Resin-impregnated decorative board including release film, release film, and method for manufacturing a resin-impregnated decorative board.

Abstract

The present invention provides a resin-impregnated decorative laminate including a release film that achieves both improved aesthetic appeal through reduced gloss and ease of removal of the hardened resin layer on the release layer. [Solution] A resin-impregnated decorative panel comprising a core substrate, a decorative sheet, a cured resin layer, and a release film, having these in order in the thickness direction, wherein the decorative sheet has, in the thickness direction from the core substrate side, a porous substrate, a design layer, and a release layer having a pattern shape, the decorative sheet and cured resin layer contain cured products of curable resin Y, and the release film has a film body and a coating layer disposed on the cured resin layer side of the film body, the coating layer contains cured products of curable resin α, the 60° gloss value of the coating layer is 30 or less, the coating layer has a first surface which is the surface on the cured resin layer side, and the RSm (average length of curved elements) of the first surface as specified in JIS B0601:2013 is 0.16 mm or less, making it a resin-impregnated decorative panel.

Description

[Technical Field]

[0001] This disclosure relates to a resin-impregnated decorative laminate including a release film, a release film, and a method for manufacturing a resin-impregnated decorative laminate. [Background technology]

[0002] Resin-impregnated decorative panels are known, which are made by impregnating a porous substrate with a melamine resin precursor and then curing it. Resin-impregnated decorative panels are used, for example, on walls, floors, and furniture. On the other hand, resin-impregnated decorative panels that express a glossy-matt finish are also known. For example, Patent Document 1 discloses a decorative panel in which a release layer is present in a part of the surface of the porous substrate, and a thermosetting resin layer is present in the remaining area of ​​the surface of the porous substrate that does not have a release layer, and the thermosetting resin is impregnated into the porous substrate and cured.

[0003] Patent Document 2 discloses a release sheet, wherein the release sheet comprises a base sheet and a surface layer forming the first surface of the release sheet, and the surface layer is formed of a cured product of an ionizing radiation-curable resin composition containing an ionizing radiation-curable resin and a silane coupling agent having an amino group, and the amount of the silane coupling agent contained in the ionizing radiation-curable resin composition is 3 parts by mass or more and 9 parts by mass or less per 100 parts by mass of the ionizing radiation-curable resin. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Patent No. 6716877 [Patent Document 2] Patent No. 7008277 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Patent Document 2 describes a method for producing a resin-impregnated decorative panel containing a release film (release sheet) by heat and pressure processing, and then peeling the release film from the resin-impregnated decorative panel to produce a resin-impregnated decorative panel with a gloss-matt finish. Specifically, when peeling the release film, in areas where a release layer is not formed, the release film is peeled away from the cured resin layer in the resin-impregnated decorative panel, and in areas where a release layer is formed, the release film is peeled away together with the cured resin layer in the resin-impregnated decorative panel. This makes it possible to express a gloss-matt finish due to the difference in gloss between the release layer and the cured resin layer. Thus, the release film is required to selectively remove the cured resin layer on the release layer after heat and pressure processing.

[0006] On the other hand, the surface shape of the release film is transferred to the surface of the cured resin layer. For example, if a release film with an uneven surface is used, the unevenness will also be transferred to the surface of the cured resin layer. When an uneven surface is created on the surface of the cured resin layer, the gloss on the surface of the cured resin layer is reduced, giving it a texture closer to that of the real thing, and it is thought that the design quality of the resin-impregnated decorative panel is improved. Normally, a heating and pressing process (hot pressing process) is performed in the manufacturing of resin-impregnated decorative panels. Therefore, a release film with an uneven surface is required to have enough heat resistance so that the unevenness does not disappear during the heating and pressing process.

[0007] Therefore, the inventors considered forming a coating layer containing a cured product of a curable resin on the surface of the film body to improve heat resistance. By providing a coating layer containing a cured product of a curable resin, it was possible to suppress the disappearance of irregularities due to the heating and pressurizing process and improve the design of the resin-impregnated decorative panel. However, it was found that the adhesion between the coating layer and the cured resin layer was reduced, making it difficult to remove the cured resin layer on the release layer.

