amount of matting agent results in streaks and unevenness during layer formation, making the product difficult to manufacture and resulting in poor surface properties. Furthermore, for matte articles exhibiting colors other than black or other dark colors, even when a matting agent is used, there is a lower limit to the 60° gloss value, similar to that of matte articles exhibiting black. In either case, it has not been easy to obtain products with excellent surface properties and excellent visibility of the matte effect. This tendency becomes more pronounced as the 60° gloss value becomes smaller.

[0071] In Matte Article A, the use of a wrinkle formation stabilizer and the small amount of the wrinkle formation stabilizer as described above stabilized wrinkle formation, resulting in the stable provision of excellent visibility and texture with a matte effect. Furthermore, by keeping the amount of wrinkle formation stabilizer used to an extremely small amount, a significant increase in viscosity of the resin composition was suppressed, making it possible to form a layer, and minimizing the effect of the particles used in the wrinkle formation stabilizer on the deterioration of surface properties. Therefore, the matte layer naturally has excellent surface properties such as scratch resistance, contamination resistance, and weather resistance, which are in accordance with the properties of the resin used in the matte layer.

[0072] As mentioned above, the 60° gloss value of the matte layer side of matte article A varies depending on the color tone, but it can exhibit extremely excellent visibility of the matte effect, with the matte layer side having a 60° gloss value of 5.0 or less, or even 4.0 or less, 3.6 or less, or 2.0 or less. Furthermore, matte articles exhibiting colors other than black or other dark colors can also have the above-mentioned 60° gloss value. The 60° gloss value of the matte layer side of matte article A is substantially the same as the 60° gloss value of the surface of the layer forming the outermost surface of the article. Furthermore, if another layer is further provided on the surface side of the matte layer, the 60° gloss value will mean the 60° gloss value of that other layer, but the reason that matte article A has a specific 60° gloss value is essentially due to the configuration of the matte layer. In this specification, the 60° gloss value on the matte layer side refers to the 60° specular gloss measured in accordance with JIS K 5600-4-7:1999, and is the average value of values ​​that can be measured from the matte layer side at any 10 locations using a gloss meter or the like.

[0073] Furthermore, the standard deviation (σ) of the 60° gloss values ​​of matte article A is preferably less than 0.30. The standard deviation (σ) of the 60° gloss values ​​is a numerical value that indicates the degree of variation in the 60° gloss values ​​at any 10 points, and the smaller the standard deviation (σ), the less variation there is, i.e., the more stable the wrinkle formation is. As shown in the examples described later, the standard deviation (σ) of the 60° gloss values ​​of matte article A is all less than 0.30, and the stable wrinkle formation and small standard deviation (σ) lead to excellent surface properties, particularly excellent scratch resistance, and excellent visibility and texture of the matte effect.

[0074] From the viewpoint of improving the surface properties and the visibility and texture of the matte effect, the standard deviation (σ) of the 60° gloss value is preferably 2.8 or less, more preferably 2.5 or less, and even more preferably 2.3 or less. There is no particular restriction on the lower limit, as the smaller the better, but since it is difficult to completely converge the standard deviation (σ) of the 60° gloss value of the matte layer surface to 0 and there is not much need to do so, the lower limit of the standard deviation (σ) of the 60° gloss value is usually set to 0.05 or more.

[0075] [Layer structure] As described above, the matte article A need only have a specific matte layer and does not need to have a substrate. That is, the matte article A may have a substrate as desired, and may also have a layer structure without a substrate. Therefore, the simplest layer structure of the matte article A is a layer structure consisting of a single matte layer only, without a substrate. Specifically, the matte article A is composed of a cured resin composition containing 0.5 to 6.0 parts by mass of a wrinkle formation stabilizer per 100 parts by mass of resin, at least one surface of the matte layer having an irregular shape formed by irregular wrinkles, and the 60° gloss value of the matte layer is 5.0 or less.

[0076] (More realistic layer structure) However, when the matte article A has a layer structure of the above single layer, options for obtaining various properties required of a matte article, such as mechanical strength, suitability for post-processing, and designability, are often limited. Therefore, the layer structure of the matte article A preferably has a substrate, i.e., a layer structure having a substrate and a matte layer. In this case, as shown in Figure 3, it is preferable that the matte article A has a substrate and a matte layer, and the surface having an irregular texture formed by irregular wrinkles of the matte layer is the surface opposite the substrate. This is because the visibility and texture of the matte effect can be improved.

[0077] [Base material] In addition to the matte layer, the matte article A may further include a substrate as desired, and as described above, it is preferable to include a substrate in order to avoid various restrictions. The substrate functions as a support on which the matte layer is provided. The form (or shape) of the substrate is not particularly limited and may be various shapes such as a film, sheet, plate, polyhedron, polygonal prism, cylinder, cone, sphere, spheroid, etc. Although films, sheets, and plates are referred to as films, sheets, and plates in the order of their relative thickness, there is no significance in strictly distinguishing between these three types in this specification, and differences between these three types do not cause differences in interpretation of the rights of the present invention.

[0078] The substrate used in this embodiment can be any substrate that is normally used as a substrate for articles such as decorative materials and decorative sheets, and representative examples include substrates made of fibrous materials such as paper, nonwoven fabric and woven fabric, resin, wood-based materials, metals, non-metallic inorganic materials, etc. The substrate may be a single layer, or may be a laminate of two or more layers made of the above materials. When the substrate is a laminate of two or more layers, it is preferable that two or more layers of different materials are laminated so that the properties of the materials in each layer complement each other. Examples of substrates made of two or more layers are A to J below. Note that " / " indicates the interface between each layer. (A) Resin / wood material (B) Resin / metal (C) Resin / fibrous materials (D) Resin / nonmetal inorganic material (E) Resin 1 / Resin 2 (F) Metal / wood materials (G) Metal / non-metallic inorganic materials (H) Metal / fibrous materials (I) Metal 1 / Metal 2 (J) Non-metallic inorganic materials / fibrous materials In the above E, resin 1 and resin 2 represent different types of resins (for example, resin 1 is an olefin resin and resin 2 is an acrylic resin). Also, in the above H, metal 1 and metal 2 represent different types of metals (for example, metal 1 is copper and metal 2 is chromium).

[0079] Furthermore, when the substrate is a laminate, the laminate may be configured such that an adhesive layer, a pressure-sensitive adhesive layer, or a primer layer (also referred to as an anchor layer or an easy-adhesion layer) is further provided between each constituent layer of the laminate as a layer for strengthening the adhesive strength between adjacent layers.

[0080] Examples of fibrous substrates include paper substrates such as kraft paper, titanium paper, linter paper, parchment paper, paraffin paper, glassine paper, parchment paper, wallpaper backing paper, tissue paper, wood-free paper, Japanese paper, paperboard, and plasterboard base paper. Furthermore, the paper substrate may further contain various resins, such as acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin, to improve interfiber strength or interlayer strength with other paper substrates and to prevent fluffing (fuzzing). Examples of such paper substrates include inter-paper reinforced paper and resin-impregnated paper. Examples of substrates in which a resin layer is laminated to a fibrous material layer include wallpaper rolls, which are commonly used in the building materials field and in which various resin layers, such as vinyl chloride resin, olefin resin, and acrylic resin, are laminated to the surface of wallpaper backing paper.

[0081] Examples of substrates for nonwoven or woven fabrics include inorganic fibers made of inorganic materials such as glass, alumina, silica, and carbon; organic fibers made of various synthetic resins such as polyester resin, acrylic resin, polyethylene, and polypropylene; protein-based or cellulose-based natural fibers such as silk, cotton, and hemp; nonwoven or woven fabrics made of various fibers such as glass fiber and carbon fiber; and composites of these.

[0082] Examples of the resin substrate include substrates made of various resins such as synthetic resins, natural resins, etc. As the synthetic resin, thermoplastic resins and curable resins can be used. Examples of thermoplastic resins include polyolefin resins such as polypropylene, polyethylene, polymethylpentene, polyolefin-based thermoplastic elastomers, and ionomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymers, and polyester-based thermoplastic elastomers; acrylic resins such as polymethyl (meth)acrylate, polybutyl (meth)acrylate, and methyl (meth)acrylate-butyl (meth)acrylate copolymers; polyamide resins such as nylon 6 and nylon 66; cellulose-based resins such as cellulose triacetate, cellophane, and celluloid; styrene-based resins such as polystyrene, acrylonitrile-styrene copolymers, and acrylonitrile-butadiene-styrene resins (ABS resins); and resin substrates made of thermoplastic resins such as polyvinyl alcohol, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polycarbonate resins, polyarylate resins, and polyimide resins. Examples of the curable resin include the ionizing radiation curable resin capable of forming the matte layer described above, and other thermosetting resins. Examples of natural resins include natural rubber, pine resin, and amber.

[0083] Examples of wood-based substrates include wood substrates made from various types of wood, such as cedar, cypress, pine, zelkova, oak, walnut, lauan, teak, rubber tree, etc. The wood substrates can be in the form of a film or sheet called veneer, or in the form of a board, such as a single board, plywood, laminated wood, particle board, or fiberboard.

[0084] Examples of metals include aluminum or aluminum-containing alloys such as duralumin, iron or iron-containing alloys such as carbon steel and stainless steel, copper or copper-containing alloys such as brass and bronze, gold, silver, chromium, nickel, cobalt, tin, titanium, etc. Furthermore, as the metal substrate made of a metal, those which have been subjected to a treatment such as plating of these metals can also be used. Non-metallic inorganic materials include non-ceramic ceramic materials such as cement, ALC (lightweight aerated concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as porcelain, earthenware, glass, and enamel; and natural stones such as limestone (including marble), granite, and andesite.

[0085] The substrate may be colored or uncolored (it may be transparent), and if it is colored, there are no particular restrictions on the coloring mode, and it may be transparently colored or opaquely colored (hiding colored), which can be selected as desired.

[0086] When the substrate is colored, examples of colorants include inorganic pigments such as white pigments such as titanium white, iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; organic pigments or dyes such as quinacridone red, isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethine azo-based black pigments, and perylene-based black pigments; metal pigments consisting of scaly foil flakes such as aluminum and brass; and pearlescent pigments consisting of scaly foil flakes such as titanium dioxide-coated mica and basic lead carbonate. For example, when the surface hue of the adherend to which the article is attached varies, an inorganic pigment such as a white pigment can be used to conceal the surface hue and improve the color stability of the picture layer and the large-area decorative layer provided as desired.

[0087] In the case of coloring synthetic resins, any of the following methods can be used: adding a colorant to the resin (mixing or kneading), applying a coating film of a paint containing the resin and the colorant, etc. In the case of coloring paper, nonwoven fabric, or woven fabric, any of the following methods can be used: mixing with pulp or fiber materials, or forming a coating film, or a combination of these. In the case of coloring wood, it can be done by dyeing with a dye or by forming a coating film, or by a combination of these. In the case of coloring metals, in addition to forming a coating film, electrolytic coloring methods that form a metal oxide film on the surface using anodization can be used. In addition, in the case of non-metallic inorganic materials, it can be done by forming a coating film or by adding a dye to the substrate, or by a combination of these.

[0088] The substrate may contain additives as needed. Examples of additives, mainly in the case of resins, include inorganic substances such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. The amount of additives added is not particularly limited as long as it does not impair surface properties, processing properties, and the like, and can be appropriately set depending on the required properties, etc.

[0089] From the viewpoint of improving the weather resistance of the matte article of this embodiment, it is preferable to use weather resistance agents such as ultraviolet absorbers and light stabilizers among the above additives. Examples of the ultraviolet absorber and light stabilizer include those exemplified above as those that can be contained in the matte layer. These ultraviolet absorbers, weathering agents such as light stabilizers, and other various additives may be used alone or in combination of two or more kinds.

[0090] The shape and dimensions of the substrate are not particularly limited and may be appropriately selected depending on the application, desired performance, and processability. When the substrate is in the form of a film, sheet, or plate, the thickness is a typical dimension in the design of the article. There are no particular restrictions on the thickness, but it is generally sufficient to set it to about 10 μm or more and 10 cm or less from the viewpoints of manufacturing processability, mechanical strength, ease of use and handling, and economic efficiency. Furthermore, when it is in the form of a film or sheet, the thickness is preferably 20 μm or more, more preferably 40 μm or more, and the upper limit is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less. When the substrate is in the form of a plate, its thickness is preferably 1 mm or more and 2 cm or less. When the base material is paper, the basis weight is usually 20 to 150 g / m 2 is preferable, and 30 to 100 g / m 2 is more preferred.

[0091] In order to enhance adhesion to other layers constituting the article or to an adherend on which the article is laminated, the substrate may be subjected to a surface treatment such as a physical surface treatment such as an oxidation method or a roughening method, or a chemical surface treatment, or a primer layer may be formed on one or both sides thereof. Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, etc. Examples of roughening methods include sandblasting, solvent treatment, etc. These surface treatments are appropriately selected depending on the type of substrate, but corona discharge treatment is generally preferred from the viewpoints of the effect of the surface treatment and operability, etc.

[0092] [Other layers] In addition to the matte layer, the matte article A may have the above-mentioned substrate and further other layers, such as a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. Cross-sectional views showing an embodiment of the matte article A having these layers are shown in Figures 3 and 4. Figures 3 and 4 are cross-sectional views showing an embodiment of the matte article A, taken along a plane parallel to the thickness direction of the matte article 1 (matte article A) (the Z direction in the figures). The matte article 1 (matte article A) shown in Figure 3 has a substrate 5 and a matte layer 4 in this order, and the matte article 1 (matte article A) shown in Figure 4 has a substrate 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a matte layer 4 in this order.

[0093] (Primer layer) When the matte article A is composed of, for example, a plurality of layers, it may have a primer layer in order to improve the interlayer adhesion between the plurality of layers as described above. When the matte article A has a layer other than the matte layer, for example, when it has a matte layer and a substrate, a primer layer can be provided between the matte layer and the substrate to improve interlayer adhesion.

[0094] The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.

[0095] Preferred examples of binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate-based urethane-acrylic copolymers (urethane-acrylic copolymers derived from polymers (polycarbonate polyols) having carbonate bonds in the polymer main chain and two or more hydroxyl groups at the terminals and side chains), vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins, and these can be used alone or in combination. The binder resin may be a resin obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to the resin and crosslinking and curing it. Among these, a polyol-based resin such as an acrylic polyol resin is preferred, and an acrylic polyol resin is more preferred, being crosslinked and cured with an isocyanate-based curing agent.

[0096] The thickness of the primer layer is preferably 0.5 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.

[0097] In order to improve adhesion to the adherend, the matte article A may also have a primer layer (also referred to as a "rear primer layer") on the side opposite to the wrinkled surface of at least one of the matte layers, or, if the matte article A has a substrate, on the side opposite to the side on which the matte layer is provided of the substrate.

[0098] (Transparent resin layer) The matte article A may have a transparent resin layer to increase its strength and, if a decorative layer is provided, to protect the decorative layer, etc. This is particularly effective when the matte article A is used as a flooring material or as frequently used fittings such as window frames, doors, door frames, and handrails. The transparent resin layer may be provided between the substrate and the matte layer, and when a decorative layer is provided, the transparent resin layer may be provided between the decorative layer and the matte layer to protect the decorative layer.

[0099] 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, vinyl chloride resins, etc. Among these, polyolefin resins and vinyl chloride resins are preferred from the viewpoint of processability, etc. Furthermore, two or more of these various resins may be laminated or mixed and used.

[0100] The transparent resin layer may be transparent enough to allow the substrate side to be visible from the transparent resin layer, and if a decorative layer is provided, may be transparent enough to allow the decorative layer to be visible, and may be colorless and transparent, colored and transparent, or translucent. That is, in this specification, "transparent" means not only colorless and transparent, but also colored and transparent and translucent.

[0101] The transparent resin layer may contain additives such as weatherproofing agents such as ultraviolet absorbers and light stabilizers, and colorants, etc. As these additives such as weatherproofing agents and colorants, those already described may be used. From the viewpoint of protecting the decorative layer and taking into consideration processability, the thickness of the transparent resin layer is preferably 20 μm to 150 μm, more preferably 40 μm to 120 μm, and even more preferably 60 μm to 100 μm.

[0102] (decorative layer) The matte article A may have a decorative layer to improve its design. The decorative layer may be provided on the surface opposite to at least one wrinkled surface of the matte layer, and may be provided between the substrate and the matte layer when a substrate is included, or in the order of the decorative layer, transparent resin layer, and matte layer when a transparent resin layer is included.

[0103] The decorative layer may be, for example, a colored layer that covers the entire surface (a so-called solid colored layer, "6a" in Fig. 4), or a patterned layer formed by printing various patterns using ink and a printing machine ("6b" in Fig. 4). Also, as shown in Fig. 4, it may be a combination of a solid colored layer and a patterned layer.

[0104] The design (pattern) of the design layer is not particularly limited and may be any desired design, such as wood grain patterns such as tree rings and vessel grooves on the surface of a wooden board, stone grain patterns on the surface of stone slabs such as marble and granite, fabric grain patterns on the surface of fabric, leather grain patterns on the surface of leather, geometric patterns, letters, figures, and combinations of these.

[0105] The ink used for the decorative layer is a mixture of a binder resin with an appropriate amount of pigment, colorant such as dye, extender pigment, solvent, stabilizer, plasticizer, catalyst, hardener, ultraviolet absorber, light stabilizer, etc. The binder resin for the decorative layer is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins containing a curing agent such as an isocyanate compound.

[0106] As the colorant, a pigment having excellent hiding power and weather resistance is preferred. The pigment may be the same as those exemplified as the pigments that can be used for the substrate. The content of the colorant is preferably 5 to 90 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 30 to 70 parts by mass, per 100 parts by mass of the resin constituting the decorative layer.

[0107] The decorative layer may contain additives such as ultraviolet absorbers, weather resistance agents such as light stabilizers, and colorants. The thickness of the decorative layer may be selected appropriately depending on the desired pattern, but from the viewpoint of concealing the base color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0108] (adhesive layer) When the matte article A has a transparent resin layer, an adhesive layer may be provided between the substrate and the transparent resin layer to improve adhesion between the two layers. When a decorative layer is further present between the substrate and the transparent resin layer, the positional relationship between the adhesive layer and the decorative layer is not particularly limited, and specifically, the decorative layer, adhesive layer, and transparent resin layer may be present in this order from the side closest to the substrate, or the adhesive layer, decorative layer, and transparent resin layer may be present in this order from the side closest to the substrate.

[0109] The adhesive layer can be made of, for example, an adhesive such as a urethane adhesive, an acrylic adhesive, an epoxy adhesive, a rubber adhesive, etc. Among these adhesives, a urethane adhesive is preferred in terms of adhesive strength. Examples of urethane adhesives include adhesives that utilize two-component curing urethane resins containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol, and a curing agent such as an isocyanate compound.

[0110] From the viewpoint of efficiently obtaining a desired adhesive strength, the thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[0111] (Performance of Matte Article A) Matte Article A has excellent surface properties, particularly excellent scratch resistance. For example, when the 60° gloss value of the matte layer side before the rubbing test described below is defined as G0 and the 60° gloss value of the matte layer side after the rubbing test is defined as G1, the change in gloss value (|(G1-G0)| / G0×100) is 20% or less, demonstrating excellent scratch resistance (particularly steel wool resistance). (Rubbing test) A matte article was placed on the base of an abrasion tester, Type II (JIS L0849:2013), and steel wool #0000 was set so that it was in contact with the matte layer of the matte article. A load of 1500 g / cm was applied. 2 The sample was moved back and forth 30 times at a moving speed of 100 mm / sec and a moving distance of 100 mm.

[0112] The rate of change in gloss value is an index of steel wool resistance, which is one of the scratch resistance properties of a matte article, and is determined by observing the range of change in gloss value before and after the rubbing test. A larger rate of change in gloss value indicates a higher gloss value after the rubbing test, i.e., poorer steel wool resistance because the surface of the matte article becomes glossy due to small scratches. Since matte article A has excellent scratch resistance, the rate of change in gloss value is 20% or less as described above, and can further be 15% or less, 10% or less, 8% or less, or 5% or less.

[0113] [Method for producing matte article A] As described above, the matte article A may have a layer structure consisting of a single matte layer or a layer structure including at least a substrate. Hereinafter, the manufacturing method of the matte article A will be described separately for the case of a single layer and the case of having a substrate and other layers.