[0008] This disclosure has been made in view of the above circumstances, and its main purpose is to provide a resin-impregnated decorative panel including a release film that achieves both improved design quality through reduced gloss and ease of removal of the cured resin layer on the release layer. [Means for solving the problem]

[0009] This disclosure provides a resin-impregnated decorative panel including a release film, having a core substrate, a decorative sheet, a cured resin layer, and a release film in this order in the thickness direction, wherein the decorative sheet has, in the thickness direction from the core substrate side, a porous substrate, a design layer, and a release layer having a pattern shape, the decorative sheet and the cured resin layer contain a cured product of a curable resin Y, the release film has a film body and a coating layer disposed on the cured resin layer side of the film body, the coating layer contains a cured product of a curable resin α, the 60° gloss value of the coating layer is 30 or less, the coating layer has a first surface which is the surface on the cured resin layer side, and the RSm (average length of curved elements) of the first surface as specified in JIS B0601:2013 is 0.16 mm or less.

[0010] This disclosure provides a release film used in the manufacture of a resin-impregnated decorative panel, having a core substrate, a decorative sheet, and a cured resin layer in this order in the thickness direction, wherein the decorative sheet has, in the thickness direction from the core substrate side, a porous substrate, a design layer, and a release layer having a pattern shape, the decorative sheet and the cured resin layer contain a cured product of a curable resin Y, the release film has a film body and a coating layer disposed on the cured resin layer side of the film body, the coating layer contains a cured product of a curable resin α, the 60° gloss value of the coating layer is 30 or less, the coating layer has a first surface which is the surface on the cured resin layer side, and the RSm (average length of curved elements) of the first surface as specified in JIS B0601:2013 is 0.16 mm or less.

[0011] In the present disclosure, there is provided a method for manufacturing a resin-impregnated decorative board, comprising: a preparation step of preparing a decorative sheet having, in this order in the thickness direction, a porous base material, a design layer, and a release layer having a pattern shape; a laminate formation step of forming a laminate having, in this order in the thickness direction: (i) a core base material, the decorative sheet, a curable resin layer containing a curable resin Y, and a release film, (ii) such that the surface of the decorative sheet on the side of the porous base material faces the core base material, and (iii) such that the curable resin Y is impregnated into the decorative sheet; a heating and pressing step of heating and pressing the laminate to cure the curable resin Y and form a cured resin layer from the curable resin layer to obtain a cured laminate; and a peeling step of peeling the release film from the cured laminate to remove the cured resin layer disposed at a position overlapping the release layer in the thickness direction while leaving the cured resin layer disposed between the patterns of the release layer. The release film has a film body and a coat layer disposed on the side of the cured resin layer with respect to the film body. The coat layer contains a cured product of a curable resin α, the 60° gloss value of the coat layer is 30 or less, the coat layer has a first surface which is the surface on the side of the cured resin layer, and the RSm (average length of curve elements) of the first surface defined in JIS B0601:2013 is 0.16 mm or less. There is provided a method for manufacturing a resin-impregnated decorative board.

Advantages of the Invention

[0012] In the present disclosure, there is an effect that a resin-impregnated decorative board including a release film can be provided, which achieves both improvement in design property due to low gloss and removability of the cured resin layer on the release layer.

Brief Description of the Drawings

[0013] [Figure 1] It is a schematic cross-sectional view illustrating a resin-impregnated decorative board including a release film in the present disclosure. [Figure 2] It is a schematic cross-sectional view illustrating a release film and a resin-impregnated decorative board in the present disclosure. [Figure 3]This is a schematic diagram illustrating the effect of surface roughness on adhesion. [Figure 4] This is a schematic diagram illustrating the effect of surface roughness on adhesion. [Figure 5] This image shows an example of a coating layer having a wrinkled structure as described in this disclosure. [Figure 6] This is a schematic cross-sectional view illustrating the release film in this disclosure. [Figure 7] This is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. [Figure 8] This is a schematic cross-sectional view illustrating a decorative sheet in this disclosure. [Figure 9] This is a schematic cross-sectional view illustrating a resin-impregnated decorative panel in this disclosure. [Figure 10] This is a schematic cross-sectional view illustrating a method for manufacturing a resin-impregnated decorative panel including a release film as described in this disclosure. [Figure 11] This is a schematic diagram illustrating the testing apparatus for the 90° tensile test in this disclosure. [Figure 12] This graph illustrates the test results of the 90° tensile test described in this disclosure. [Modes for carrying out the invention]

[0014] The embodiments will be described below with reference to the drawings, etc. However, this disclosure can be implemented in many different ways and is not limited to the embodiments described below. In addition, the drawings may schematically represent the width, thickness, and shape of each part compared to the actual form in order to make the explanation clearer, but this is merely an example and should not be interpreted as limiting.