[0114] First, in the case of a single layer, the matte article A can be produced by the following method. The matte layer is preferably produced by a process comprising the steps of: applying the above-mentioned matte layer-forming resin composition, i.e., a resin composition containing wrinkle formation stabilizer 1 having an average particle size of 1 μm or more and the smaller of 100% or less of the thickness of the matte layer or 30 μm or less, and wrinkle formation stabilizer 2 having an average particle size less than 1 μm, in a total amount of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin, to the release layer-bearing surface of the release support; and irradiating the resin composition with light having a wavelength of at least 100 nm but less than 200 nm to cure the resin composition and form a matte layer. If the resin composition contains a solvent, a solvent drying process may be performed after the coating layer-forming process. The releasable support having the release layer may be peeled off when the matte article A is to be used.

[0115] Next, when the substrate and other layers are present, the matte article A can be produced by the following method. The matte article A is preferably produced, for example, through a process of forming a matte layer by applying a resin composition for forming a matte layer, the resin composition containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin, to one main surface of a substrate (preferably a substrate sheet), and a matte layer-forming process of curing the coating layer by irradiating the coating layer with light having a wavelength of at least 100 nm but less than 200 nm to form a matte layer. If the resin composition contains a solvent, a solvent drying process may be performed after the coating layer-forming process.

[0116] The above-mentioned method for producing matte article A can be particularly suitable for producing a matte article A having a 60° gloss value of 5.0 or less on the matte layer side. In particular, the method for producing matte article A is distinct from conventional methods for producing matte articles such as matte decorative materials and matte decorative sheets in that it can achieve a matte (low gloss, low luster) surface having a 60° gloss value of 5.0 or less by suppressing the amount of μm-order particles added to a low content of 6.0 parts by mass or less per 100 parts by mass of resin. This production method makes it possible to easily obtain the matte article A. Specifically, in forming the matte layer, a resin composition for forming the matte layer, which contains a wrinkle formation stabilizer, is irradiated with ultraviolet light having a short wavelength (short wavelength) of at least 100 nm or more and less than 200 nm, thereby forming wrinkles on at least one surface of the matte layer, making it easier to stably impart the visibility and texture of the matte effect to the matte article (matte layer).

[0117] Although the details of the mechanism by which wrinkles form on at least one surface of the matte layer when the resin composition for forming the matte layer is irradiated with such low-wavelength ultraviolet light, thereby expressing the visibility and texture of the matte effect, are unknown, it is presumed to be due to the following mechanism.

[0118] When a matte layer-forming resin composition is applied to a predetermined thickness and irradiated with short-wavelength ultraviolet light, the energy of the ultraviolet light penetrates only the surface portion and does not reach the layers below, so that only the surface portion of the resin composition begins to harden, and as a result, only the surface undergoes cure shrinkage, resulting in the formation of wrinkles. In this way, it is thought that wrinkles are formed when the matte layer-forming resin composition is cured only in a certain thickness direction from the surface due to irradiation with short-wavelength ultraviolet light. Furthermore, a comparison between the Examples and Comparative Examples described below shows that when the wrinkle formation stabilizer is not included, wrinkle formation becomes unstable, and the visibility of the matte effect is not stably and sufficiently achieved across the entire matte layer. Therefore, the stable development of the visibility of the matte effect cannot be explained by curing only the surface portion with low-wavelength ultraviolet light. In other words, in order for the matte article A to stably form wrinkles and thereby achieve the visibility of the matte effect, it is essential that the wrinkle formation stabilizer is included. Considering that the stable visibility of the matte effect due to the stabilization of wrinkle formation is not achieved when the wrinkle formation stabilizer is not included, it is believed that the wrinkle formation stabilizer functions like a nucleus that triggers wrinkle formation, and the resin in the surface portion of the resin composition gathers around the nucleus, forming convex wrinkles (protrusions), and as the convex wrinkles (protrusions) are formed, concave wrinkles are also formed, resulting in stable wrinkle formation. The wrinkles formed in this manner are thought to stably impart the visibility of the matte effect to the matte article A due to the light diffusion effect resulting from their shape, and also stably impart texture.

[0119] The wrinkle formation stabilizer and the resin composition for forming a matte layer containing the wrinkle formation stabilizer used in this manufacturing method are the same as those described above as the wrinkle formation stabilizer and the resin composition for forming a matte layer that can be used in Matte Article A.

[0120] In this manufacturing method, it is preferable to irradiate the resin composition for forming the matte layer with light having a wavelength of at least 100 nm but less than 200 nm. This irradiation allows the energy of the ultraviolet light to penetrate only the surface portion, preventing the energy from reaching the layers below. Therefore, only the surface portion of the resin composition begins to harden. This causes curing shrinkage only at the surface, stabilizing wrinkle formation. The surface layer of the resin composition becomes a wrinkled cured product, forming a matte layer. Then, curing progresses from the surface-prone portion, where curing proceeds slowly, to deeper portions further away in the depth direction, forming a cured resin composition layer. Thus, the resin composition hardens throughout its entire thickness, forming a matte layer with wrinkles that exhibit a light-diffusing effect on the surface. From the viewpoint of promoting the progress of curing into the deeper portions, it is preferable to perform another irradiation treatment after irradiation with light having a wavelength of at least 100 nm but less than 200 nm, as described below.

[0121] Examples of light with a wavelength of at least 100 nm but less than 200 nm include "excimer light," which includes light in the ultraviolet wavelength range from excited dimers, i.e., excimers, formed by discharge of rare gases such as Ar, Kr, Xe, and Ne, halides of rare gases such as halogens F, Cl, I, and Br, or mixtures of these gases. Examples of wavelengths and excimer sources of excimer light include light with a wavelength of 126 nm radiated from the excimer of Ar2 (hereinafter abbreviated as "126 nm (Ar2)"), 146 nm (Kr2), 157 nm (F2), 172 nm (Xe2), and 193 nm (ArF). While spontaneous emission and highly coherent laser light generated by stimulated emission can both be used as excimer light, spontaneous emission is usually sufficient. Discharge lamps that emit such light (ultraviolet light) are also called "excimer lamps." Excimer light has a single wavelength peak and is characterized by a narrower half-width wavelength than ordinary ultraviolet light (e.g., ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). The use of such excimer light stabilizes wrinkle formation and stably improves the visibility and texture of the matte effect.

[0122] From the viewpoint of stabilizing wrinkle formation and stably improving the visibility and texture of the matte effect, 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, with the upper limit being less than 200 nm, and particularly preferably 172 nm (Xe2). Thus, in this production method, from the viewpoint of stably improving the visibility and texture of the matte effect, it is preferable to use light with a shorter wavelength, and it can be said that, among low-wavelength ultraviolet rays (wavelength: 280 nm or less), low-wavelength ultraviolet rays in the region of less than 200 nm are preferred.

[0123] In this production method, the integrated light amount of the light of the above wavelength is preferably 1 mJ / cm from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect. 2 More preferably, 10 mJ / cm 2 More preferably, 30 mJ / cm 2 More preferably, 50 mJ / cm 2 There is no particular upper limit, but from the viewpoint of productivity, such as reducing the number of lamps required for irradiation of wavelength light and improving production efficiency, the upper limit is preferably 1,000 mJ / cm. 2 Less than or equal to 500 mJ / cm 2 or less, more preferably 300 mJ / cm 2 The following is the result. From the same viewpoint, the ultraviolet light output density is preferably 0.01 W / cm or more, more preferably 0.1 W / cm or more, and even more preferably 0.5 W / cm or more, with the upper limit being preferably 10 W / cm or less, more preferably 5 W / cm or less, and even more preferably 3 W / cm or less. Furthermore, the oxygen concentration during irradiation with light of the above wavelengths 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.

[0124] In the matte layer forming step of the present production method, in addition to the irradiation with light having a wavelength of at least 100 nm and less than 200 nm, other treatments that contribute to curing of the resin composition for forming the matte layer may be carried out. For example, to stabilize the formation of wrinkles due to the difference in the degree of curing between the surface portion and the deep portion away from the surface in the depth direction and to promote the curing progress to the deep portion, the resin composition for forming the matte layer may be pre-cured overall by pre-irradiation with light having a wavelength of 200 nm or more, for example, light having a wavelength of 380 nm or more, preferably light having a wavelength of 385 nm or more and 400 nm or less, and then irradiated with light having a wavelength of 100 nm or more and less than 200 nm. Alternatively, after irradiation with light having a wavelength of 100 nm or more and less than 200 nm, post-curing may be performed to further cure the resin composition. The necessity of pre-curing and post-curing can be determined appropriately depending on the desired properties required of the matte layer (e.g., surface properties such as scratch resistance and contamination resistance, and processing properties). Furthermore, although the above-mentioned wavelength light belongs to the ultraviolet ray family, other ionizing radiations, such as electron beams, can also be used. For example, electron beams are preferably used in post-curing to improve the surface properties of the matte layer.

[0125] In this manufacturing method, the matte layer can be formed by applying a resin composition for forming the matte layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating, to a coating layer (uncured resin layer), and irradiating the coating layer with light having a wavelength of at least 100 nm and less than 200 nm.

[0126] Furthermore, the matte article obtained by this production method may have other layers such as a transparent resin layer in addition to the substrate described above as a layer that can be used in the matte article A. For example, the decorative layer, adhesive layer, and primer layer can be formed by applying a coating liquid containing a composition for forming each layer by the above-mentioned known method, and drying and curing it as necessary. When a transparent resin layer is formed, a resin film for forming the transparent resin layer can be formed by dry lamination or the like.

[0127] [Decorative material A] Typical uses of the matte article A include using the matte article A as it is, as a decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or laminating, compounding, or combining with an adherend to be used as a decorative material (hereinafter, such decorative materials using the matte article A may be referred to as "decorative material A"). The choice of which to use can be determined as desired. When an adherend is included, the decorative member A comprises the adherend and the above-mentioned matte article A, specifically, laminated such that the surface of the adherend requiring decoration faces the surface of the matte article A opposite to the surface on which wrinkles are formed in the matte layer to provide the visibility and texture of the matte effect. When the matte article A is in the form of a sheet, it also has the characteristic of being easily laminated on the adherend.

[0128] (adherent material) The adherend may be a member made of a material appropriately selected from the materials exemplified above as materials that can be used as the substrate. The adherend may be selected appropriately from the above depending on the application. When the application is for interior components of buildings such as walls, ceilings, floors, etc., or exterior components such as exterior walls, roofs, eaves ceilings, fences, gates, etc., or fittings or fixtures such as window frames, doors, handrails, baseboards, moldings, etc., it is preferable to use at least one member selected from wood members made of wood-based materials, metal members made of metal, and resin members made of resin. When the application is for exterior components such as entrance doors, or fittings such as window frames and doors, it is preferable to use at least one member selected from metal members and resin members.

[0129] The thickness of the adherend may be appropriately selected depending on the application and material, and is preferably 0.1 mm to 100 mm, more preferably 0.3 mm to 5 mm, and even more preferably 0.5 mm to 3 mm.

[0130] (adhesive layer) In order to obtain excellent adhesion, the adherend and the matte article A are preferably attached via an adhesive layer.

[0131] The adhesive used in the adhesive layer is not particularly limited, and any known adhesive can be used, and may be appropriately selected depending on the application. Preferred examples include moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives.

[0132] Resins used in these adhesives include, for example, 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, which can be used alone or in combination. Two-component curing urethane adhesives and ester adhesives that use an isocyanate compound or the like as a curing agent can also be used. The adhesive layer may also contain a pressure-sensitive adhesive, which may be appropriately selected from various pressure-sensitive adhesives such as acrylic, urethane, silicone, and rubber-based pressure-sensitive adhesives.

[0133] The thickness of the adhesive layer is not particularly limited, but from the viewpoint of obtaining excellent adhesiveness, it is preferably from 1 μm to 100 μm, more preferably from 5 μm to 50 μm, and even more preferably from 10 μm to 30 μm.

[0134] (Manufacturing method of decorative material A) The decorative member A can be produced through a step of laminating the matte article A and the adherend. This step is a step of laminating an adherend and a matte article A, in which the surface of the adherend that requires decoration is opposed to the surface of the matte article A opposite to the surface on which wrinkles are formed in the matte layer to provide the visibility and texture of the matte effect, or, if the matte article A has a substrate, to the surface facing the substrate. Examples of methods for laminating the adherend and the matte article A include a lamination method in which the matte article A is pressed onto the plate-shaped adherend with a pressure roller via an adhesive layer.

[0135] When a hot melt adhesive (heat-sensitive adhesive) is used as the adhesive, the heating temperature is preferably 160°C or higher and 200°C or lower, although this depends on the type of resin that makes up the adhesive, and for reactive hot melt adhesives, the heating temperature is preferably 100°C or higher and 130°C or lower. Vacuum forming is generally performed while heating, and the temperature is preferably 80°C or higher and 130°C or lower, and more preferably 90°C or higher and 120°C or lower.

[0136] (Use of decorative material A) The decorative member A obtained as described above can be cut as desired and the surface or end grain can be decorated with grooves, chamfers, etc. using a cutting machine such as a router or cutter. It is suitable for a variety of uses, including interior building components such as walls, ceilings, and floors; exterior building components such as exterior walls, eaves ceilings, roofs, fences, and fences; fixtures and fittings such as window frames, doors, door frames, handrails, baseboards, moldings, and other fittings; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; various furniture and components used in wet areas such as kitchens, toilets, bathrooms, and washbasins; surface decorative panels for cabinets and other appliances and office equipment; and interior and exterior components for vehicles. When in sheet form, the matte article A is suitable for use as a decorative sheet for the various components listed above. Furthermore, in consideration of the characteristics of Matte Article A, such as excellent surface properties, particularly scratch resistance, and excellent visibility and texture of the matte effect, the matte article A is suitable for use in applications where scratch resistance is particularly required, such as flooring materials among interior building materials, and frequently used building materials such as window frames, doors, door frames, and handrails. Furthermore, in addition to the various components described above, the matte article A can be used alone or in a laminated or composite form with other materials as packaging materials, antiglare films for displays, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, and various certificates, keys of various keyboards, transparent panels (window glass, etc.) for windows, doors, partitions, etc., artificial leather, etc.

[0137] [Matte article B] Among the matte articles A of this embodiment, those employing two types of wrinkle stabilizers are particularly preferred, i.e., matte articles having a matte layer, the matte layer being composed of a cured resin composition containing wrinkle stabilizer 1 having 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 or 30 μm or less, and wrinkle stabilizer 2 having an average particle size less than 1 μm, the total amount of wrinkle stabilizer 1 and wrinkle stabilizer 2 being 0.5 parts by mass or more to 6.0 parts by mass or less per 100 parts by mass of resin, at least one surface of the matte layer having an irregular shape formed by irregular wrinkles, and the 60° gloss value of the matte layer being 5.0 or less (hereinafter simply referred to as "matte article B"). With this configuration, matte article B has excellent visibility of the matte effect and texture.

[0138] [Matte layer] The matte layer in matte article B is a layer constituted by a cured product of a resin composition containing wrinkle formation stabilizer 1 having 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 or 30 μm or less, and wrinkle formation stabilizer 2 having an average particle size of less than 1 μm, the total amount of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 being 0.5 to 6.0 parts by mass per 100 parts by mass of resin. That is, in this embodiment, the matte layer is a layer containing wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 in amounts of 0.5 to 6.0 parts by mass per 100 parts by mass of the resin that forms the matte layer.

[0139] (Wrinkle formation stabilizer) As the wrinkle formation stabilizer, wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, which were explained as being employed in the above-mentioned matte article A, are employed. Regarding the wrinkle formation stabilizer, the average particle size, type, content, etc. of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, the effects achieved by using the wrinkle formation stabilizer, and the differences between the wrinkle formation stabilizer and the matting agent are the same as those explained for Matte Article A above.

[0140] (Matte layer surface shape) The surface shape of the matte layer of matte article B must have irregularities formed by irregular wrinkles on at least one surface, and is the same as that described above for matte article A. 1 and 2, which are used to explain the surface shape of the matte layer of matte article A, can also be applied to the surface shape of the matte layer of matte article B.

[0141] (resin) The resin used to form the matte layer of the matte article B is the same as that described for the matte article A above.

[0142] (Resin composition) The resin composition used to form the matte layer of the matte article B is the same as that described for the matte article A above.

[0143] [60° gloss value] The 60° gloss value of Matte Article B is 5.0 or less, which is the same as the 60° gloss value explained above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same.

[0144] [Layer structure] The layer structures of the matte article B, such as the simplest layer structure and a more realistic layer structure, are the same as those described for the matte article A above.

[0145] [Base material] The substrate of Matte Article B is the same as that described for Matte Article A above.

[0146] [Other layers] In addition to the matte layer, the matte article B may have the above-mentioned substrate and other layers, such as a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. as needed. These other layers are the same as those described above for the matte article A. Therefore, the layer configurations shown in Figures 3 and 4 can also be applied to the matte article B.

[0147] [Method for manufacturing matte article B] The method for producing the matte article B is the same as the method for producing the matte article A described above.

[0148] [Decorative material B] Typical uses of the matte article B include using the matte article B as it is, as a decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or laminating, compounding, or combining with an adherend to be used as a decorative material (hereinafter, such decorative materials using the matte article B may be referred to as "decorative material B"). The choice of which to use can be determined as desired. The form of the matte article B in the decorative member B, the adherend, the adhesive layer, the use of the decorative member B, etc. are the same as those explained for the decorative member A above.

[0149] [Matte article C] Among the matte articles A of this embodiment, those employing a specific type of wrinkle stabilizer, i.e., a matte article having a matte layer, the matte layer being composed of a cured product of a resin composition containing 0.5 to 6.0 parts by mass of wrinkle stabilizer 1, per 100 parts by mass of resin, with an average particle diameter of 1 μm or more and an upper limit of either 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller, and at least one surface of the matte layer having an irregular texture formed by irregular wrinkles, and the 60° gloss value of the matte layer being 5.0 or less (hereinafter simply referred to as "matte article C"). By having such a configuration, matte article C also has excellent visibility of the matte effect and excellent texture.

[0150] [Matte layer] The matte layer in the matte article C is a layer constituted by a cured product of a resin composition containing 0.5 to 6.0 parts by mass of wrinkle stabilizer 1, relative to 100 parts by mass of resin, and having an average particle diameter of 1 μm or more, and an upper limit of either 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. That is, in this embodiment, the matte layer is a layer containing 0.5 to 6.0 parts by mass of wrinkle stabilizer 1, relative to 100 parts by mass of resin that forms the matte layer.

[0151] (Wrinkle formation stabilizer) As the wrinkle formation stabilizer, the wrinkle formation stabilizer 1 described above as being employed in the matte article A is employed. Regarding the wrinkle formation stabilizer, the average particle size, type, content, etc. of the wrinkle formation stabilizer 1, the effects achieved by using the wrinkle formation stabilizer, and the differences between the wrinkle formation stabilizer and the matting agent are the same as those explained for the matte article A above.

[0152] (Matte layer surface shape) The surface shape of the matte layer of Matte Article C must have irregularities on at least one surface formed by irregular wrinkles, and is the same as that described above for Matte Article A. 1 and 2, which are used to explain the surface shape of the matte layer of Matte Article A, can also be applied to the surface shape of the matte layer of Matte Article C.

[0153] (resin) The resin used to form the matte layer of the matte article C is the same as that described for the matte article A above.

[0154] (Resin composition) The resin composition used to form the matte layer of the matte article C is the same as the resin composition described for the matte article A above.

[0155] [60° gloss value] The 60° gloss value of Matte Article C is 5.0 or less, which is the same as the 60° gloss value described above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same.

[0156] [Layer structure] The layer structures of the matte article C, such as the simplest layer structure and a more realistic layer structure, are the same as those described for the matte article A above.

[0157] [Base material] The substrate of Matte Article C is the same as that described for Matte Article A above.

[0158] [Other layers] In addition to the matte layer, the matte article C may have the above-mentioned substrate and other layers, such as a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. as needed. These other layers are the same as those described for the matte article A. Therefore, the layer configurations shown in Figures 3 and 4 can also be applied to the matte article C.

[0159] [Method for producing matte article C] The method for producing the matte article C is the same as the method for producing the matte article A described above.

[0160] [Decorative material C] Typical uses of the matte article C include using the matte article C as it is, as a decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or laminating, compounding, or combining with an adherend to be used as a decorative material (hereinafter, such decorative materials using the matte article C may be referred to as "decorative material C"). The choice of which to use can be determined as desired. The form of the matte article C, the adherend, the adhesive layer, the manufacturing method of the decorative member C, the uses of the decorative member C, etc. in the decorative member C are the same as those explained for the decorative member A above.

[0161] [Matte article D] Among the matte articles A of this embodiment, a matte article that employs a specific type of wrinkle stabilizer, i.e., a matte article having a matte layer, the matte layer being made of a cured resin composition containing 0.5 to 6.0 parts by mass of a wrinkle stabilizer with an average particle size of less than 1 μm per 100 parts by mass of resin, at least one surface of the matte layer having an irregular texture formed by irregular wrinkles, and the 60° gloss value of the matte layer being 5.0 or less (hereinafter simply referred to as "matte article D"). By having such a configuration, matte article D has excellent visibility of the matte effect and excellent texture.

[0162] [Matte layer] The matte layer in Matte Article D is a layer constituted by a cured product of a resin composition containing a wrinkle formation stabilizer having an average particle size of less than 1 μm in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin. That is, in this embodiment, the matte layer is a layer containing the wrinkle formation stabilizer having an average particle size of less than 1 μm in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin forming the matte layer.

[0163] (Wrinkle formation stabilizer) The wrinkle formation stabilizer used is the wrinkle formation stabilizer 2 having an average particle size of less than 1 μm, which was explained as being used in the matte article A above. Regarding the wrinkle formation stabilizer, the average particle size, type, content, etc. of the wrinkle formation stabilizer 2, the effects achieved by using the wrinkle formation stabilizer, and the differences between the wrinkle formation stabilizer and the matting agent are the same as those explained for the matte article A above.

[0164] (Matte layer surface shape) The surface shape of the matte layer of Matte Article D must have irregularities on at least one surface formed by irregular wrinkles, and is the same as that described above for Matte Article A. 1 and 2, which are used to explain the surface shape of the matte layer of Matte Article A, can also be applied to the surface shape of the matte layer of Matte Article D.

[0165] (resin) The resin used to form the matte layer of the matte article D is the same as that described for the matte article A above.

[0166] (Resin composition) The resin composition used to form the matte layer of the matte article D is the same as the resin composition described for the matte article A above.

[0167] [60° gloss value] The 60° gloss value of Matte Article C is 5.0 or less, which is the same as the 60° gloss value described above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same.

[0168] [Layer structure] The layer structures of the matte article D, such as the simplest layer structure and a more realistic layer structure, are the same as those described for the matte article A above.

[0169] [Base material] The substrate of Matte Article D is the same as that described for Matte Article A above.

[0170] [Other layers] In addition to the matte layer, the matte article D may have the above-mentioned substrate and other layers, such as a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. as needed. These other layers are the same as those described for the matte article A. Therefore, the layer configurations shown in Figures 3 and 4 can also be applied to the matte article D.

[0171] [Method for producing matte article D] The method for producing the matte article D is the same as the method for producing the matte article A described above.

[0172] [Decorative material D] Typical uses of the matte article D include using the matte article D as it is, as a decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or laminating, compounding, or combining with an adherend to be used as a decorative material (hereinafter, such decorative materials using the matte article D may be referred to as "decorative material D"). Which use to make can be determined as desired. The form of the matte article D, the adherend, the adhesive layer, the manufacturing method of the decorative member D, the uses of the decorative member D, etc. in the decorative member D are the same as those explained for the decorative member A above.

[0173] [Matte article E] The matte article of this embodiment is a matte article (hereinafter also referred to simply as "matte article E") in which the matte layer of the above-mentioned matte article A is a matte, easy-to-decontaminate layer. Specifically, it is a matte article having a matte layer, the matte layer being composed of a cured product of a resin composition containing 0.5 to 6.0 parts by mass of a wrinkle formation stabilizer per 100 parts by mass of resin, at least one surface of the matte layer having an irregular shape composed of irregular wrinkles, the 60 ° gloss value of the matte layer being 5.0 or less, and the matte layer being a matte, easy-to-decontaminate layer. By having such a configuration, matte article E has excellent surface properties, particularly easy decontamination, and also has excellent visibility and texture of the matte effect.

[0174] [Matte layer (matte, easy-to-decontaminate layer)] The matte layer in the matte article E is a matte, easy-to-decontaminate layer that particularly exhibits easy decontamination properties, and is a layer composed of a cured product of a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass relative to 100 parts by mass of the resin. That is, in this embodiment, the matte layer is a matte, easy-to-decontaminate layer that mainly exhibits easy decontamination properties, and is a layer containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass relative to 100 parts by mass of the resin that forms the matte, easy-to-decontaminate layer.

[0175] (Wrinkle formation stabilizer) The wrinkle formation stabilizer is the same as that used in the above-mentioned matte article A. By using the wrinkle formation stabilizer, the formation of wrinkles on the surface of the matte, easy-to-decontaminate layer is stabilized, and the texture is stably obtained along with visibility due to the matte effect caused by the light diffusion effect at the refractive index difference interface between the surface and air. In addition, as will be described later, having wrinkles provides excellent easy decontamination properties. The fact that at least one of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, the effects achieved by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those explained for matte article A above.

[0176] (Surface shape of matte easy-to-decontaminate layer) The surface shape of the matte, easy-to-decontaminate layer of matte article E must have irregularities on at least one surface formed by irregular wrinkles, and is the same as that described for the matte layer of matte article A. 1 and 2, which are used to explain the surface shape of the matte layer of matte article A, can also be applied to the matte, easy-to-decontaminate layer of matte article E. Having the surface shape of the matte, easy-to-decontaminate layer as described for the matte layer of matte article A improves surface properties, particularly the easy decontamination property, and the visibility and texture of the matte effect.

[0177] Here, the effect obtained by the surface shape of the matte, easy-to-decontaminate layer includes the effect of stably expressing the visibility and texture of the excellent matte effect obtained by the matte layer of matte article A, but the important effect of matte article F is easy decontamination. As described above, the matte, easy-to-decontaminate layer has an uneven shape formed by irregular wrinkles. The irregular wrinkles are preferably formed by a plurality of protrusions and a recess formed by being surrounded by the plurality of protrusions, and the protrusions preferably have linear protrusions. If the protrusions are linear, when contaminants are wiped off, the contaminants move smoothly along the linear wrinkles, making decontamination easier, thereby particularly improving the ease of decontamination. Furthermore, since the wrinkles have a smooth, linear shape, as shown in Figure 1, when contaminants are wiped off, the contaminants move smoothly along the linear wrinkles, making decontamination easier, and the surface is also consistently easy to decontaminate.

[0178] (resin) The resin used to form the matte, easy-to-decontaminate layer of the matte article E is the same as that described for the matte article A above.

[0179] (Easy decontamination agent) The matte, easy-to-decontaminate layer of the matte article E preferably contains an easy-to-decontaminate agent. As described above, even without the easy-to-decontaminate agent, the matte, easy-to-decontaminate layer has excellent easy-to-decontaminate properties due to the wrinkles it has. However, the use of the easy-to-decontaminate agent further improves the easy-to-decontaminate properties. As the easy-to-decontaminate agent, those used as antifouling agents, liquid repellents, etc. for articles such as decorative materials and decorative sheets, for example, fluororesins, silicone resins, and fluorine-silicone copolymer resins, as well as surfactants that do not contain fluorine or silicone, can also be used.

[0180] Among them, fluororesins are preferred, and specifically include the fluorine-containing silicon compound etc. that has hydrolyzable silyl group.As the fluorine-containing silicon compound that has hydrolyzable silyl group, for example, can be mentioned compounds that exist as fluorine-containing organic group that perfluoropolyether group, perfluoroalkylene group, perfluoroalkyl group etc. are bonded to the silicon atom of hydrolyzable silyl group via linking group or directly.In addition, perfluoropolyether group refers to a divalent group that has a structure that perfluoroalkylene group and etheric oxygen atom are bonded alternately. Commercially available examples of such fluorine-containing silicon compounds include "KP-801," "KY-130," "KY-178," and "X-71-195" manufactured by Shin-Etsu Chemical Co., Ltd., and "OPTOOL DSX," "OPTOOL DSX-E," and "OPTOOL UF503" manufactured by Daikin Industries, Ltd., and from the viewpoints of productivity and antifouling properties, "X-71-195," "OPTOOL DSX-E," and "OPTOOL UF503" are preferred.

[0181] From the viewpoint of more efficiently improving the ease of decontamination, the content of the easy-to-decontaminate agent per 100 parts by mass of resin is preferably 0.5 parts by mass or more, more preferably 1.0 parts by mass or more, and even more preferably 1.5 parts by mass or more, with the upper limit being preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, and even more preferably 10.0 parts by mass or less.

[0182] (Resin composition) The resin composition used to form the matte, easy-to-decontaminate layer of matte article E (resin composition for forming the matte, easy-to-decontaminate layer) is the same as the resin composition described for matte article A above, except that it may contain an easy-to-decontaminate agent as already described.

[0183] [60° gloss value] The 60° gloss value of Matte Article E is 5.0 or less, which is the same as the 60° gloss value described above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same.

[0184] [Layer structure] The matte article E does not necessarily have a substrate, as with the matte article A. Therefore, the simplest layer structure of the matte article E may be a single layer structure consisting of only a matte, easy-to-decontaminate layer, without a substrate. Furthermore, similar to the above-mentioned Matte Article A, when the Matte Article E has a layer structure of a single layer, options for obtaining various properties required of a matte article, such as mechanical strength, suitability for post-processing, designability, etc., are often limited. Therefore, the layer structure of the Matte Article E preferably has a substrate, i.e., a layer structure having a substrate and a matte layer.

[0185] [Base material] In addition to the matte layer, the matte article E may further have a substrate as desired, and as described above, it is preferable to have a substrate in order to avoid various restrictions. The substrate functions as a support on which the matte layer is provided. Furthermore, considering that the matte article E is usually used by being attached to an adherend, the form (or shape) of the substrate is preferably a film, sheet, or plate, and more preferably a film or sheet. Other than that, the substrate of the matte article E is the same as that described for the matte article A above.

[0186] [Other layers] In addition to the above-described matte layer (matte, easily decontaminated layer) and substrate, the matte article E may optionally have other layers, such as a primer layer, a transparent resin layer, a decorative layer, or an adhesive layer. Cross-sectional views showing an embodiment of the matte article E having these layers are shown in Figures 3 and 4. Figures 3 and 4 are also cross-sectional views showing an embodiment of the matte article E. These cross-sectional views are obtained by cutting the matte article 1 (matte article E) along a plane parallel to its thickness direction (the Z direction in the figure). The matte article 1 (matte article E) shown in Figure 3 has, in order, a substrate 5 and a matte layer (matte, easy-to-decontaminate layer) 4, and the matte article 1 (matte article E) shown in Figure 4 has, in order, a substrate 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a matte layer (matte, easy-to-decontaminate layer) 4.

[0187] (Primer layer) The primer layer that the matte article E may have is the same as that described for the matte article A above.

[0188] (Transparent resin layer) The transparent resin layer that the matte article E may have is the same as that described for the matte article A above.

[0189] (decorative layer) The decorative layer that the matte article E may have is the same as that described above for the matte article A.

[0190] (adhesive layer) The adhesive layer that the matte article E may have is the same as that described above for the adhesive layer of the matte article A.

[0191] (Performance of Matte Article E) Matte Article E has excellent surface properties, particularly excellent ease of decontamination. For example, in a staining test conducted in accordance with "15.3 C Method" of JIS K6902:2007 (Test methods for thermosetting resin high-pressure decorative laminates) using acetone (material number 3), household ammonia (material number 4), 10% citric acid (material number 5), black oil-based marker (material number 12), and crayon (material number 14) as contaminants, Matte Article E has a cleanability of at least grade 3 or higher (grade 3 to grade 0) when evaluated according to the grades 0 to 5 criteria in "15.3.5.2 Cleaning Procedure." Matte Article E also has a stain resistance of at least grade 3 or higher (grade 3 or 5) when evaluated according to the grades 5, 3, and 1 criteria in "15.3.6.2 Stain Resistance."

[0192] [Method for producing matte article E] The manufacturing method for matte article E differs from that for matte article A in that the resin composition for forming the matte, easy-to-decontaminate layer may contain an easy-to-decontaminate agent. However, other aspects, such as the average particle size and type of wrinkle formation stabilizer, the type of resin contained in the resin composition for forming the matte, easy-to-decontaminate layer, the content of the wrinkle formation stabilizer, the application method and thickness of the resin composition for forming the matte, easy-to-decontaminate layer, and the irradiation conditions in the matte, easy-to-decontaminate layer formation process, are the same as those described for the manufacturing method for matte article A. In addition, when the matte, easily decontamination layer (matte layer) is used as a single layer, or when the substrate and other layers are present, the steps of the manufacturing method are the same as those described for the manufacturing method of the matte article A above.

[0193] [Decorative material E] Typical uses of the matte article E include using the matte article E as it is, as a decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or laminating, compounding, or combining with an adherend to be used as a decorative material (hereinafter, such decorative materials using the matte article E may be referred to as "decorative material E"). The choice of use can be determined as desired. The form of the matte article E in the decorative member E, the adherend, the adhesive layer, the manufacturing method of the decorative member E, the uses of the decorative member E, etc. are the same as those described for the decorative member A above.

[0194] [Matte article F] The matte article of this embodiment is a matte article (hereinafter simply referred to as "Matte Article F") similar to the above-described Matte Article A, except that the matte layer is a matte light-resistant layer, and the resin composition constituting the matte light-resistant layer further contains a hydroxyphenyltriazine-based UV absorber. Specifically, the matte article has a matte layer, the matte layer is made of a cured resin composition containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by weight per 100 parts by weight of resin, and the hydroxyphenyltriazine-based UV absorber. At least one surface of the matte layer has an irregular texture formed by irregular wrinkles, the 60° gloss value of the matte layer is 5.0 or less, and the matte layer is a matte light-resistant layer. With this configuration, Matte Article F has excellent light resistance, and the visibility and texture of the matte effect are also excellent.

[0195] [Matte layer (matte light-resistant layer)] The matte layer in the matte article F is a matte light-resistant layer that particularly exhibits light resistance, and is a layer constituted by a cured product of a resin composition that contains a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass relative to 100 parts by mass of the resin, and also contains a hydroxyphenyltriazine-based ultraviolet absorber. That is, in this embodiment, the matte layer is a matte light-resistant layer that particularly exhibits light resistance, and is a layer that contains a wrinkle formation stabilizer and a hydroxyphenyltriazine-based ultraviolet absorber in an amount of 0.5 to 6.0 parts by mass relative to 100 parts by mass of the resin that forms the matte, easy-to-decontaminate layer.

[0196] (Wrinkle formation stabilizer) The wrinkle formation stabilizer used is the same as that described for use in the above-mentioned Matte Article A. The use of the wrinkle formation stabilizer stabilizes the formation of wrinkles on the surface of the matte light-resistant layer, thereby providing a stable texture and visibility due to the matte effect caused by the light diffusion effect at the refractive index difference interface between the surface and air. Furthermore, as will be described later, even when used in an outdoor environment such as an exterior component exposed to sunlight, wind, rain, and changes in temperature, there is also the effect of less change in gloss compared to conventional matting agents. The fact that at least one of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, the effects achieved by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those explained for matte article A above.

[0197] In addition, in relation to the main use of the matte article F, by using a wrinkle formation stabilizer, superior effects can be obtained compared to conventional matte agents in the following respects. Since the matte product F has excellent light resistance, it is widely used in environments exposed to sunlight, wind, rain, and temperature changes, such as exterior walls, eaves, roofs, fences, and other exterior components. Generally, when a resin layer containing particles of a matting agent or the like is exposed to outdoor sunlight, wind, rain, and temperature changes, the particles near the surface tend to fall off over time. Therefore, when the gloss of the layer surface is reduced solely by adding a matting agent, the falling off of such particles will cause a change in gloss over time during outdoor exposure. The change in gloss due to this mechanism during outdoor exposure becomes more pronounced with a lower gloss specification with a higher content of matting agent. In particular, the 60° gloss value G 60 When adding a matting agent to achieve a surface with a gloss of 10 or less, it is necessary to add approximately 50 parts by mass or more of the matting agent per 100 parts by mass of resin (although this depends on the type and dispersion form of the resin and matting agent), and the change in gloss when exposed to the outdoors due to the matting agent falling off will be significant.

[0198] In the matte light-resistant layer of the matte article F, as will be demonstrated in the examples and comparative examples described later, the 60° gloss value G 60 Even when a surface having a 60° gloss value G of 5.0 or less is realized by adding a matting agent, the content of the wrinkle formation stabilizer per 100 parts by mass of resin can be about 10 parts by mass or less. For example, in the examples described later, when the total content of the wrinkle formation stabilizer is a maximum of 6 parts by mass, the 60° gloss value G 60 It achieves a low gloss of 5.0 or less, or even 2.0 or less. Therefore, in the case of the matte article F, as will be demonstrated in the examples and comparative examples described later, when the same low gloss surface is realized, the 60° gloss value G 60 When a value of 10 or less is achieved, the particle content is significantly reduced compared to conventional matte decorative materials, matte articles such as decorative sheets, and the change in gloss due to outdoor exposure over time is small.

[0199] (Surface shape of matte light-resistant layer) The surface shape of the matte light-resistant layer of matte article F must have irregular wrinkles on at least one surface, and is the same as that described above for the matte layer of matte article A. Figures 1 and 2, which are used to explain the surface shape of the matte layer of matte article A, can also be applied to the matte light-resistant layer of matte article F. Having the surface shape of the matte light-resistant layer have the surface shape described above for the matte layer of matte article A improves light resistance, visibility of the matte effect, and texture.

[0200] (resin) The resin used to form the matte light-resistant layer of Matte Article F is the same as that described for Matte Article A above.

[0201] (ultraviolet absorber) The matte light-resistant layer of the matte article F contains a hydroxyphenyltriazine-based ultraviolet absorber as an ultraviolet absorber. Excellent light resistance cannot be obtained without the inclusion of this ultraviolet absorber. Preferred examples of the hydroxyphenyltriazine-based ultraviolet absorber include those represented by the following general formula (1):

[0202] [ka]

[0203] In general formula (1), R 11 is a single bond or a divalent organic group, and R 12 is a hydrocarbon group or -C(=O)OR 15 an ester group represented by -OC(=O)R 16 or an acyloxy group represented by -OR 17 and R is an alkoxy group represented by 13 , R 14 , R 15 , R 16 and R 17 are each independently a monovalent organic group, and n 11 and n 12 are each independently an integer of 0 to 5.

[0204] As represented by the general formula (1), the hydroxyphenyltriazine-based ultraviolet absorber has a large molecular structure, and therefore has a molecular structural characteristic that makes it difficult for the absorber to bleed out of the matte light-resistant layer due to steric hindrance, thereby enabling the matte article F to maintain excellent light resistance for a long period of time.

[0205] R 11 Preferred examples of the divalent organic group include aliphatic hydrocarbon groups such as alkylene groups and alkenylene groups, with alkylene groups being more preferred from the viewpoint of weather resistance. The number of carbon atoms in these aliphatic hydrocarbon groups is preferably 1 or more, with the upper limit being preferably 20 or less, more preferably 12 or less, even more preferably 8 or less, and particularly preferably 4 or less. The alkylene group and alkenylene group may be linear, branched, or cyclic, with linear or branched being preferred.

[0206] R 12 Preferred examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group, with an alkyl group being more preferred. The number of carbon atoms in the alkyl group is preferably 1 or more, more preferably 3 or more, and even more preferably 6 or more, with the upper limit being preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less. The alkyl group and alkenyl group may be linear, branched, or cyclic, with linear or branched being preferred, and branched being more preferred.

[0207] R 13 and R 14 Examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group, and aromatic hydrocarbon groups such as an aryl group and an arylalkyl group are preferred, with an aryl group being preferred.

[0208] R 13 and R 14The number of carbon atoms in the aryl group is preferably 6 or more, with the upper limit being preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less. The number of carbon atoms in the arylalkyl group is preferably 7 or more, with the upper limit being preferably 20 or less, more preferably 12 or less, and even more preferably 10 or less.

[0209] R 15 , R 16 and R 17 Examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. Aliphatic hydrocarbon groups such as an alkyl group and an alkenyl group are preferred, and an alkyl group is more preferred. 15 , R 16 and R 17 When is an alkyl group or an alkenyl group, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, and even more preferably 12 or less.

[0210] The above R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 The group may have a substituent such as a halogen atom, a hydroxyl group, an amino group, or an alkyl group having 1 to 4 carbon atoms.

[0211] Also, n 11 and n 12 are each independently an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2. 11 and n 12 is an integer equal to or greater than 2, multiple R 13 and R 14 may be the same or different, and are preferably the same from the viewpoint of availability.

[0212] Among the hydroxyphenyltriazine-based ultraviolet absorbers represented by the general formula (1), those represented by the following chemical formulas (2) to (4) are particularly preferred. The ultraviolet absorber represented by the chemical formula (2) is a compound represented by the general formula (1) where R 11 is an ethylene group, R 12 -OC(=O)R 16 An acyloxy group (R 16 is a 3-heptyl group), R 13 and R 14 is a hydrogen atom, and is available as a commercial product ("ADK STAB LA-46 (product number)", melting point: 106°C, manufactured by ADEKA Corporation).