[0015] In this specification, when describing a manner in which one member is placed on another member, the term "above" or "below" includes, unless otherwise specified, both cases: when the other member is placed directly above or directly below the member so as to be in contact with it, and when the other member is placed above or below the member via yet another member. Similarly, in this specification, when describing a manner in which one member is placed on the surface of a member, the term "on the surface" includes, unless otherwise specified, both cases: when the other member is placed directly above or directly below the member so as to be in contact with it, and when the other member is placed above or below the member via yet another member.

[0016] A. Resin-impregnated decorative board containing release film Figure 1 is a schematic cross-sectional view illustrating a resin-impregnated decorative panel including a release film in this disclosure. As shown in Figure 1, the resin-impregnated decorative panel 50 including a release film comprises a core substrate 20, a decorative sheet 10, a cured resin layer 30, and a release film 40, with the thickness direction D T In this order, the decorative sheet 10 has the thickness direction D T In this invention, the core substrate 20 side is in order to have a porous substrate 1, a design layer 2, and a release layer 3 having a pattern shape. The decorative sheet 10 and the cured resin layer 30 also contain a cured product of a curable resin Y. In this disclosure, the release film 40 has a film body 41 and a coating layer 42 positioned on the cured resin layer 30 side of the film body 41. The coating layer 42 contains a cured product of a curable resin α, and the 60° gloss value of the coating layer 42 is within a predetermined range. The coating layer 42 also has a first surface S1 which is the surface on the cured resin layer 30 side, and the RSm (average length of the curved element) of the first surface S1 is within a predetermined range.

[0017] According to this disclosure, a resin-impregnated decorative panel including a release film is made in which the release film has a specific coating layer (a coating layer containing a cured product of a curable resin, having a 60° gloss value within a predetermined range, and having an RSm of the first surface within a predetermined range), thereby achieving both improved design due to reduced gloss and ease of removal of the cured resin layer on the release layer.

[0018] As described above, Patent Document 2 describes a method for producing a resin-impregnated decorative panel containing a release film (release sheet) by heat and pressure processing, and then peeling the release film from the resin-impregnated decorative panel to produce a resin-impregnated decorative panel with a gloss-matt finish. Specifically, as shown in Figure 2, when peeling off the release film 40, in areas where the release layer 3 is not formed, the release film 40 is peeled off from the hardened resin layer 31. At the same time, in areas where the release layer 3 is formed, the release film 40 is peeled off together with the hardened resin layer 32. This results in a resin-impregnated decorative panel 100 that expresses a gloss-matt finish due to the difference in gloss between the release layer 3 and the hardened resin layer 31. Thus, the release film is required to selectively remove the hardened resin layer on the release layer after heat and pressure processing.

[0019] On the other hand, the surface shape of the release film is transferred to the surface of the cured resin layer. For example, if a release film with an uneven surface is used, the unevenness will also be transferred to the surface of the cured resin layer. When an uneven surface is created on the surface of the cured resin layer, the gloss on the surface of the cured resin layer is reduced, giving it a texture closer to that of the real thing, and it is thought that the design quality of the resin-impregnated decorative panel is improved. Normally, a heating and pressing process (hot pressing process) is performed in the manufacturing of resin-impregnated decorative panels. Therefore, a release film with an uneven surface is required to have enough heat resistance so that the unevenness does not disappear during the heating and pressing process.