[0213] [ka]

[0214] The ultraviolet absorber represented by chemical formula (3) is a compound represented by the general formula (1) above, wherein R 11 is a single bond, R 12 is an isooctyl group, R 13 and R 14 is a phenyl group, and n 11 and n 12 is available as a commercial product ("Tinuvin 1600 (product number)", melting point: 120°C, manufactured by BASF).

[0215] [ka]

[0216] The ultraviolet absorber represented by chemical formula (4) is a compound represented by the general formula (1) above, wherein R 11 is a single bond, R 12 is a hexyl group, R 13 and R 14 is a hydrogen atom, and is available as a commercial product ("Tinuvin 1577 (product number)", melting point: 148°C, manufactured by BASF).

[0217] [ka]

[0218] In Matte Article F, the content of the hydroxyphenyltriazine-based UV absorber is preferably 0.1 parts by mass or more, more preferably 1.0 parts by mass or more, even more preferably 2.0 parts by mass or more, and even more preferably 3.0 parts by mass or more, relative to 100 parts by mass of the resin in the resin composition for forming the matte light-resistant layer. From the viewpoint of suppressing bleed-out, the upper limit is preferably 10.0 parts by mass or less, more preferably 8.0 parts by mass or less, even more preferably 7.0 parts by mass or less, and even more preferably 6.0 parts by mass or less. Thus, by using a specific UV absorber, loss of the UV absorber due to bleed-out can be suppressed, and therefore excellent light resistance can be obtained even with a smaller amount than that normally blended. Furthermore, by using an ionizing radiation-curable resin as the resin used in the resin composition for forming the matte light-resistant layer, bleed-out can be further suppressed, and therefore excellent light resistance can be obtained even with a smaller amount.

[0219] (Resin composition) The resin composition used to form the matte light-resistant layer of Matte Article F (resin composition for forming the matte light-resistant layer) is the same as the resin composition described for Matte Article A above, except that it contains a hydroxyphenyltriazine-based ultraviolet absorber as described above.

[0220] [60° gloss value] The 60° gloss value of Matte Article F is 5.0 or less, which is the same as the 60° gloss value described above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same.

[0221] [Layer structure] Matte Article F does not necessarily have a substrate, as with Matte Article A. Therefore, the simplest layer structure of Matte Article E may be a single layer structure consisting of only a matte lightfast layer, without a substrate. Furthermore, similar to the above-mentioned matte article A, when matte article F has a layer structure of a single layer, options for obtaining various properties required of a matte article, such as mechanical strength, suitability for post-processing, designability, etc., are often limited. Therefore, the layer structure of matte article F preferably has a substrate, i.e., a layer structure having a substrate and a matte layer.

[0222] [Base material] In addition to the matte layer, the matte article F may further have a substrate as desired, and as mentioned above, it is preferable to have a substrate in order to avoid various restrictions. The substrate functions as a support on which the matte layer is provided. Furthermore, considering that the matte article F is usually used by being attached to an adherend, the form (or shape) of the substrate is preferably a film, sheet, or plate, and more preferably a film or sheet. The substrate of the matte article F is the same as that described for the matte article A above.

[0223] [Other layers] In addition to the above-mentioned matte layer (matte light-resistant layer) and substrate, the matte article F may optionally have other layers, such as a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. Cross-sectional views showing an embodiment of the matte article F having these layers are shown in Figures 3 and 4. Figures 3 and 4 are also cross-sectional views showing an embodiment of the matte article F. These are cross-sectional views of the matte article 1 (matte article F) cut along a plane parallel to its thickness direction (the Z direction in the figures). The matte article 1 (matte article F) shown in Figure 3 has a substrate 5 and a matte layer (matte light-resistant layer) 4 in this order, and the matte article 1 (matte article F) shown in Figure 4 has a substrate 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a matte layer (matte light-resistant layer) 4 in this order.

[0224] (Primer layer) The primer layer that the matte article F may have is the same as that described above for the matte article A.

[0225] (Transparent resin layer) The transparent resin layer that the matte article F may have is the same as that described above for the matte article A.

[0226] (decorative layer) The decorative layer that the matte article F may have is the same as that described above for the matte article A.

[0227] (adhesive layer) The adhesive layer that the matte article F may have is the same as that described above for the matte article A.

[0228] (Performance of Matte Product F) Matte Article F has excellent surface properties, particularly excellent light resistance. For example, when a 200-hour weather resistance test is conducted using an "S-UV (rainy)" weather resistance tester, the 60° gloss value of the matte light-resistant layer side before the weather resistance test is defined as G0, and the 60° gloss value of the matte light-resistant layer side after the weather resistance test is defined as G1. The change in gloss value (|(G1-G0)| / G0×100) is 20% or less, demonstrating excellent light resistance.

[0229] The rate of change in gloss value, which is the range of change in gloss value before and after the weather resistance test, is used as an index of the light resistance of Matte Article F. The larger the rate of change in gloss value, the higher the gloss value after the weather resistance test, i.e., the gloss of the surface of Matte Article F becomes higher due to deterioration, indicating poor light resistance. Since the matte article F of this embodiment has excellent light resistance, the rate of change in gloss value is 20% or less as described above, and can further be 15% or less, 10% or less, or 8% or less.

[0230] [Method for producing matte article F] The manufacturing method for Matte Article F differs from that for Matte Article A in that the resin composition for forming the matte light-resistant layer contains a hydroxyphenyltriazine-based ultraviolet absorber. However, other aspects, such as the average particle size and type of wrinkle formation stabilizer, the type of resin contained in the resin composition for forming the matte light-resistant layer, the content of the wrinkle formation stabilizer, the application method and thickness of the resin composition for forming the matte light-resistant layer, and the irradiation conditions in the matte light-resistant layer formation step, are the same as those described for the manufacturing method for Matte Article A. In addition, when the matte lightfast layer (matte layer) is a single layer, or when the substrate and other layers are present, the steps of the manufacturing method are the same as those described for the manufacturing method of the matte article A above.

[0231] [Decorative material F] Typical uses of the matte article F include using the matte article F as it is, as a decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or laminating, compounding, or combining with an adherend to be used as a decorative material (hereinafter, such decorative materials using the matte article F may be referred to as "decorative material F"). The choice of use can be determined as desired. The form of the matte article F in the decorative member F, the adherend, the adhesive layer, the manufacturing method of the decorative member F, the uses of the decorative member F, etc. are the same as those explained for the decorative member A above.

[0232] [Matte article G] The matte article of this embodiment is a matte article (hereinafter also referred to simply as "matte article G") in which the matte layer of the above-mentioned matte article A is a matte writing layer. Specifically, it is a matte article having a matte layer, the matte layer being composed of a cured product of a resin composition containing 0.5 to 6.0 parts by mass of a wrinkle formation stabilizer per 100 parts by mass of resin, at least one surface of the matte layer having an irregular shape composed of irregular wrinkles, the 60° gloss value of the matte layer being 5.0 or less, and the matte layer being a matte writing layer. By having such a configuration, matte article G has excellent visibility due to the matte effect and excellent marker erasability.

[0233] [Matte layer (matte writing layer)] The matte layer in the matte article G is a matte writing layer that exhibits marker erasability in particular, and is a layer composed of a cured product of a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin. That is, in this embodiment, the matte layer is a matte writing layer that exhibits marker erasability in particular, and is a layer containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin that forms the matte writing layer.

[0234] (Wrinkle formation stabilizer) The wrinkle formation stabilizer used is the same as that described above as being employed in Matte Article A. By using the wrinkle formation stabilizer, the formation of wrinkles on the surface of the matte writing layer is stabilized, thereby providing a matte effect due to the light diffusion effect at the refractive index difference interface between the surface and air, and also providing stable marker erasability as well as visibility. The fact that at least one of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, the effects achieved by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those explained for matte article A above.

[0235] (Surface shape of matte writing layer) The surface shape of the matte writing layer of matte article G must have irregular creases on at least one surface, and is the same as that described above for the matte layer of matte article A. Figures 1 and 2, which are used to explain the surface shape of the matte layer of matte article A, can also be applied to the matte writing layer of matte article G. Having the surface shape of the matte writing layer have the surface shape described above for the matte layer of matte article A improves visibility and marker erasability due to the matte effect.

[0236] Here, the effect obtained by the surface shape of the matte writing layer includes the effect of stably expressing the visibility and texture of the excellent matte effect obtained by the matte layer of matte article A, but the important effect of matte article G is marker erasability. As described above, the matte writing layer has an uneven shape formed by irregular wrinkles. The irregular wrinkles are preferably formed by a plurality of protrusions and a plurality of recesses formed by the protrusions, and the protrusions preferably have linear protrusions. When the protrusions are linear, the marker moves smoothly along the linear wrinkles when wiped off, making it easier to erase, thereby particularly improving marker erasability. Furthermore, since the wrinkles have a smooth, linear shape, as shown in Figure 1, when wiping off the marker, the marker moves smoothly along the linear wrinkles, making it easy to erase, and the marker erasability is also stable.

[0237] (resin) The resin used to form the matte writing layer of Matte Article G is the same as that described for Matte Article A above.

[0238] (Resin composition) The resin composition used to form the matte writing layer of the matte article G (resin composition for forming the matte writing layer) is the same as the resin composition described for the matte article A above.

[0239] [60° gloss value] The 60° gloss value of Matte Article G is 5.0 or less, which is the same as the 60° gloss value described above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same.

[0240] [Layer structure] The matte article G does not necessarily have a substrate, as with the matte article A. Therefore, the simplest layer structure of the matte article G may be a single layer structure consisting of only a matte, easy-to-decontaminate layer, without a substrate. Furthermore, similar to the above-mentioned matte article A, when the matte article G has a layer structure of a single layer, options for obtaining various properties required of a matte article, such as mechanical strength, suitability for post-processing, designability, etc., are often limited. Therefore, the layer structure of the matte article G preferably has a substrate, i.e., a layer structure having a substrate and a matte layer.

[0241] [Base material] In addition to the matte layer, the matte article G may further have a substrate as desired, and as described above, it is preferable to have a substrate from the viewpoint of avoiding various constraints. The substrate functions as a support on which the matte layer is provided. Furthermore, considering that the matte article G is usually used by being attached to an adherend, the form (or shape) of the substrate is preferably a film, sheet, or plate, and more preferably a film or sheet. Other than that, the materials constituting the substrate of the matte article G are the same as those described for the substrate of the matte article A above.

[0242] The substrate used in the matte article G preferably has a substrate (substrate sheet) as a form sheet and a colored layer. In this case, the colored layer may be provided using ink containing the above-mentioned colorant so as to have a desired color tone. The ink used for the colored layer is a mixture of a binder resin with the above-mentioned colorant, extender pigment, solvent, stabilizer, plasticizer, catalyst, hardener, ultraviolet absorber, light stabilizer, etc., as appropriate.

[0243] The binder resin of the ink used to form the colored layer of the substrate sheet is not particularly limited, and examples thereof include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, etc. In addition, various types of resins can be used, such as one-component curing resins and two-component curing resins containing a curing agent such as an isocyanate compound. The content of the colorant is preferably 5 to 90 parts by mass, more preferably 15 to 80 parts by mass, and even more preferably 30 to 70 parts by mass, per 100 parts by mass of the resin constituting the colored layer.

[0244] The colored layer may contain additives such as weathering agents, including ultraviolet absorbers and light stabilizers. The thickness of the colored layer may be selected appropriately depending on the desired color tone, etc., but from the viewpoint of concealing the base color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, more preferably 1 μm or more and 10 μm or less, and even more preferably 2 μm or more and 5 μm or less.

[0245] In addition, as a method other than forming the colored layer, in the case of coloring a synthetic resin, any means can be employed, such as adding a colorant to the resin (kneading or mixing), forming a coating film by applying a paint containing a resin and a colorant, etc. In the case of coloring paper, nonwoven fabric, or woven fabric, any means, such as mixing with pulp or a fiber material, or forming a coating film, or a combination of these, can be used. In the case of coloring wood, it can be done by dyeing with a dye or by forming a coating film, or by a combination of these. In the case of coloring metals, in addition to forming a coating film, electrolytic coloring methods that form a metal oxide film on the surface using anodization can be used. In addition, in the case of non-metallic inorganic materials, it can be done by forming a coating film or by adding a dye to the substrate, or by a combination of these.

[0246] The colored layer of the base sheet is basically a layer consisting of a so-called solid colored layer that covers the entire surface, but may have a picture layer having various patterns, such as a dot pattern, as desired.

[0247] [Other layers] In addition to the above-described matte layer (matte writing layer) and substrate, the matte article G may optionally have other layers, such as a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. Cross-sectional views showing an embodiment of a matte article G having these layers are shown in Figures 34 and 35. These are cross-sectional views of a matte article 1 (matte article G) cut along a plane parallel to its thickness direction (the Z direction in the figure). The matte article 1 (matte article G) shown in Figure 34 has, in order, a substrate 5 (a two-layer laminate structure of a substrate sheet 51 and a colored layer 52) and a matte layer (matte writing layer) 4, and the matte article 1 (matte article G) shown in Figure 35 has, in order, a colored substrate sheet 5 (a two-layer laminate structure of a substrate sheet 51 and a colored layer 52), an adhesive layer 6, a transparent resin layer 7, a primer layer 8, and a matte layer (matte writing layer) 4.

[0248] (Primer layer) The primer layer that the matte article G may have is the same as that described for the matte article A above.

[0249] (Transparent resin layer) The transparent resin layer that the matte article G may have is the same as that described for the matte article A above.

[0250] (decorative layer) The decorative layer that the matte article G may have is the same as that described above for the matte article A.

[0251] (adhesive layer) The adhesive layer that the matte article G may have is the same as that described above for the matte article A.

[0252] (Performance of Matte Product G) Matte article G has excellent marker erasability, and for example, meets the requirements of JIS S6052:2014 for "a pen with a round tip and a medium nib." 1) Black marker (Note 1)A medium-sized marker is one with a line thickness of approximately 1.5mm to 2.5mm. The marker was tested for smearing properties according to the following methods a) to c) and the color difference (ΔE * ab) is 3.0 or less, which means that the ink has excellent marker erasability. (Marker removal test) a) Use the marker to fill in an area of ​​2cm x 4cm on the matte writing layer of the sheet. b) After one minute has passed since the marking, erase the marking using an unused melamine foam whiteboard eraser (2cm x 2cm, whiteboard eraser (Auto Co., Ltd.)). c) Repeat steps a) and b) above 50 times.

[0253] Color difference (ΔE * ab) The measured values ​​of lightness and chromaticity before the test are * 1, a * 1 and b * 1, and the measured values ​​of lightness and chromaticity after the above test are L * 2, a * 2 and b * 2, the calculated value is obtained using the following formula. ΔE * ab=〔(L * 2-L * 1) 2 +(a * 2-a * 1) 2 +(b * 2-a * 2) 2 〕 1 / 2 Also, L * , a * , b * is specified in the color display method of JIS Z8781-5:2013, and can be measured using a commercially available spectrophotometer (for example, the spectrophotometer / color difference meter "SE6000" (model number), manufactured by Nippon Denshoku Industries Co., Ltd.).

[0254] [Method for manufacturing matte article G] Regarding the manufacturing method of matte article G, the average particle size and type of wrinkle formation stabilizer, the type of resin contained in the resin composition for forming the matte writing layer, the content of the wrinkle formation stabilizer, the application method and thickness of the resin composition for forming the matte writing layer, and the irradiation conditions in the matte writing layer formation process are the same as those described above for the manufacturing method of matte article A. Furthermore, when the matte writing layer (matte layer) is a single layer, or when the substrate and other layers are present, the steps of the manufacturing method are the same as those described for the manufacturing method of the matte article A above.

[0255] [Decorative material G] Typical uses of the matte article G include writing boards such as whiteboards and blackboards, in which the matte article G is used alone or laminated, composited, or combined with an adherend (hereinafter, decorative members using these matte articles G may be referred to as "decorative members G"). The form to be used may be determined as desired. When an adherend is included, the decorative member G (writing board) comprises the adherend and the matte article G of the above-described embodiment, specifically, the surface of the adherend that requires writability is stacked opposite the surface of the matte article G opposite to the surface on which wrinkles form in the matte writing layer to provide visibility and marker erasability.

[0256] The adherend may be appropriately selected from those described above as adherends that can be used in the decorative member A, but considering its use as a writing board, flat plates, sheets (or films) made of various materials are preferred. The thickness of the adherend may be appropriately selected depending on the use and material, and is preferably 0.1 mm to 100 mm, more preferably 0.3 mm to 5 mm, and even more preferably 0.5 mm to 3 mm. Furthermore, in consideration of ease of lamination onto an adherend, the matte article G of this embodiment preferably has a sheet form as described above.

[0257] Other than that, the form of the matte article G, the adherend, the adhesive layer, the manufacturing method of the decorative member G, etc. in the decorative member G are the same as those explained for the decorative member A above.

[0258] The decorative member G (writing board) obtained as described above can be cut as desired, and the surface and end grain can be grooved, chamfered, bent, or otherwise decorated as desired using a cutting machine such as a router or cutter.

[0259] [Matte article H] The matte article of this embodiment is a matte article (hereinafter also referred to simply as "Matte Article H") in which the matte layer of the above-mentioned Matte Article A is a matte-imparting layer. Specifically, it is a matte article having a matte layer, the matte layer being made of a cured product of a resin composition containing 0.5 to 6.0 parts by mass of a wrinkle formation stabilizer per 100 parts by mass of resin, at least one surface of the matte layer having an irregular texture formed by irregular wrinkles, the 60° gloss value of the matte layer being 5.0 or less, and the matte layer being a matte-imparting layer. By having such a configuration, Matte Article H can easily meet diverse customer needs and can be used as a product that imparts excellent visibility and texture of a matte effect, i.e., a shaping sheet.

[0260] [Matte layer (matt-imparting layer)] The matte layer in the matte article H is a matte-imparting layer that can easily meet the diversifying needs of customers and that imparts excellent matte visibility and texture, and is a layer composed of a cured product of a resin composition that contains 0.5 to 6.0 parts by mass of a wrinkle formation stabilizer relative to 100 parts by mass of the resin. That is, in this embodiment, the matte layer is a matte-imparting layer that can easily meet the diversifying needs of customers and that imparts excellent matte visibility and texture, and is a layer that contains 0.5 to 6.0 parts by mass of a wrinkle formation stabilizer relative to 100 parts by mass of the resin that forms the matte-imparting layer.

[0261] (Wrinkle formation stabilizer) The wrinkle formation stabilizer used is the same as that described above as being employed in Matte Article A. Use of the wrinkle formation stabilizer stabilizes the formation of wrinkles on the surface of the matte writing layer, thereby imparting a texture as well as visibility due to the matte effect resulting from the light diffusion effect at the refractive index difference interface between the surface and air. In addition, the fact that at least one of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, the effects achieved by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those explained for matte article A above.

[0262] (Surface shape of matte layer) The surface shape of the matte layer of matte article H must have irregular wrinkles on at least one surface, and is the same as that described above for the matte layer of matte article A. Figures 1 and 2, which are used to explain the surface shape of the matte layer of matte article A, can also be applied to the matte layer of matte article H. Having the surface shape of the matte layer as described above for the matte layer of matte article A makes it possible to easily meet the diverse needs of customers and to impart excellent visibility and texture to the matte effect.

[0263] (resin) The resin used to form the matte layer of the matte article H is the same as that described for the matte article A above.

[0264] (Resin composition) The resin composition used to form the matte layer of the matte article H (resin composition for forming the matte layer) is the same as the resin composition described for the matte article A above.

[0265] Furthermore, for the matte article H, since it is necessary to peel off the matte article H after molding using the matte article H, it is preferable that the matte molding layer has releasability. From this viewpoint, it is preferable that the matte molding layer contains a release agent, that is, it is preferable that the resin composition for forming the matte molding layer contains a release agent. Examples of the release agent include fluorine-based release agents and silicone-based release agents, and from the viewpoint of obtaining lower cost and higher releasability, silicone-based release agents are preferred.

[0266] Examples of silicone-based release agents include those having a polysiloxane structure as a basic structure. Among these, modified silicone oils having organic groups introduced into at least one of the side chains and terminals are preferred, and modified silicone oils having organic groups introduced into both terminals are more preferred. From the viewpoint of achieving a more sophisticated design, preferred organic groups include reactive functional groups such as (meth)acrylic groups, amino groups, epoxy groups, mercapto groups, carbinol groups, phenol groups, and carboxyl groups, and non-reactive functional groups such as polyether groups, aralkyl groups, fluoroalkyl groups, alkyl groups, fatty acid amide groups, and phenyl groups. Among these, reactive functional groups are preferred, and (meth)acrylic groups are particularly preferred, i.e., (meth)acrylic-modified silicone oils are particularly preferred. Furthermore, these organic groups may have substituents such as nitrogen atoms, sulfur atoms, hydroxyl groups, and alkyl groups.

[0267] The content of the release agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and even more preferably 1 to 2 parts by mass, relative to 100 parts by mass of the resin forming the matte layer. When the content of the release agent is within the above range, the effect of adding the release agent can be efficiently obtained.

[0268] [60° gloss value] The 60° gloss value of Matte Article H is 5.0 or less, which is the same as the 60° gloss value explained above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same. Because Matte Article H is mainly used as a shaping sheet, the 60° gloss value of Matte Article H also means the 60° gloss value that Matte Article H can impart (the 60° gloss value of a shaped object). If the matte-imparting sheet of this embodiment has a stable matte effect and texture due to stable wrinkle formation, a decorative material formed using this sheet can also be a luxurious decorative material with a stable matte effect visibility and texture. Furthermore, the 60° gloss value of the shaped sheet and the 60° gloss value of the decorative material obtained using this sheet will basically be the same if the color tones of the two are similar, although there will be some differences.

[0269] [Layer structure] The matte article H does not necessarily have to have a substrate, as with the matte article A. Therefore, the simplest layer structure of the matte article H may be a single layer structure consisting of only a matte-imparting layer, without a substrate. Furthermore, similar to the above-mentioned matte article A, when the matte article H has a layer structure of a single layer, options for obtaining various properties required of a matte article, such as mechanical strength, suitability for post-processing, designability, etc., are often limited. Therefore, the layer structure of the matte article H preferably has a substrate, i.e., a layer structure having a substrate and a matte layer.

[0270] [Base material] In addition to the matte layer, the matte article H may further have a substrate as desired, and as described above, it is preferable to have a substrate in order to avoid various restrictions. The substrate functions as a support on which the matte layer is provided. Furthermore, considering that the matte article H is usually used by being attached to an adherend, the form (or shape) of the substrate is preferably a film, sheet, or plate, and more preferably a film or sheet. Other than that, the materials constituting the substrate of the matte article H are the same as those described for the substrate of the matte article A above.

[0271] [Other layers] In addition to the matte layer (matt-imparting layer) and substrate, the matte article H may optionally have other layers, such as a primer layer, a resin layer, or an adhesive layer. Cross-sectional views showing an embodiment of the matte article H having these layers are shown in Figures 41 and 42. These are cross-sectional views of the matte article 1 (matte article H) cut along a plane parallel to its thickness direction (the Z direction in the figure). The matte article 1 (matte article H) shown in Fig. 41 has, in order, a substrate 5 and a matte-imparting layer 4, and the matte article 1 (matte article H) shown in Fig. 42 has, in order, a substrate 5, an adhesive layer 6, a resin layer 7, a primer layer 8, and a matte-imparting layer 4. As mentioned above, the matte article H is used as a shaping sheet, and unlike other matte articles, it is not used as a decorative member itself, so it does not need to have a decorative layer.

[0272] (Primer layer) The primer layer that the matte article H may have is the same as that described for the matte article A above.

[0273] (resin layer) Since the matte article H is used as a shaping sheet, it may have a resin layer to increase its strength. When the matte article H is used repeatedly as a shaping sheet, durability is required, so having a resin layer is effective. The resin layer may be provided between the substrate sheet and the matte layer. Other details, such as the type of resin, are the same as those for the transparent resin layer described for the matte article A above.

[0274] (adhesive layer) The adhesive layer that the matte article H may have is the same as that described above for the adhesive layer of the matte article A.

[0275] [Method for manufacturing matte article H] Regarding the manufacturing method for matte article H, the average particle size and type of wrinkle formation stabilizer, the type of resin contained in the resin composition for forming the matte-imparting layer, the content of the wrinkle formation stabilizer, the application method and thickness of the resin composition for forming the matte-imparting layer, and the irradiation conditions in the matte-imparting layer formation process are the same as those described for the manufacturing method for matte article A above. In addition, when the matte layer (matte layer) is a single layer, or when the substrate and other layers are present, the steps of the manufacturing method are the same as those described for the manufacturing method of the matte article A above.

[0276] [Matte cosmetic material H] As mentioned above, the matte article H is used as a shaping sheet, and unlike other matte articles, it is not used as a decorative member itself. The product shaped using the matte article H is called matte decorative material H, and its manufacturing method will be described below.

[0277] (Matte decorative material H manufacturing method) The method for producing a matte decorative material H is characterized by using the above-described matte article H as a shaping sheet for shaping. The matte article H is suitably used as a shaping sheet in the method for producing a matte decorative material. The matte article H has stable visibility and texture of the matte effect due to stable wrinkle formation, and therefore the matte decorative material H obtained by shaping using this has a luxurious feel with the visibility of the matte effect and texture.

[0278] One preferred embodiment of the method for producing the matte decorative material H is to use an embossing roller on which the matte article H is placed to form a shape. This allows the wrinkles that the matte article H has to be formed on the shaping target member, and the wrinkles make it possible to impart a stable matte effect with visibility and a luxurious feel. In this case, the matte article H functions as a substitute for an embossing plate, and therefore, as the shaping target member, any member that can be used without particular limitation as long as it is one that can be given a textured shape on its surface using an embossing plate.

[0279] Another preferred embodiment of the method for producing the matte decorative material H is to place a substrate impregnated with a resin composition and a matte article H so that the matte-imparting layer of the matte article H faces the substrate, heat and pressure molding is performed to cure the resin composition, and then shaping is performed by peeling off the matte article H. This embodiment is a method that is preferably employed for producing thermosetting resin decorative boards such as melamine resin decorative boards, diallyl phthalate (DAP) resin decorative boards, polyester decorative boards, guanamine resin decorative boards, and phenolic resin decorative boards, which are mainly used for surface decorative boards for general furniture such as chests of drawers, shelves, and desks, building materials such as doors, and various counters.

[0280] As the substrate impregnated with the resin composition, for example, a fiber substrate or a paper substrate impregnated with a thermosetting resin can be used. The thermosetting resin contained in the resin composition can be any resin that cures at room temperature or upon heating, and preferred examples thereof include melamine resin, urea resin, melamine-urea resin, guanamine resin, diallyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, etc. Examples of thermosetting resins include melamine resin, urea resin, melamine-urea resin, guanamine resin, sulfonamide resin, etc., and melamine resin, diallyl phthalate resin, polyester resin, guanamine resin, phenol resin, etc. are particularly commonly used resins.

[0281] In addition to the substrate impregnated with the resin composition, a fiber substrate or paper substrate impregnated with a thermosetting resin may be used as a reinforcing layer. In this case, the thermosetting resin is preferably a phenolic resin, i.e., a phenolic resin-impregnated paper that is commonly used as a core paper for melamine resin decorative boards, etc. More specifically, for example, a grammage of 150 to 250 g / m 2 Examples include those obtained by impregnating kraft paper of the above type with a phenolic resin and drying it at about 100 to 140° C. The fiber substrate or paper substrate impregnated with a thermosetting resin used as the reinforcing layer may be one or more sheets.

[0282] The conditions for the hot and pressure molding may be adjusted appropriately depending on the type of thermosetting resin used, and are not particularly limited. However, the temperature is usually 100°C or higher and 200°C or lower, and preferably 120°C or higher and 160°C or lower, the pressure is 0.1 MPa or higher, preferably 0.49 MPa or higher, and the upper limit is preferably approximately 1.47 MPa or lower, and the time is 10 seconds to 120 minutes.

[0283] Other than that, the components forming the resin decorative board may be the same as those used in conventional resin decorative boards, and there are no particular limitations.

[0284] The matte decorative material H obtained as described above can be cut as desired and the surface or end grain can be decorated as desired, such as by groove processing or chamfering, using a cutting machine such as a router or cutter. It can be used for a variety of applications, such as interior components for buildings such as walls, ceilings, and floors; exterior components such as exterior walls, eaves ceilings, roofs, fences, and fences; fittings or fixtures such as window frames, doors, door frames, handrails, baseboards, moldings, and other building components; general furniture such as chests of drawers, shelves, and desks; kitchen furniture such as dining tables and sinks; surface decorative panels for cabinets and the like for home appliances and office automation equipment; interior and exterior components for vehicles; and even packaging materials and antiglare films for displays. That is, the matte article H of this embodiment is suitable for use as a shaping sheet for shaping uneven shapes into these various components. Among the matte decorative materials H, resin decorative panels are preferably used mainly as surface decorative panels for general furniture such as chests of drawers, shelves, and desks, as well as for fixtures such as doors, and various counters.

[0285] [Matte Product Manufacturing Method I] The method for producing a matte article of this embodiment includes: The method includes a step of sequentially subjecting a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of resin and containing a photopolymerization initiator to the following irradiation treatments (1) and (2) to cure the resin composition and form a matte layer: At least one surface of the matte layer has an uneven shape formed by irregular wrinkles, Produce a matte article in which the 60° gloss value of the matte layer is 5.0 or less. (hereinafter, this may be simply referred to as "Production Method I"). (1) Irradiation with light having a wavelength of 100 nm or more and less than 200 nm (2) Irradiation treatment with at least one of electron beams and light with wavelengths of 200 nm or more and 400 nm or less A manufacturing method including such steps makes it possible to easily manufacture a matte article having excellent surface properties as well as excellent visibility and texture of the matte effect.

[0286] Production method I differs from the production method described above as the production method for matte article A in that it requires the irradiation treatment (2) above. However, the other aspects, such as the irradiation treatment (1), the wrinkle formation stabilizer, the matte layer and its surface shape, the resin and resin composition that form the matte layer, the 60° gloss value of the resulting matte article, and the layers that constitute the resulting matte article, are basically the same as those described above for matte article A. Production Method I will be explained in more detail below.

[0287] [Step of forming matte layer] The process for forming the matte layer involves sequentially subjecting a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 to 6.0 parts by mass per 100 parts by mass of resin and containing a photopolymerization initiator to the irradiation treatments (1) and (2) described above, thereby hardening the resin composition and forming the matte layer. Production method I includes a step of sequentially subjecting a resin composition containing a predetermined amount of a wrinkle formation stabilizer and a photopolymerization initiator to the two types of irradiation treatments (1) and (2) described above, curing the resin composition, and forming a wrinkled matte layer on at least one surface, thereby enabling the easy production of a matte layer having excellent surface properties as well as the visibility and texture of the matte effect. That is, the matte layer of the matte article obtained by production method I (hereinafter, the matte article obtained by production method I may be referred to as "matte article I") can be said to be a layer having an uneven shape composed of irregular wrinkles on at least one surface, obtained by sequentially subjecting a resin composition containing a predetermined amount of a wrinkle formation stabilizer and a photopolymerization initiator to the two types of irradiation treatments (1) and (2) described above, curing the resin composition.

[0288] (Wrinkle formation stabilizer) In the manufacturing method I, the wrinkle formation stabilizer used is the same as that used in the matte article A described above. The fact that at least one of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, the effects achieved by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those explained for matte article A above.

[0289] (Matte layer surface shape) The surface shape of the matte layer of matte article I obtained by production method I is required to have irregularities on at least one surface formed by irregular wrinkles, and is the same as that described above for the matte layer of matte article A. Figures 1 and 2, which are used to explain the surface shape of the matte layer of matte article A, can also be applied to the matte layer of matte article I. Having the surface shape of the matte layer of matte article A described above allows matte article I to have excellent surface properties as well as excellent visibility and texture of the matte effect.

[0290] (resin) In the production method I, the resin used to form the matte layer is the same as that described for the matte article A above.

[0291] (Photopolymerization initiator) In Production Method I, the matte layer contains a predetermined amount of a wrinkle formation stabilizer and is formed by curing a resin composition containing a photopolymerization initiator, and therefore contains a photopolymerization initiator. This differs from the above-mentioned Matte Article A in that it must contain a photopolymerization initiator. By using a photopolymerization initiator to moderately cure the resin in the resin composition that forms the matte layer, the wrinkles in the matte layer, which are primarily produced by using a wrinkle formation stabilizer, can be maintained, and the visibility and texture of the matte effect of the matte article I obtained by production method I can be improved. Furthermore, by promoting the curing of the resin composition, excellent surface properties can also be obtained. In particular, when ultraviolet irradiation is used in the irradiation treatment (2) described below, the inclusion of a photopolymerization initiator is effective in obtaining excellent surface properties.

[0292] Examples of the photopolymerization initiator include those exemplified as photopolymerization initiators that can be contained in the resin composition constituting the matte layer of the above-mentioned matte article A, namely, acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzil dimethyl ketal, benzoyl benzoate, α-acyloxime ester, thioxanthones, etc., as well as compounds having these as basic structures. In the present embodiment, as the photopolymerization initiator, these can be used alone or in combination of two or more kinds.

[0293] From the viewpoint of maintaining the wrinkle shape and stably improving the matte effect, the content of the photopolymerization initiator is preferably 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the resin forming the matte layer, and the upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, even more preferably 1.5 parts by mass or less, and still more preferably 1.0 part by mass or less.

[0294] (Resin composition) In manufacturing method I, the resin composition used to form the matte layer (resin composition for forming the matte layer) differs from that of the above-mentioned matte article A in that it must contain a photopolymerization initiator as described above. However, other additives such as various weathering agents that may be contained are the same as those described for the resin composition of the above-mentioned matte article A.

[0295] (irradiation treatment) In the manufacturing method I of this embodiment, when the resin composition for forming the matte layer is cured to form the matte layer, the following irradiation treatments (1) and (2) must be carried out in this order. (1) Irradiation with light having a wavelength of 100 nm or more and less than 200 nm (2) Irradiation treatment with at least one of electron beams and light with wavelengths of 200 nm or more and 400 nm or less

[0296] The irradiation treatment (1) above is the same as the irradiation treatment (1) described in the manufacturing method of the above-mentioned matte article A. In forming the matte layer, the irradiation treatment (1) involves irradiating a resin composition for matte formation, which contains a wrinkle formation stabilizer and a photopolymerization initiator, with ultraviolet light of a short wavelength of 100 nm or more and less than 200 nm, thereby forming wrinkles on at least one surface of the matte layer. Regarding the necessity of the irradiation treatment (2) above, by performing the irradiation treatment (2) following the irradiation treatment (1) above, the resin composition with the wrinkles retained can be cured as is by irradiating it with at least one of electron beams and light (ultraviolet light) with a wavelength longer than the above-mentioned short wavelengths, and therefore it becomes possible to easily produce a matte article I that has excellent surface properties as well as stable visibility and texture of the matte effect.

[0297] In the manufacturing method I of this embodiment, after the irradiation treatment (1) above, an irradiation treatment (2) using at least one of an electron beam and ultraviolet light having a wavelength of 200 nm or more and 400 nm or less is performed. As described above, the irradiation treatment (2) hardens the shape of the wrinkles formed by the irradiation treatment (1) above, thereby stably obtaining excellent visibility and texture of the matte effect, and also hardening the resin forming the matte layer, thereby obtaining excellent surface characteristics.

[0298] The electron beam irradiation conditions employed in the irradiation treatment (2) are not particularly limited as long as the resin composition for forming the matte layer is cured, but the electron beam acceleration voltage is preferably 10 kV or more, more preferably 30 kV or more, even more preferably 50 kV or more, and even more preferably 75 kV or more, with the upper limit being preferably 300 kV or less, more preferably 250 kV or less, and even more preferably 200 kV or less. When the electron beam acceleration voltage is within the above range, the shape of the wrinkles is more likely to be maintained as is, thereby stably improving the visibility and texture of the matte effect, and excellent surface properties are efficiently obtained by curing the resin composition for forming the matte layer. From the same viewpoint, the electron beam irradiation dose is preferably 5 kGy or more, more preferably 10 kGy or more, and even more preferably 15 kGy or more, with the upper limit being preferably 150 kGy or less, more preferably 125 kGy or less, and even more preferably 100 kGy or less. The electron beam source is not particularly limited as long as it can achieve the above-mentioned irradiation conditions, and various electron beam accelerators such as Cockcroft-Walton type, Van de Graaf type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, and high frequency type can be used.

[0299] (2) The ultraviolet light of 200 nm or more and 400 nm or less used in the irradiation treatment can be irradiated using an ultraviolet light irradiation device using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp, etc. Also, excimer light of 200 nm or more and 400 nm or less, such as 222 nm (KrCl), 247 nm (KrF), or 308 nm (XeCl), may be used.

[0300] (2) The wavelength of the ultraviolet light used in the irradiation treatment is preferably 330 nm or more, with the upper limit preferably being 390 nm or less. When the wavelength of the ultraviolet light is within this range, the shape of the wrinkles is easily maintained, thereby stably improving the visibility and texture of the matte effect, and excellent surface properties are efficiently obtained by curing the resin composition for forming the matte layer. From the same viewpoint, the output of the ultraviolet irradiation device that can be used in the irradiation treatment (2) is preferably 50 W / cm or more, more preferably 100 W / cm or more, with the upper limit being preferably 300 W / cm or less, more preferably 200 W / cm or less. The irradiation speed is preferably 1 r / min or more, more preferably 3 r / min or more, with the upper limit being preferably 50 r / min or less, more preferably 10 r / min or less.

[0301] In the manufacturing method I of this embodiment, if the irradiation treatment (2) is performed using at least one of electron beams and ultraviolet rays, excellent surface properties can be obtained, as well as excellent visibility and texture of the matte effect.

[0302] In Manufacturing Method I of this embodiment, an irradiation treatment for (3) pre-curing may be performed before the irradiation treatments (1) and (2) above. By performing the irradiation treatment for (3) pre-curing, the visibility and texture of the matte effect of the matte layer are improved, and the surface characteristics are also improved. The wavelength light used in the irradiation treatment for (3) pre-curing can be, for example, light with a wavelength of more than 320 nm, preferably light with a wavelength of more than 320 nm and not more than 400 nm, and more preferably light with a wavelength of 385 nm or more and not more than 400 nm. The resin composition for forming the matte layer can be pre-cured overall by irradiating it with light of this wavelength in advance. Whether or not pre-curing is necessary can be determined appropriately depending on the desired properties of the matte layer (for example, surface properties such as processing characteristics and stain resistance). Furthermore, although the light of the above wavelength belongs to the ultraviolet ray category, it is also possible to use other ionizing radiations other than ultraviolet ray, such as electron beams.

[0303] In manufacturing method I of this embodiment, the matte layer is formed by applying a resin composition for forming the matte layer by a known method such as gravure printing, bar coating, roll coating, reverse roll coating, or comma coating to form a coated layer (uncured resin layer), and then sequentially performing the irradiation treatments (1) and (2) described above. When the matte decorative material obtained by the manufacturing method of this embodiment has a substrate described below, the resin composition for forming the matte layer can be applied to at least one main surface of the substrate, and a matte agent will be formed on that main surface.

[0304] (60° gloss value) The 60° gloss value of Matte Article I obtained by Production Method I is 5.0 or less, which is the same as the 60° gloss value described above for Matte Article A. Therefore, the standard deviation (σ) of the 60° gloss value is also the same. According to the manufacturing method I of this embodiment, by using a small amount of wrinkle formation stabilizer as described above, employing a resin composition containing a photopolymerization initiator, and performing irradiation treatment under the specific conditions (1) and (2) above, it has become possible to stably obtain excellent visibility and texture of a matte effect. Furthermore, by limiting the amount of wrinkle formation stabilizer used to a small amount, a significant increase in viscosity of the resin composition can be suppressed, which makes it easy to form a layer, and the matte layer naturally has excellent surface properties such as stain resistance, scratch resistance, and weather resistance according to the properties of the resin used.

[0305] [Formation of other layers] The matte article I obtained by manufacturing method I may have other layers such as a substrate and a transparent resin layer, as described below. A manufacturing method for a matte article having other layers will be described using the matte article shown in Figures 3 and 4, which will be described later, as an example. Figures 3 and 4 are cross-sectional views showing one embodiment of the matte article I obtained by manufacturing method I of this embodiment, and are cross-sectional views of the matte article 1 (matte article I) cut along a plane parallel to its thickness direction (the Z direction in the figures).

[0306] In the case of a matte article having a substrate 5 and a matte layer 4 as shown in FIG. 3, a resin composition for forming the matte layer is applied to one main surface of the substrate, and the above-mentioned irradiation treatments (1) and (2) are sequentially carried out to cure the resin composition and form a matte layer, thereby obtaining the matte article shown in FIG. 3.

[0307] For a matte article having a substrate 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a matte layer 4 as shown in FIG. 4, a coating liquid containing a composition for forming the decorative layer and the adhesive layer is applied to one main surface of the substrate using the known method described above, and dried and cured as necessary to form the decorative layer and the adhesive layer. Next, a resin film for forming the transparent resin layer is formed on the adhesive layer by dry lamination, and a composition for forming the primer layer is applied to the transparent resin layer using the known method described above, and dried and cured as necessary to form the primer layer. Furthermore, a resin composition for forming the matte layer is applied to the primer layer, and the above-mentioned irradiation treatments (1) and (2) are sequentially performed to cure the resin composition and form the matte layer, thereby obtaining the matte article shown in FIG. 4. Note that unnecessary layers may be omitted as appropriate depending on the desired performance.

[0308] 3 and 4 show that the matte article I is a matte article having a substrate. However, as described below, it may also have a layer structure without a substrate, i.e., a single layer consisting of only a matte layer. In this case, the manufacturing method for the matte article I is similar to the manufacturing method for the single-layer structure described for the matte article A above, and may include a coating layer forming step of applying a resin composition for forming a matte layer to the release layer-bearing surface of a releasable support, and a matte layer forming step of curing the resin composition to form a matte layer. During the curing step, the above-described irradiation treatments (1) and (2) may be performed in sequence. Also, as in the above, a solvent drying step may be included if necessary, and the release support having the release layer may be peeled off before use.

[0309] [Other layers] The matte article I obtained by production method I may have, in addition to the matte layer as described above, other layers as needed, such as a substrate, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. Each of the above layers that the matte article I produced by production method I may have will be described below.

[0310] [Base material] As described above for Matte Article A, Matte Article I may further include a substrate in addition to the matte layer, if desired, and as described above, it is preferable to include a substrate in order to avoid various constraints. That is, the simplest layer structure of Matte Article I is a single layer structure consisting of only a matte layer without a substrate, as with Matte Article A. Furthermore, when a substrate is included, it is preferable to include a substrate on at least one surface of the matte layer opposite to the wrinkled surface, in order to improve the visibility and texture of the matte effect, as described above. The substrate that can be used in Matte Article I is the same as that described for Matte Article A above.

[0311] (Primer layer) The primer layer that the matte article I may have is the same as that described for the matte article A above.

[0312] (Transparent resin layer) The transparent resin layer that the matte article I may have is the same as that described above for the matte article A.

[0313] (decorative layer) The decorative layer that the matte article I may have is the same as that described above for the matte article A.

[0314] (adhesive layer) The adhesive layer that the matte article I may have is the same as that described above for the matte article A.

[0315] [Decorative material I] Typical uses of the matte article I obtained by production method I include using the matte article I as it is as a decorative material that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or it can be laminated, composited, or combined with an adherend to be used as a decorative material (hereinafter, such decorative materials using the matte article I may be referred to as "decorative material I"). The choice of use can be determined as desired. The form of the matte article I in the decorative member I, the adherend, the adhesive layer, the manufacturing method of the decorative member I, the uses of the decorative member I, etc. are the same as those explained for the decorative member A above.

[0316] [Article manufacturing method J] The method for manufacturing an article according to the present embodiment includes: The method includes a step of sequentially performing the following irradiation treatments (1) and (2) on a resin composition not containing a photopolymerization initiator, thereby curing the resin composition and forming a surface wrinkle layer. (hereinafter, this may be simply referred to as "Manufacturing Method J"). (1) Irradiation with light having a wavelength of 100 nm or more and less than 200 nm (2) Irradiation treatment with at least one of electron beams and light with wavelengths of 200 nm or more and 400 nm or less A manufacturing method including these steps makes it possible to easily manufacture a decorative material with excellent surface properties. Furthermore, by employing the irradiation treatments with the above characteristics (1) and (2) when curing the surface layer, excellent surface properties can be obtained without adding a photopolymerization initiator, and the matte effect can also be made visible.

[0317] Manufacturing method J differs from the manufacturing method described above as the manufacturing method for matte article A in that the resin composition may not contain a photopolymerization initiator and in that the irradiation treatment (2) above is required. However, the other aspects, such as the irradiation treatment (1), the wrinkle formation stabilizer, the matte layer (corresponding to the "surface wrinkle layer" in manufacturing method J) and its surface shape, the resin and resin composition that form the matte layer (surface wrinkle layer), the 60° gloss value of the resulting article, and each layer that constitutes the resulting article, are basically the same as those described above for matte article A. Manufacturing method J will be described in more detail below.

[0318] [Step of forming a surface wrinkle layer] The process of forming the surface wrinkle layer involves sequentially subjecting a resin composition that does not contain a photopolymerization initiator to the irradiation treatments (1) and (2) described above, thereby curing the resin composition and forming the surface wrinkle layer. Production method J includes a step of forming a wrinkled surface layer by sequentially subjecting a resin composition not containing a photopolymerization initiator to the above-mentioned two types of irradiation treatment (1) and (2) and curing the resin composition to form a wrinkled surface layer having wrinkles on at least one surface, thereby making it possible to easily produce an article with excellent surface properties. In other words, the wrinkled surface layer possessed by the article obtained by production method J can be said to be a layer having wrinkles on at least one surface obtained by sequentially subjecting a resin composition not containing a photopolymerization initiator to the above-mentioned two types of irradiation treatment (1) and (2) and curing the resin composition. Furthermore, the surface wrinkle layer preferably contains a wrinkle formation stabilizer, as described below. Even without the wrinkle formation stabilizer, the surface wrinkle layer will have wrinkles by sequentially performing the above two types of irradiation treatments, but the inclusion of the wrinkle formation stabilizer makes it easier to stabilize wrinkle formation. Furthermore, the stabilized wrinkle formation makes it easier to obtain an uneven shape formed by irregular wrinkles on at least one surface of the surface wrinkle layer, and the 60° gloss value of the surface wrinkle layer is 5.0 or less, making it easier to stably obtain excellent visibility of the matte effect.

[0319] The wrinkles in the surface wrinkle layer can provide a visible matte effect, and according to manufacturing method J, by subjecting a resin composition that does not contain a photopolymerization initiator to two specific types of irradiation treatment, not only can the resin composition be hardened to obtain excellent surface properties, but the wrinkles in the surface wrinkle layer can also provide a visible matte effect. In order to promote the formation of wrinkles in the surface wrinkle layer and to stably obtain the visibility of the matte effect, the resin composition for forming the surface wrinkle layer preferably contains a wrinkle formation stabilizer. First, the wrinkle formation stabilizer will be described.

[0320] (Wrinkle formation stabilizer) In the production method J, the wrinkle formation stabilizer preferably used is the wrinkle formation stabilizer described above as being employed in the matte article A. The fact that at least one of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, the type of wrinkle formation stabilizer, the effects achieved by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those explained for the above-mentioned matte article A.

[0321] When a wrinkle formation stabilizer is used, the content thereof is preferably 0.5 to 6.0 parts by mass per 100 parts by mass of the resin that forms the surface wrinkle layer. Other preferable ranges are the same as those described for the matte article A above.

[0322] (surface shape of the surface wrinkle layer) The surface wrinkle layer of article J (hereinafter also referred to simply as "article J") obtained by manufacturing method J is a layer composed of a cured product of a resin composition for forming a surface wrinkle layer that does not contain a photopolymerization initiator, preferably a resin composition that contains a wrinkle formation stabilizer. As described above, wrinkles are formed by two specific types of irradiation treatment, and even if the resin composition does not contain a photopolymerization initiator or a wrinkle formation stabilizer, the curing of the resin composition proceeds, resulting in a layer that not only obtains excellent surface properties but also exhibits a matte effect due to the light diffusion effect caused by the shape of the wrinkles. Furthermore, by further using a wrinkle formation stabilizer, the formation of the wrinkles is stabilized, resulting in a layer that can stably exhibit the visibility of the matte effect.

[0323] The surface shape of the wrinkled surface layer of the article J is basically the same as that described above for the matte layer of the matte article A. Figures 1 and 2 can also be applied to the wrinkled surface layer of the article J obtained by the manufacturing method J. Fig. 1 is a schematic plan view showing one embodiment of an article J obtained by manufacturing method J, and is a schematic image of the surface of the article obtained in the example. Fig. 1 shows that the article J obtained by manufacturing method J has wrinkles formed on its surface, i.e., on the surface of the surface wrinkle layer.

[0324] Regarding the surface shape of the wrinkled surface layer of Article J, even if a wrinkle formation stabilizer is not contained, at least one surface of the wrinkled surface layer has an uneven shape composed of irregular wrinkles. When a wrinkle formation stabilizer is contained, the uneven shape composed of irregular wrinkles is more stably expressed, and the visibility of the matte effect can be stably expressed. Thus, in Article J, even if a wrinkle formation stabilizer is not contained, the wrinkled surface layer is literally a layer having wrinkles and can be a layer that can express the visibility of the matte effect. However, by using a wrinkle formation stabilizer, the wrinkles are stably formed, and it can be said that the layer can be a layer that can express the visibility of the matte effect stably.

[0325] (resin) In manufacturing method J, the resin used to form the matte layer is the same as that described for matte article A above.

[0326] (Resin composition) In manufacturing method J, the resin composition used to form the matte layer (resin composition for forming the matte layer) does not contain a photopolymerization initiator and differs from the above-mentioned matte article A in that it may not contain a photopolymerization initiator. However, other additives such as various weathering agents that may be contained are the same as those described for the resin composition of the above-mentioned matte article A.

[0327] (irradiation treatment) In manufacturing method J, the above-mentioned irradiation treatments (1) and (2) must be carried out in order. These irradiation treatments are the same as those described in manufacturing method I. Note that in manufacturing method I, the irradiation treatment for (3) preliminary curing may be carried out as desired, but in manufacturing method J, (3) preliminary curing is not necessary.

[0328] (60° gloss value) Article J obtained by manufacturing method J has a visible matte effect due to the wrinkles in the surface wrinkle layer, and the visibility of this effect is improved by using a wrinkle formation stabilizer. The 60° gloss value of Article J is preferably 5.0 or less, and Article J can be said to be a matte article with a visible matte effect. Otherwise, the 60° gloss value of Article J is basically the same as that described for Matte Article A above. Therefore, the standard deviation (σ) of the 60° gloss value is also the same.

[0329] According to the manufacturing method J of this embodiment, a resin composition containing no photopolymerization initiator is used, and by performing the irradiation treatment under the specific conditions (1) and (2) above, wrinkles are formed on the surface of the wrinkled surface layer, thereby achieving a visible matte effect. Furthermore, the wrinkle formation stabilizer preferably used ensures stable visibility of the wrinkled matte effect, and by limiting the amount used to a small amount as described above, a significant increase in the viscosity of the resin composition is suppressed, facilitating layer formation, and naturally providing the surface properties, such as excellent contamination resistance, scratch resistance, and weather resistance, that correspond to the properties of the resin used for the wrinkled surface layer.

[0330] [Formation of other layers] The formation of other layers in manufacturing method J is the same as that described for manufacturing method I above. Therefore, the matte article J obtained by production method J can have a layer structure having a substrate and other layers as shown in Figures 3 and 4, or can have a layer structure having only a matte layer. In both cases where a layer structure having only a matte layer is used, and where a layer structure having a substrate and other layers is used, the production method is the same as that described for production method I above.

[0331] [Other layers] The matte article J obtained by production method J may have, in addition to the matte layer as described above, other layers as needed, such as a substrate, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. Each of the above layers that may be included in the matte article J that can be produced by production method J will be described below.

[0332] [Base material] As explained above for Matte Article A, Matte Article J may further include a substrate in addition to the matte layer, if desired, and as mentioned above, it is preferable to include a substrate in order to avoid various constraints. That is, the simplest layer structure of Matte Article J is a single layer structure consisting of only a matte layer, without a substrate, as in Matte Article A. Furthermore, when a substrate is included, it is preferable to include a substrate on at least one surface of the matte layer opposite to the wrinkled surface, in order to improve the visibility and texture of the matte effect, as mentioned above. The substrate that can be used in the matte article J is the same as that described for the matte article A above.

[0333] (Primer layer) The primer layer that the matte article J may have is the same as that described for the matte article A above.

[0334] (Transparent resin layer) The transparent resin layer that the matte article J may have is the same as that described for the matte article A above.

[0335] (decorative layer) The decorative layer that the matte article J may have is the same as that described above for the matte article A.

[0336] (adhesive layer) The adhesive layer that the matte article J may have is the same as that described above for the adhesive layer of the matte article A.

[0337] [Decorative material J] Typical uses of the article J obtained by the manufacturing method J include using the matte article J as it is as a decorative member that forms the surface of buildings, various furniture, vehicles, home appliances, etc., or it can be laminated, composited, or combined with an adherend to be used as a decorative member (hereinafter, such decorative members using the matte article J may be referred to as "decorative member J"). Which one to use can be determined as desired. The form of the matte article J in the decorative member J, the adherend, the adhesive layer, the manufacturing method of the decorative member J, the use of the decorative member J, etc. are the same as those described for the decorative member A above. [Example]

[0338] Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples in any way.

[0339] (Evaluation method: 60° gloss value) For the articles obtained in the examples and comparative examples, the 60° specular gloss was measured at any 10 points using a gloss meter ("Microgloss (model name)", manufactured by BYK Gardner) in accordance with K 5600-4-7:1999, and the average value of the 10 points was taken as the 60° gloss value.

[0340] (Standard deviation (σ) of 60° gloss value) For the articles obtained in the examples and comparative examples, the 60° specular gloss was measured at 10 random points using a gloss meter ("Microgloss (model name)" manufactured by BYK Gardner) in accordance with K 5600-4-7:1999, and the standard deviation (σ) was calculated based on the measurements at these 10 points. The standard deviation (σ) value is an index of the stability of wrinkle formation; a value of 0.3 or less indicates high stability of wrinkle formation, while a value of less than 0.30 indicates insufficient stability of wrinkle formation.

[0341] (Evaluation of texture (uniformity of surface condition)) The surface texture (uniformity of surface condition) of the articles obtained in the Examples and Comparative Examples was evaluated by 20 random adults, and the evaluation was based on the following criteria. A: 18 or more people evaluated that the surface condition was uniform and the matte effect was highly visible. B: 15 or more and 17 or less judged that the surface condition was uniform and the matte effect was highly visible. C: 14 or less people evaluated that the surface condition was uniform and the matte effect was highly visible.

[0342] (Evaluation of scratch resistance (steel wool resistance)) The following rubbing test was carried out on the articles obtained in Examples 1A to 3A and Comparative Examples 1A and 2A. The 60° gloss value of the matte layer side before the rubbing test was defined as G0, and the 60° gloss value of the matte layer side after the rubbing test was defined as G1. The rate of change in gloss value (|(G1-G0)| / G0×100) was calculated. A change of 20% or less was deemed to have excellent steel wool resistance and was rated as passing. (Rubbing test) The obtained article was placed on the base of an abrasion tester, Type II (JIS L0849:2013), and steel wool #0000 was set so that it was in contact with the matte layer of the matte article. A load of 1500 g / cm was applied. 2 The sample was moved back and forth 30 times at a moving speed of 100 mm / sec and a moving distance of 100 mm.

[0343] (Evaluation of abrasion resistance (scratch resistance)) The articles obtained in Examples 1A to 3A and Comparative Examples 1A and 2A were subjected to a scratch test using a paint adhesion tester (Hoffman Scratch Hardness Tester (product name), manufactured by BYK Gardner) to measure the maximum load at which continuous scratches did not occur. A higher maximum load indicates better abrasion resistance (scratch resistance).

[0344] (Evaluation of ease of decontamination) For the articles obtained in Examples 1E to 3E and Comparative Examples 1E and 2E, a staining test was conducted in accordance with "15.3 C Method" of JIS K6902:2007 (Testing Methods for Thermosetting Resin High-Pressure Decorative Laminates) using acetone (material number 3), household ammonia (material number 4), 10% citric acid (material number 5), black oil-based marker (material number 12), and crayon (material number 14) as staining substances, and cleanability was evaluated according to a scale of 0 to 5 based on "15.3.5.2 Cleaning Procedure." The closer to grade 0, the better the cleanliness. In addition, stain resistance was evaluated based on the criteria of grades 5, 3, and 1 in accordance with "15.3.6.2 Stain Resistance." The closer to grade 5, the better the stain resistance. The above was the evaluation of ease of decontamination.

[0345] (Evaluation of light resistance) The articles obtained in Examples 1F to 3F and Comparative Examples 1F to 3F were subjected to a 200-hour weather resistance test using an "S-UV (rain)" weather resistance tester. The 60° gloss value of the matte light-resistant layer side before the weather resistance test was defined as G0, and the 60° gloss value of the matte light-resistant layer side after the weather resistance test was defined as G1. The rate of change in gloss value (|(G1-G0)| / G0×100) was calculated. A change of 20% or less was deemed to have excellent light resistance and was rated as passing.

[0346] (Evaluation of marker erasability) The products obtained in Examples 1G to 3G and Comparative Examples 1G and 2G were subjected to a test for the ease of removal of the marker, using a black marker as specified in JIS S6052:2014, according to the following methods a) to c). The lightness and chromaticity before and after the test were measured using a spectrophotometer (model "SE6000", manufactured by Nippon Denshoku Industries Co., Ltd.), and the color difference (ΔE * ab) was calculated. ΔE * ab=〔(L * 2-L * 1) 2 +(a * 2-a * 1) 2 +(b *2-a * 2) 2 〕 1 / 2 (Marker removal test) a) Use the marker to fill in an area of ​​2cm x 4cm on the matte writing layer of the sheet. b) After one minute has passed since the marking, erase the marking using an unused melamine foam whiteboard eraser (2cm x 2cm, whiteboard eraser (Auto Co., Ltd.)). c) Repeat steps a) and b) above 50 times.

[0347] Example 1A A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). On the primer layer, a resin composition for forming a matte layer (polyfunctional urethane (meth)acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied by a gravure method (coating amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate was then irradiated with ultraviolet light (wavelength: 365 nm, UV output density: 200 W / cm) using a high-pressure mercury lamp to form a matte layer on the substrate, yielding a matte article comprising a substrate and a matte layer. The 60° gloss value and the rate of change in gloss value of the resulting matte article were measured using the methods described above. The measurement results are shown in Table 1A.

[0348] [Examples 2A and 3A] Matte articles were obtained in the same manner as in Example 1A, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte layer was changed to the amount shown in Table 1A. The 60° gloss value and the rate of change in gloss value of the matte layer side of the obtained matte articles are shown in Table 1A.

[0349] [Comparative Example 1A] An article was obtained in the same manner as in Example 1A, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value and the rate of change in gloss value of the matte layer side of the obtained article are shown in Table 1A.

[0350] [Comparative example 2A] An article was obtained in the same manner as in Example 1A, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used instead, and only electron beam irradiation was performed (acceleration voltage: 75 kV, exposure dose: 30 kGy (3 Mrad)). The 60° gloss value and gloss value change rate of the matte layer side of the obtained article are shown in Table 1A.

[0351] [Table 1]

[0352] The results in Table 1A confirm that the 60° gloss value of the matte layer side of the matte article A of this embodiment is 2.0 or less, demonstrating excellent visibility of the matte effect. Regarding abrasion resistance, the gloss value change rate was 20% or less, and the scratch resistance was 400 g, demonstrating excellent abrasion resistance (steel wool resistance and scratch resistance). Furthermore, the standard deviation (σ) was less than 0.30, confirming stable wrinkle formation. It is believed that stable wrinkle formation contributes to the visibility of the matte effect, texture, and abrasion resistance.

[0353] On the other hand, the product of Comparative Example 1A, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 8, but the matte effect was not consistently visible, and although there were some areas where the gloss value was the same as in the Examples, there were also some areas where the gloss was high, making the surface condition unstable and it could not be said to have an excellent texture. The instability can also be seen from the fact that the standard deviation of the gloss value was 0.30 or more. The article of Comparative Example 2A, which contained a matting agent (15.0 parts by mass), was found to contain no wrinkles in the surface layer corresponding to the matte layer, and its 60° gloss value was 8.3, which was inferior to the gloss values ​​of the matte articles of the Examples, and it was also found to have an inferior texture. Furthermore, the gloss value change rate of the article of Comparative Example 2A was 23.7%, and its scratch resistance was 300 g, confirming its poor abrasion resistance.

[0354] Furthermore, optical microscope images of Examples 1A to 3A (FIGS. 5 to 7, respectively) confirm that the matte articles of these Examples have irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1A (FIG. 8) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2A (FIG. 9) reveals no wrinkles like those observed on the matte articles of the Examples, and instead reveals a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article A of this embodiment exhibits an extremely excellent matte effect due to the wrinkles on its surface. Furthermore, the matte article A of this embodiment exhibits a high surface texture and a luxurious feel due to the formation of wrinkles. However, although the surface of Comparative Example 1A had slight wrinkles, it did not consistently achieve a matte effect, and the surface texture was monotonous, making it less luxurious.

[0355] Example 1B A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). On the primer layer, a resin composition for forming a matte layer (polyfunctional urethane (meth)acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied by a gravure method (coating amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate was then irradiated with ultraviolet light from a high-pressure mercury lamp (wavelength: 365 nm, UV output density: 200 W / cm) to form a matte layer on the substrate, thereby obtaining a matte article having a substrate and a matte layer. The 60° gloss value of the obtained matte article was measured from the matte layer side and was found to be 1.4.

[0356] [Examples 2B and 3B] A matte article was obtained in the same manner as in Example 1B, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte layer was changed to the amount shown in Table 1B. The 60° gloss value and texture evaluation of the matte layer side of the obtained matte decorative material are shown in Table 1B. The texture evaluation is also shown in Table 1B.

[0357] [Comparative example 1B] An article was obtained in the same manner as in Example 1B, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1B.

[0358] [Comparative Example 2B] An article was obtained in the same manner as in Example 1B, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used instead, and only electron beam irradiation was performed (acceleration voltage: 75 kV, exposure dose: 30 kGy (3 Mrad)). The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1B.

[0359] [Table 2]

[0360] The results in Table 1B confirm that the 60° gloss value of the matte layer side of the matte article B of this embodiment is 1.8 or less, and that the article has extremely excellent visibility of the matte effect and excellent texture. Furthermore, the standard deviation (σ) is less than 0.30, which confirms that wrinkle formation is stable, and it is believed that the stable wrinkle formation is linked to the visibility of the matte effect and texture.

[0361] On the other hand, the product of Comparative Example 1B, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 13, but the matte effect was not consistently visible, and although there were some areas where the gloss value was the same as in the Examples, there were also some areas where the gloss was high, making the surface condition unstable (not uniform) and it could not be said to have an excellent texture. The instability can also be seen from the fact that the standard deviation of the gloss value was 0.30 or more. Furthermore, even though the article of Comparative Example 2B, which contained a matting agent, contained 15.0 parts by mass, which was greater than the amount of wrinkle formation stabilizer contained in the Examples, no wrinkles formed in the surface layer corresponding to the matte layer, and its 60° gloss value was 8.3, which was inferior to the gloss value of the matte articles of the Examples, and it was confirmed that the texture was also inferior.

[0362] Furthermore, optical microscope images of Examples 1B to 3B (FIGS. 10 to 12, respectively) confirm that the matte decorative materials of these Examples have irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1B (FIG. 13) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2B (FIG. 14) reveals no wrinkles like those of Matte Article B of the Examples, and instead reveals a convex shape corresponding to the contour shape of the matting agent. These results confirm that Matte Article B of this embodiment exhibits an extremely excellent matte effect in visibility and texture due to the wrinkles on its surface.

[0363] Example 1C A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). A resin composition for forming a matte layer (multifunctional urethane (meth)acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle diameter: 3 μm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied on the primer layer by a gravure method (coating amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm 2), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate was then irradiated with ultraviolet light from a high-pressure mercury lamp (ultraviolet output density: 200 W / cm) to form a matte layer on the substrate, yielding a matte article comprising a substrate and a matte layer. The 60° gloss value of the resulting matte article was measured from the matte layer side and found to be 1.5. The texture evaluation is also shown in Table 1C.

[0364] [Examples 2C and 3C] Matte articles were obtained in the same manner as in Example 1C, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte layer was changed to the amount shown in Table 1C. The 60° gloss value and texture evaluation of the matte layer side of the obtained matte articles are shown in Table 1C.

[0365] [Comparative example 1C] An article was obtained in the same manner as in Example 1C, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1C.

[0366] [Comparative Example 2C] An article was obtained in the same manner as in Example 1C, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used instead, and only electron beam irradiation was performed (acceleration voltage: 75 kV, exposure dose: 30 kGy (3 Mrad)). The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1C.

[0367] [Table 3]

[0368] The results in Table 1C confirm that the 60° gloss value of the matte layer side of the matte article C of this embodiment is 1.8 or less, and that the article has extremely excellent visibility of the matte effect. Furthermore, the standard deviation (σ) is less than 0.30, which confirms that wrinkle formation is stable. It is believed that the stable wrinkle formation is linked to the visibility and texture of the matte effect.

[0369] On the other hand, the product of Comparative Example 1C, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 18, but the matte effect was not consistently visible, and although there were some areas where the gloss value was the same as in the Examples, there were also some areas where the gloss was high, making the surface condition unstable (not uniform) and it could not be said to have an excellent texture. The instability can also be seen from the fact that the standard deviation of the gloss value was 0.30 or more. Furthermore, the decorative material of Comparative Example 2C, which contains a large amount of matting agent, does not form wrinkles in the surface layer corresponding to the matte layer, and its 60° gloss value is 8.3, which is inferior to the gloss value of the matte articles of the Examples, and it was confirmed that the texture is also inferior.

[0370] Furthermore, optical microscope images of Examples 1C to 3C (FIGS. 15 to 17, respectively) confirm that the matte articles of these Examples have irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1C (FIG. 18) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2C (FIG. 19) reveals no wrinkles like those of the matte articles of the Examples, but rather a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article C of this embodiment exhibits an extremely excellent matte effect in visibility and texture due to the wrinkles on its surface.

[0371] Example 1D A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). A resin composition for forming a matte layer (multifunctional urethane acrylate oligomer (number of functional groups: 4): 65 parts by mass, multifunctional acrylate monomer (number of functional groups: 4): 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle diameter: 5 nm): 5.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied on the primer layer by a gravure method (coating amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate was then irradiated with ultraviolet light from a high-pressure mercury lamp (ultraviolet output density: 200 W / cm) to form a matte layer on the substrate, thereby obtaining a matte article having a substrate and a matte layer. The 60° gloss value of the obtained matte article was measured from the matte layer side and was found to be 1.5.

[0372] Examples 2D and 3D Matte articles were obtained in the same manner as in Example 1D, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte layer was changed to the amount shown in Table 1D. The 60° gloss value and texture evaluation of the matte layer side of the obtained matte articles are shown in Table 1D. The texture evaluation is also shown in Table 1D.

[0373] [Comparative Example 1D] An article was obtained in the same manner as in Example 1D, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1D.

[0374] [Comparative example 2D] An article was obtained in the same manner as in Example 1D, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used instead, and only electron beam irradiation was performed (acceleration voltage: 75 kV, exposure dose: 30 kGy (3 Mrad)). The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1D.

[0375] [Table 4]

[0376] The results in Table 1D confirm that the 60° gloss value of the matte layer side of the matte article D of this embodiment is 2.0 or less, and that the article has extremely excellent visibility of the matte effect and excellent texture. Furthermore, the standard deviation (σ) is less than 0.30, which confirms that wrinkle formation is stable. It is believed that the stable wrinkle formation contributes to the visibility of the matte effect and texture.

[0377] On the other hand, the product of Comparative Example 1D, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 23, but the matte effect was not consistently visible, and although there were some areas where the gloss value was the same as in the Examples, there were also some areas where the gloss was high, making the surface condition unstable (not uniform) and it could not be said to have an excellent texture. The instability can also be seen from the fact that the standard deviation of the gloss value was 0.30 or more. Furthermore, even though the decorative material of Comparative Example 2D, which contains a matting agent, contained 15.0 parts by mass, which is greater than the amount of wrinkle formation stabilizer contained in the Examples, no wrinkles formed in the surface layer corresponding to the matte layer, and its 60° gloss value was 8.3, which was inferior to the gloss value of the matte articles of the Examples, and it was confirmed that the texture was also inferior.

[0378] Furthermore, optical microscope images of Examples 1D to 3D (FIGS. 20 to 22, respectively) confirm that the matte decorative materials of these Examples have irregular wrinkles uniformly distributed across their entire surfaces. On the other hand, an optical microscope image of Comparative Example 1D (FIG. 23) reveals, as previously mentioned, that slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2D (FIG. 24) reveals no wrinkles like those of the matte articles of the Examples, but rather a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article D of this embodiment exhibits an extremely excellent matte effect in visibility and texture due to the wrinkles on its surface.

[0379] Example 1E A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). On the primer layer, a resin composition for forming a matte, easily decontaminationable layer (multifunctional urethane (meth)acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied by a gravure method (coating amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2The substrate was then irradiated with ultraviolet light (wavelength: 365 nm, ultraviolet output density: 200 W / cm) in a nitrogen atmosphere (oxygen concentration 200 ppm or less), and then further irradiated with ultraviolet light using a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm) to form a matte, easy-to-decontaminate layer on the substrate, thereby obtaining a matte article having a substrate (sheet) and a matte, easy-to-decontaminate layer. The 60° gloss value of the obtained matte article was measured using the above-mentioned method. The measurement results are shown in Table 1E. The ease of decontamination was also evaluated using the above-mentioned method. The evaluation results are shown in Table 1E.

[0380] [Examples 2E and 3E] A matte article was obtained in the same manner as in Example 1E, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte, easy-to-decontaminate layer was changed to the amount shown in Table 1E. The 60° gloss value of the obtained matte article was measured using the method described above. The measurement results are shown in Table 1E. The ease of decontamination was also evaluated using the method described above. The evaluation results are shown in Table 1E.

[0381] [Comparative Example 1E] An article was obtained in the same manner as in Example 1E, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte, easy-to-decontaminate layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value of the obtained article was measured using the above-mentioned method. The measurement results are shown in Table 1E. Furthermore, the ease of decontamination was evaluated using the above-mentioned method. The evaluation results are shown in Table 1E.

[0382] [Comparative Example 2E] In Example 1E, an article was obtained in the same manner as in Example 1E, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte, easy-to-decontaminate layer was 0 parts by mass, and instead 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used, and only electron beams (acceleration voltage: 75 kV, exposure dose: 3 c0 kGy (3 Mrad)) were irradiated. The 60° gloss value of the obtained article was measured using the above-mentioned method. The measurement results are shown in Table 1E. The ease of decontamination was also evaluated using the above-mentioned method. The evaluation results are shown in Table 1E.

[0383] [Table 5]

[0384] From the results of Table 1E, it was confirmed that the 60° gloss value of the matte, easy-to-decontaminate layer side of the matte article E of this embodiment is 1.8 or less, and that the article has extremely excellent visibility of the matte effect. Regarding the ease of decontamination, the cleanability was graded 3 for black oil-based markers and crayons, but graded 0 for other contaminants, demonstrating excellent cleanability. In addition, the stain resistance was graded 5 for all contaminants, demonstrating excellent stain resistance, confirming that the article has excellent easy decontamination properties. Furthermore, it was confirmed that wrinkle formation was stable because the standard deviation (σ) was less than 0.30, and it is believed that the stability of wrinkle formation is linked to the visibility, texture, and stain resistance of the matte effect.

[0385] On the other hand, the product of Comparative Example 1E, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 28, but the matte effect was not consistently visible, and although there were some areas where the gloss value was the same as in the Examples, there were also some areas where the gloss was high, making the surface condition unstable and it could not be said to have an excellent texture. The instability can also be seen from the fact that the standard deviation of the gloss value was 0.30 or more. Even though the article of Comparative Example 2E, which contains a matte agent, contained 15.0 parts by mass, which is greater than the amount of wrinkle formation stabilizer in the examples, no wrinkles formed in the surface layer corresponding to the matte, easy-to-decontaminate layer, and its 60° gloss value was 8.3, which was inferior to the gloss value of the matte articles of the examples, and it was also confirmed to have an inferior texture. Furthermore, with regard to the ease of decontamination of the item of Comparative Example 2E, the cleanability of black oil-based markers and crayons was graded 4 and 5, respectively, and the stain resistance was graded 3 and 1, respectively, confirming that the item had poor ease of decontamination.

[0386] Furthermore, optical microscope images of Examples 1E to 3E (FIGS. 25 to 27, respectively) confirm that the matte articles of these Examples have irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1E (FIG. 28) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2E (FIG. 29) reveals no wrinkles like those observed on the matte articles of the Examples, and instead reveals a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article E of this embodiment exhibits an excellent visibility of the matte effect due to the wrinkles on its surface. Furthermore, the matte article E of this embodiment exhibits a high-quality surface texture and a luxurious feel due to the formation of wrinkles. However, although the surface of Comparative Example 1E had slight wrinkles, the matte effect was not consistently visible, and the surface texture was monotonous, making it less luxurious.

[0387] [Example 1F] A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by gravure coating to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied to the colored layer to form a primer layer (thickness: 2 μm). A resin composition for forming a matte light-resistant layer (multifunctional urethane (meth)acrylate) was applied to the primer layer. The following mixture was applied by gravure coating (amount applied: 5 g / m): 65 parts by mass of tri-oligomer, 35 parts by mass of monofunctional acrylate monomer, 3.0 parts by mass of wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm), 3.0 parts by mass of wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm), 1.0 part by mass of ultraviolet absorber (trade name: ADK STAB LA-46, hydroxyphenyltriazine-based ultraviolet absorber, manufactured by ADEKA CORPORATION), and 0.8 parts by mass of photopolymerization initiator (benzophenone-based). 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate was then irradiated with ultraviolet light (wavelength: 365 nm, UV output density: 200 W / cm) in a nitrogen atmosphere (oxygen concentration: 200 ppm or less), and then further irradiated with ultraviolet light using a high-pressure mercury lamp (wavelength: 365 nm, UV output density: 200 W / cm), thereby forming a matte light-resistant layer on the substrate, and a matte article having a substrate sheet and a matte light-resistant layer was obtained. The 60° gloss value and the rate of change in gloss value of the obtained matte article were measured using the above-mentioned methods. The measurement results are shown in Table 1F. The evaluation results evaluated using the above-mentioned methods are also shown in Table 1F.

[0388] [Examples 2F and 3F] Matte articles were obtained in the same manner as in Example 1F, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte light-resistant layer was changed to the amount shown in Table 1F. The 60° gloss value and the rate of change in gloss value of the matte light-resistant layer side of the obtained matte articles are shown in Table 1F. The evaluation results evaluated by the above-mentioned methods are also shown in Table 1F.

[0389] [Comparative Example 1F] An article was obtained in the same manner as in Example 1F, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte light-resistant layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value and the rate of change in gloss value of the matte light-resistant layer side of the obtained article are shown in Table 1F. The evaluation results evaluated by the above methods are also shown in Table 1F.

[0390] [Comparative Example 2F] An article was obtained in the same manner as in Example 1F, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte light-resistant layer was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used instead, and only ultraviolet light (wavelength: 365 nm, ultraviolet output density: 200 W / cm) was irradiated using a high-pressure mercury lamp. The 60° gloss value and the rate of change in gloss value of the matte light-resistant layer side of the obtained article are shown in Table 1F. The evaluation results evaluated using the above methods are also shown in Table 1F.

[0391] [Comparative Example 3F] An article was obtained in the same manner as in Example 1F, except that the amount of UV absorber used in the resin composition for forming the matte light-resistant layer was 0 parts by mass, i.e., no UV absorber was used. The 60° gloss value and the rate of change in gloss value of the matte light-resistant layer side of the obtained article are shown in Table 1F. The evaluation results evaluated by the above methods are also shown in Table 1F.

[0392] [Table 6]

[0393] The results in Table 1F confirm that the 60° gloss value of the matte light-resistant layer side of the matte article F of this embodiment is 1.8 or less, which indicates that the matte effect is highly visible and that the article also has excellent texture. Regarding light resistance, the gloss value change rate was 20% or less in all cases, which indicates that the article has excellent light resistance. Furthermore, it was confirmed that wrinkle formation was stable because the standard deviation (σ) was less than 0.30, and it is believed that the stability of wrinkle formation is linked to the visibility, texture, and light resistance of the matte effect.

[0394] On the other hand, the product of Comparative Example 1F, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 33, but the matte effect was not consistently visible, and although there were some areas where the gloss value was the same as in the Examples, there were also some areas where the gloss was high, making the surface condition unstable and it could not be said to have an excellent texture. The instability can also be seen from the fact that the standard deviation of the gloss value was 0.30 or more. The article of Comparative Example 2F, which contained a matting agent, contained 15.0 parts by mass, which was greater than the content of the wrinkle formation stabilizer in the Examples, but no wrinkles formed in the surface layer corresponding to the matte light-resistant layer, and its 60° gloss value was 8.3, which was inferior to the gloss value of the matte articles of the Examples. It was confirmed that even if a greater amount of matting agent was used than the amount of wrinkle formation stabilizer used in the Examples, the 60° gloss value of the Examples was not achieved. Furthermore, the article of Comparative Example 3F, which did not contain an ultraviolet absorber, contained a wrinkle formation stabilizer, so its 60° gloss value before the test was small at 1.4, and although it had excellent texture, its 60° gloss value increased by 64.3%, and it could not be said to have excellent lightfastness.

[0395] Furthermore, optical microscope images of Examples 1F and 2F (FIGS. 30 and 31, respectively) confirm that the matte articles of these Examples have uniformly irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1F (FIG. 32) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2F (FIG. 33) reveals no wrinkles like those of the matte articles of the Examples, but rather a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article F of this embodiment exhibits an extremely excellent matte effect with visibility due to the wrinkles on its surface.

[0396] [Example 1G] A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). On the primer layer, a resin composition for forming a matte writing layer (polyfunctional urethane (meth)acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm): 3 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied by a gravure method (coating amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate was then irradiated with ultraviolet light from a nitrogen atmosphere (oxygen concentration 200 ppm or less), and then further irradiated with ultraviolet light from a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm), forming a matte writing layer on the substrate, thereby obtaining a matte article having a substrate and a matte writing layer. The 60° gloss value of the obtained matte article was measured using the method described above. The measurement results are shown in Table 1G. The marker erasability was also evaluated using the method described above. The evaluation results are shown in Table 1G.

[0397] [Examples 2G and 3G] A matte article was obtained in the same manner as in Example 1G, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte writing layer was changed to the amount shown in Table 1G. The 60° gloss value of the obtained matte article was measured using the method described above. The measurement results are shown in Table 1G. In addition, marker erasability was evaluated using the method described above. The evaluation results are shown in Table 1G.

[0398] [Comparative Example 1G] An article was obtained in the same manner as in Example 1G, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte writing layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value of the obtained article was measured using the method described above. The measurement results are shown in Table 1G. Marker erasability was also evaluated using the method described above. The evaluation results are shown in Table 1G.

[0399] [Comparative Example 2G] An article was obtained in the same manner as in Example 1G, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte writing layer was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used instead, and only electron beam irradiation was performed (acceleration voltage: 75 kV, exposure dose: 30 kGy (3 Mrad)). The 60° gloss value of the obtained article was measured using the method described above. The measurement results are shown in Table 1G. In addition, marker erasability was evaluated using the method described above. The evaluation results are shown in Table 1G.

[0400] [Table 7]

[0401] The results in Table 1G confirm that the 60° gloss value of the matte writing layer side of the matte article G of this embodiment is 2.0 or less, and that the article has excellent visibility due to the matte effect. Furthermore, the color difference in terms of marker erasability is small and excellent, and the texture is also excellent. Furthermore, it was confirmed that the standard deviation (σ) was less than 0.30, so that wrinkle formation was stable, and it is believed that the stability of wrinkle formation is linked to the visibility of the matte effect, texture, and marker erasability.

[0402] On the other hand, the article of Comparative Example 1, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 39, but did not provide stable visibility due to the matte effect, and although there were some areas where the gloss value was the same as in the Examples, there were also some areas where the gloss was high, making the surface condition unstable (not uniform) and it could not be said to have an excellent texture. The instability can also be seen from the fact that the standard deviation of the gloss value was 0.30 or more. The article of Comparative Example 2G, which contained a matting agent but had not been irradiated with excimer light on its surface, had no wrinkles on the surface layer corresponding to the matte writing layer, and its 60° gloss value was 8.3, which was inferior to the gloss value of the writing sheet of the example, confirming that it had inferior visibility due to the matte effect and also inferior texture. It was also confirmed that the marker erasability of the article of Comparative Example 2G was poor, with a large color difference.

[0403] Furthermore, optical microscope images of Examples 1G to 3G (FIGS. 36 to 38, respectively) confirm that the matte articles of these Examples have uniformly irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1G (FIG. 39) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2G (FIG. 40) reveals no wrinkles like those of the matte articles of the Examples, and instead reveals a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article G of this embodiment exhibits excellent visibility due to the wrinkles on its surface, and also exhibits excellent marker erasability, resulting in an excellent texture.

[0404] Example 1H A corona discharge-treated PET sheet (thickness: 100 μm) was used as a substrate, and a resin composition containing an acrylic resin and a urethane resin as binder resins was applied to one side of the substrate to form a primer layer (thickness: 2 μm). Onto the primer layer, a resin composition for forming a matte layer (polyfunctional urethane (meth)acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle diameter: 3 μm): 1.0 part by mass, photopolymerization initiator (benzophenone type): 0.8 part by mass) was applied by gravure method (application amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 0.6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate sheet was then irradiated with ultraviolet light (wavelength: 365 nm, ultraviolet output density: 200 W / cm) in a nitrogen atmosphere (oxygen concentration: 200 ppm or less), and then further irradiated with ultraviolet light using a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm) to form a matte layer on the substrate sheet, thereby obtaining a matte article having a substrate (sheet) and a matte layer.

[0405] Next, titanium paper base paper ("PM-602K (product name), manufactured by KJ Specialty Paper Co., Ltd., basis weight: 60 g / m 2 A thermosetting uncured resin composition containing 60 parts by mass of melamine formaldehyde resin, 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was impregnated onto a substrate (thickness: 100 μm) using an impregnation device so that the uncured resin composition was 60 g / m 2 The resin was impregnated to a ratio of 100% (when dried) and then dried to obtain a resin-impregnated decorative sheet. The obtained resin-impregnated decorative sheet was then coated with a reinforcing layer (a 245 g / m2 substrate obtained by impregnating kraft paper with a liquid uncured resin composition made of phenolic resin). 2The titanium paper base paper and the reinforcing layer were laminated on top of three layers of phenolic resin-impregnated core paper ("Ohta Core," manufactured by Ohta Sangyo Co., Ltd.) so that they were in contact with each other, and then laminated so that the decorative layer of the resin-impregnated decorative sheet faced the matte-imparting layer of the matte product. This was sandwiched between two mirror-finished plates and heat-molded using a heat press at a pressure of 0.98 MPa and a heating temperature of 150°C for 10 minutes to thermoset the uncured resin composition, forming a cured resin layer containing melamine resin. The matte product was peeled off from the thermosetting resin layer to obtain a resin decorative material (melamine resin decorative board) molded to the shape (matte surface) of the matte-imparting layer of the matte product. The 60° gloss value of the surface of the resulting matte decorative material on which the matte surface was molded was measured using the method described above. The measurement results are shown in Table 1H.

[0406] [Example 2H] A matte article was obtained in the same manner as in Example 1H, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte layer was changed to the amount shown in Table 1H. A matte decorative material (melamine resin decorative board) was obtained using the obtained matte article in the same manner as in Example 1H. The 60° gloss values ​​of the obtained matte decorative material are also shown in Table 1H.

[0407] [Comparative Example 1H] An article was obtained in the same manner as in Example 1H, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass. A decorative material (melamine resin decorative board) was obtained using the obtained article in the same manner as in Example 1H. The 60° gloss values ​​of the obtained decorative material are also shown in Table 1H.

[0408] [Comparative example 2H] In Example 1H, the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, and 15.0 parts by mass of a matting agent (average particle diameter: 5.0 μm) was used instead, and an article was obtained in the same manner as in Example 1H, except that ultraviolet light was irradiated using a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm). A decorative material (melamine resin decorative board) was obtained using the obtained article in the same manner as in Example 1H. The 60° gloss values ​​of the obtained decorative material are also shown in Table 1H.

[0409] [Table 8]

[0410] From the results in Table 1H, it was confirmed that the matte decorative material obtained using matte article H of this embodiment has a 60° gloss value of 1.4 to 1.8, and is a matte article that can impart an extremely excellent matte effect with visibility. Furthermore, it was confirmed that the standard deviation (σ) was less than 0.30, so that wrinkle formation was stable, and it is believed that the stable formation of wrinkles leads to the visibility of the matte effect and the provision of texture.

[0411] On the other hand, the article of Comparative Example 1H, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 46, but the matte effect was not consistently visible, and an excellent texture could not be imparted. The fact that a stable matte effect could not be obtained is also evident from the fact that the standard deviation of the gloss value was 0.30 or more. Although the product of Comparative Example 2H, which contained a matting agent, contained 15.0 parts by mass, which was a greater amount than the wrinkle formation stabilizer content in the Examples, no wrinkles formed in the surface layer corresponding to the matte-imparting layer, and the decorative material obtained using this had a 60° gloss value of 8.3, which was inferior to the gloss value of the matte-imparting sheet of the Examples, despite the use of a greater amount of matting agent than the wrinkle formation stabilizer in the Examples, and it was confirmed that the texture was also inferior.

[0412] Furthermore, optical microscope images of Examples 1H to 3H (FIGS. 43 to 45, respectively) confirm that the matte-type sheets of these Examples have uniformly irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1H (FIG. 46) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2H (FIG. 47) reveals no wrinkles like those of the matte articles of the Examples, but rather a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article H of this embodiment exhibits an extremely excellent matte effect visibility due to the wrinkles on its surface, and can impart excellent matte effect visibility and texture to the surface.

[0413] [Example 1I] A corona discharge-treated polypropylene sheet (thickness: 100 μm) was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). A resin composition for forming a matte layer (polyfunctional urethane (meth)acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle diameter: 3 μm): 3 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied on the primer layer by a gravure method (coating amount: 5 g / m 2 (drying)), and then irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (wavelength: 395 nm, ultraviolet light intensity: 6 W / cm 2 ), and then irradiated with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe), ultraviolet light output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2The substrate was then irradiated with an electron beam (acceleration voltage: 75 kV, exposure dose: 30 kGy (Mrad)) to form a matte layer on the substrate, yielding a matte article having a substrate and a matte layer. The 60° gloss value of the resulting matte article was measured from the matte layer side and was found to be 1.5.

[0414] [Examples 2I and 3I] Matte articles were obtained in the same manner as in Example 1I, except that the amount of wrinkle formation stabilizer in the resin composition for forming the matte layer was changed to the amount shown in Table 1I. The 60° gloss value and texture evaluation of the matte layer side of the obtained matte articles are shown in Table 1I.

[0415] [Example 4I] A matte article was obtained in the same manner as in Example 1I, except that the electron beam was replaced with ultraviolet light (wavelength: 365 nm, ultraviolet light output density: 200 W / cm) using a high-pressure mercury lamp. The 60° gloss value and texture evaluation of the matte layer side of the obtained matte article are shown in Table 1I.

[0416] [Comparative Example 1I] An article was obtained in the same manner as in Example 1I, except that the amount of wrinkle formation stabilizer used in the resin composition for forming the matte layer was 0 parts by mass, i.e., no wrinkle formation stabilizer was used. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1I.

[0417] [Comparative Example 2I] An article was obtained in the same manner as in Example 1I, except that the amount of wrinkle formation stabilizer used was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle diameter: 8.0 μm) was used, and the irradiation treatment (1) was not performed, and only electron beam irradiation (acceleration voltage: 75 kV, exposure dose: 30 kGy (3 Mrad)) was performed. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1I.

[0418] [Comparative Example 3I] An article was obtained in the same manner as in Example 1I, except that the irradiation treatment (electron beam irradiation) in (2) was not performed. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1I.

[0419] [Comparative Example 4I] An article was obtained in the same manner as in Example 1I, except that the irradiation treatment (1) in Example 1I was not performed. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1I.

[0420] [Comparative Example 5I] An article was obtained in the same manner as in Example 4I, except that the irradiation treatment (1) in Example 4I was not performed. The 60° gloss value and texture evaluation of the matte layer side of the obtained article are shown in Table 1I.

[0421] [Table 9] *1 The surface layer did not harden, so the gloss value could not be measured and the texture could not be evaluated.

[0422] From the results in Table 1I, it was confirmed that the matte articles of the Examples had a 60° gloss value of 2.0 or less on the matte layer side, and were articles with extremely excellent visibility of the matte effect and excellent texture. From the above, it was confirmed that the matte article I obtained by production method I of this embodiment has excellent surface properties and excellent visibility of the matte effect, and it was also confirmed that matte article I can be easily produced by production method I of this embodiment.

[0423] On the other hand, the article of Comparative Example 1I, which did not contain a wrinkle formation stabilizer, had some wrinkles on its surface as shown in Figure 51, but the matte effect was not consistently visible. Although there were some areas with the same gloss value as the Examples, there were also some areas with high gloss, making the surface condition unstable (not uniform), and it could not be said to have excellent texture. The article of Comparative Example 2I, which contained a matte agent, contained 15.0 parts by mass, which is greater than the amount of wrinkle formation stabilizer used in the Examples. However, no wrinkles were formed in the surface layer corresponding to the matte layer, and the 60° gloss value was 8.3, which was inferior to the gloss value of the matte article of the Examples, and it was also confirmed that the texture was inferior. In Comparative Example 3I, which did not undergo the irradiation treatment (2), wrinkles were formed and cured only on the outermost surface, but the interior of the surface layer was uncured, making it impossible to measure the 60° gloss value. Therefore, the surface properties were poor, and the texture could not be evaluated. In addition, in the articles of Comparative Example 4I, which did not undergo the irradiation treatment (1) but underwent the electron beam irradiation treatment (2), and Comparative Example 5I, which did not undergo the irradiation treatment (1) but underwent the ultraviolet irradiation treatment (2), wrinkles did not form, so the gloss value was extremely high and the matte effect was not visible.On the other hand, because the gloss value was high, problems with the texture evaluation (uniformity of surface condition) were not noticeable, and the results were good.

[0424] Optical microscope images of Examples 1I to 3I (FIGS. 48 to 50, respectively) confirm that the matte articles of these Examples have irregular wrinkles on their surfaces. On the other hand, an optical microscope image of Comparative Example 1I (FIG. 51) reveals that, as mentioned above, slight wrinkles have occurred on the surface, and although there are areas with wrinkles similar to those of the Examples, the wrinkle formation is unstable (not uniform), and wrinkle-free areas are mixed in. Furthermore, an optical microscope image of Comparative Example 2I (FIG. 52) reveals no wrinkles like those of the matte articles of the Examples, and instead reveals a convex shape corresponding to the contour shape of the matting agent. These results confirm that the matte article I obtained by Manufacturing Method I of this embodiment exhibits an extremely excellent matte effect due to the wrinkles on its surface.

[0425] [Example 1J] A corona discharge-treated polypropylene sheet (thickness: 100 μm) was used as a substrate, and a printing ink (binder resin: two-component curing acrylic-urethane resin) was applied to one side of the substrate by a gravure method to form a colored layer (thickness: 3 μm). A resin composition containing an acrylic resin and a urethane resin as binder resins was applied on the colored layer to form a primer layer (thickness: 2 μm). A resin composition for forming a surface wrinkle layer (multifunctional urethane (meth)acrylate oligomer: 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle diameter: 3 μm): 3 parts by mass) was applied on the primer layer by a gravure method (coating amount: 5 g / m 2 (drying)), and irradiate with ultraviolet light using an excimer light irradiation device (wavelength: 172 nm (Xe2), ultraviolet output density: 1 W / cm, cumulative light amount: 10 to 100 mJ / cm 2 The substrate was then irradiated with an electron beam (acceleration voltage: 75 kV, exposure dose: 30 kGy (3 Mrad)) to form a wrinkled surface layer on the substrate, thereby obtaining an article having the substrate and the wrinkled surface layer. The 60° gloss value of the obtained article was measured from the wrinkled surface layer side and was 1.5.

[0426] [Examples 2J and 3J] An article was obtained in the same manner as in Example 1J, except that the amount of wrinkle formation stabilizer in the resin composition for forming the surface wrinkle layer was changed to the amount shown in Table 1J. The 60° gloss value of the surface wrinkle layer side of the obtained article is shown in Table 1J.

[0427] [Example 4J] An article was obtained in the same manner as in Example 1J, except that the electron beam was replaced with ultraviolet light (wavelength: 365 nm, ultraviolet output density: 200 W / cm) using a high-pressure mercury lamp. The 60° gloss values ​​of the surface wrinkle layer side of the obtained article are shown in Table 1J.

[0428] [Comparative example 1J] An article was obtained in the same manner as in Example 1J, except that (2) the irradiation treatment in Example 1J was...

Claims

1. A matte article having a matte layer, the matte layer being composed of a cured product of a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of resin, The wrinkle formation stabilizer includes a wrinkle formation stabilizer 1 having 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 or 30 μm or less, and a wrinkle formation stabilizer 2 having an average particle size of less than 1 μm, At least one surface of the matte layer has an uneven shape formed by irregular wrinkles, the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and concave portions formed by being surrounded by the plurality of linear protrusions, and the convex portions and the concave portions are classified based on the brightness difference of an image of 255 gradations corresponding to the height distribution in the uneven shape, with gradations of 0 to 127 being concave portions and gradations of 128 to 255 being convex portions, A matte article, wherein the 60° gloss value of the matte layer is 5.0 or less.

2. 10. The matte article of claim 1, wherein the matte layer does not contain a matting agent.

3. 3. The matte article according to claim 1, wherein the matte layer is provided over the entire surface.

4. 4. The matte article according to claim 1, wherein the resin is an ionizing radiation curable resin.

5. The matte article according to any one of claims 1 to 4, further comprising a substrate.

6. 6. The matte article according to claim 5, wherein the surface of the matte layer opposite to the substrate has an irregular shape formed by the irregular wrinkles.

7. 7. The matte article according to claim 5, wherein the substrate is a synthetic resin sheet.

8. 8. The matte article according to claim 5, further comprising a transparent resin layer between the substrate and the matte layer.

9. The 60° gloss value of the matte layer side before the rubbing test described below was G ０ The 60° gloss value of the matte layer side after the rubbing test was G １ The rate of change in the gross value (|(G １ -G ０ ) | / G ０ 9. The matte article according to claim 1, wherein the value of (x100) is 20% or less. (Rubbing test) The matte article was placed on the base of an abrasion tester Type II (JIS L0849:2013), and steel wool #0000 was set so as to contact the matte layer of the matte article, and a load of 1500 g / cm ２ The sample was moved back and forth 30 times at a moving speed of 100 mm / sec and a reciprocating moving distance of 100 mm.

10. The matte article according to any one of claims 1 to 9, which is used as a flooring material or a building material.

11. A flooring material comprising an adherend and the matte article according to any one of claims 5 to 8, the adherend and the substrate of the matte article facing each other via an adhesive layer.

12. A fitting member having an adherend and the matte article according to any one of claims 5 to 8, the adherend and the substrate of the matte article facing each other via an adhesive layer.

13. The matte article according to any one of claims 1 to 8, wherein the matte layer is a matte, easy-to-decontaminate layer.

14. 14. The matte article according to claim 13, wherein the matte, easily decontaminated layer contains at least one easily decontaminated agent selected from the group consisting of fluororesins, silicone resins, and fluorine-silicone copolymer resins.

15. The matte article according to claim 14, wherein the easy-to-decontaminate agent is contained in an amount of 0.5 parts by mass or more and 25.0 parts by mass or less per 100 parts by mass of the resin.

16. The matte article according to any one of claims 1 to 8, wherein the matte layer is a matte light-resistant layer, and the resin composition constituting the matte light-resistant layer further contains a hydroxyphenyltriazine-based ultraviolet absorber.

17. 17. The matte article according to claim 16, wherein the hydroxyphenyltriazine-based ultraviolet absorber is represented by the following general formula (1): 【Chemistry 1】 (In general formula (1), R １１ is a single bond or a divalent organic group, and R １２ is a hydrocarbon group or —C(═O)OR １５ an ester group represented by —O—C(═O)R １６ or an acyloxy group represented by —OR １７ and R １３ , R １４ , R １５ , R １６ and R １７ are each independently a monovalent organic group, and n １１ and n １２ are each independently an integer of 0 to 5.

18. The matte article according to any one of claims 1 to 8, wherein the matte layer is a matte writing layer.

19. 19. The matte article according to claim 18, wherein the substrate comprises a substrate sheet and a colored layer.

20. 20. The matte article according to claim 18 or 19, which is used as a writing board.

21. The matte article according to any one of claims 1 to 8, wherein the matte layer is a matte-imparting layer and is used for shaping.

22. A method for producing a matte article, comprising molding using the matte article according to claim 21.

23. 23. The method for producing a matte article according to claim 22, wherein the shaping is performed using an embossing roller with the matte article placed on the roller.

24. 24. The method for producing a matte article according to claim 23, wherein a substrate impregnated with a resin composition and the matte article are arranged so that the matte-imparting layer of the matte article faces the substrate, and the matte article is heated and press-molded to cure the resin composition, and then the matte article is peeled off.

25. 25. The method for producing a matte article according to claim 24, wherein the resin composition comprises a melamine resin or a diallyl phthalate resin (DAP).

26. The method includes a step of sequentially subjecting a resin composition containing a wrinkle formation stabilizer in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of resin and containing a photopolymerization initiator to the following irradiation treatments (1) and (2) to cure the resin composition and form a matte layer: The resin composition further includes, as the wrinkle formation stabilizer, a wrinkle formation stabilizer 1 having 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 a wrinkle formation stabilizer 2 having an average particle size of less than 1 μm, At least one surface of the matte layer has an uneven shape formed by irregular wrinkles, the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and concave portions formed by being surrounded by the plurality of linear protrusions, and the convex portions and the concave portions are classified based on the brightness difference of an image of 255 gradations corresponding to the height distribution in the uneven shape, with gradations of 0 to 127 being concave portions and gradations of 128 to 255 being convex portions, The 60° gloss value of the matte layer is 5.0 or less. Method for producing a matte article. (1) Irradiation treatment with light having a wavelength of 100 nm or more and less than 200 nm (2) Irradiation treatment with at least one of electron beam and light with a wavelength of 200 nm or more and 400 nm or less

27. The method for producing a matte article according to claim 26, wherein the light having the wavelength (1) is light having a wavelength of 100 nm or more and 185 nm or less.

28. The method for producing a matte article according to claim 26 or 27, wherein the irradiation treatment (2) is an electron beam irradiation treatment.

29. The method for producing a matte article according to any one of claims 26 to 28, wherein (3) irradiation treatment for preliminary curing is carried out before the irradiation treatment.

30. The method for producing a matte article according to claim 29, wherein the irradiation treatment for preliminary curing (3) is an irradiation treatment with light having a wavelength of more than 320 nm and not more than 400 nm.

31. The method for producing a matte article according to any one of claims 26 to 30, wherein the content of the photopolymerization initiator is 0.1 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin.

32. The method for producing a matte article according to any one of claims 26 to 31, wherein the resin composition is applied to at least one main surface of a substrate, and the matte layer is formed on at least one main surface of the substrate.

33. A method for curing a resin composition containing no photopolymerization initiator, comprising the steps of (1) and (2) below, in order, to perform irradiation treatments to harden the resin composition and form a surface wrinkle layer, The resin composition includes a resin and a wrinkle formation stabilizer, and the wrinkle formation stabilizer includes a wrinkle formation stabilizer 1 having 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 surface wrinkle layer and 30 μm or less, and a wrinkle formation stabilizer 2 having an average particle size of less than 1 μm, At least one surface of the surface wrinkle layer has an uneven shape formed by irregular wrinkles, The irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions, and the convex portions and the concave portions are classified based on the brightness difference of an image of 255 gradations corresponding to the height distribution in the uneven shape, with gradations of 0 to 127 being concave portions and gradations of 128 to 255 being convex portions. The method of manufacturing the article. (1) Irradiation treatment with light having a wavelength of 100 nm or more and less than 200 nm (2) Irradiation treatment with at least one of electron beam and light with a wavelength of 200 nm or more and 400 nm or less

34. The method for manufacturing an article according to claim 33, wherein the resin composition contains the wrinkle formation stabilizer 1 in an amount of 0.5 parts by mass or more and 6.0 parts by mass or less per 100 parts by mass of the resin, and the 60° gloss value of the surface wrinkle layer is 5.0 or less.

35. The method for manufacturing an article according to claim 33 or 34, wherein the irradiation treatment (2) is irradiation treatment with light having a wavelength of 200 nm or more and 400 nm or less.

36. The method for manufacturing an article according to any one of claims 33 to 35, wherein the resin composition is applied to at least one main surface side of a substrate, and the surface wrinkle layer is formed on at least one main surface side of the substrate.

37. The method for manufacturing an article according to claim 36, wherein the surface of the surface wrinkle layer opposite to the substrate side has an uneven shape formed by the irregular wrinkles.

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