[0020] Therefore, the inventors considered improving heat resistance by forming a coating layer 42 containing cured resin on the surface of the film body 41, as shown in Figure 2. By providing a coating layer 42 containing cured resin, it was possible to suppress the disappearance of irregularities due to the heating and pressurizing process, thereby improving the design of the resin-impregnated decorative panel. On the other hand, it was found that the adhesion between the coating layer 42 and the cured resin layer 32 was reduced, making it difficult to remove the cured resin layer 32 from the release layer 3. The reason for the reduced adhesion is presumed to be that the coating layer 42 contains a resin with a high crosslinking density (cured resin). Thus, providing a coating layer 42 containing cured resin presents the challenge of difficulty in achieving both improved design due to the reduced gloss of the cured resin layer 32 and ease of removal of the cured resin layer 32 from the release layer 3.

[0021] In order to solve the above problems, we conducted extensive research and, as shown in Figure 2, focused on the surface roughness of the first surface S1 of the coating layer 42. In particular, we found that by adjusting the RSm (average length of curved elements) of the first surface S1 to a predetermined range, it is possible to achieve both improved aesthetics through reduced gloss and ease of removal of the hardened resin layer on the release layer. Specifically, this can be achieved by adjusting the RSm (average length of curved elements) to be smaller than conventional methods. Here, if the RSm (average length of curved elements) is large, as shown in Figure 3(a), the number of downwardly convex parts (protrusions) in the coating layer 42 becomes relatively smaller. At the same time, the proportion of internal space in which the coating layer 42 and the hardened resin layer 30 do not adhere becomes relatively larger. Conversely, if the RSm (average length of curved elements) is small, as shown in Figure 3(b), the number of downwardly convex parts (protrusions) in the coating layer 42 becomes relatively larger. At the same time, the proportion of internal space in which the coating layer 42 and the hardened resin layer 30 do not adhere becomes relatively smaller. Comparing Figure 3(a) and Figure 3(b), in the case of Figure 3(a) (when the RSm of the first surface is small), the contact area between the coating layer 42 and the cured resin layer 30 increases, and the adhesion between the two improves. As a result, while improving the aesthetic appearance through reduced gloss, the ease of removing the cured resin layer on the release layer can also be improved.

[0022] 1. Release film The release film in this disclosure is a component that is peeled off from the cured laminate (resin-impregnated decorative laminate including the release film) during the manufacturing of the resin-impregnated decorative laminate. The release film has a film body and a coating layer positioned on the cured resin layer side of the film body.

[0023] (1) Film body The film body preferably contains a resin. Examples of the resin include polyolefin resins, polyester resins, and acrylic resins, with polyolefin resins or polyester resins being preferred.

[0024] Examples of polyolefin resins include olefin homopolymers, copolymers of two or more olefins, and copolymers of one or more olefins with one or more polymerizable monomers that can polymerize with olefins. Examples of the olefins (monomer units) include ethylene, propylene, butene, and hexene. The copolymer may be binary, ternary, or quaternary. The copolymer may also be a random copolymer or a block copolymer.

[0025] Specific examples of polyolefin resins include polyethylene resins and polypropylene resins, with polypropylene resins being preferred. An example of a polypropylene resin is a propylene homopolymer. Another example of a polypropylene resin is a copolymer of propylene and another α-olefin. Examples of other α-olefins include at least one of ethylene, butene-1, hexene-1, and heptene-1,4-methylpentene-1. It is preferable that polypropylene resins have propylene as the main monomer unit. Similarly, it is preferable that polyethylene resins have ethylene as the main monomer unit.

[0026] Examples of polyester resins include condensation polymers of compositions containing at least dicarboxylic acids and diols. The above compositions may also contain other monomers polymerizable with dicarboxylic acids or diols. Examples of dicarboxylic acids include terephthalic acid and 2,6-naphthalenedicarboxylic acid. Examples of diols include ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,4-cyclohexanedimethanol. Specific examples of polyester resins include polyethylene terephthalate and polybutylene terephthalate.

[0027] The film body preferably has a melting point such that it does not melt during the heating and pressurizing process described later. The melting point of the film body is, for example, 130°C or higher, may be 140°C or higher, or 150°C or higher. The melting point of the film body is, for example, 270°C or lower. The method for measuring the melting point of the film body is as follows. • Measuring device: Differential scanning calorimeter (DSC) ·Measurement standard…JIS K7121-1987 • Measurement procedure 1) Cut out a sample from the film, take approximately 5 mg, place it in the DSC measurement container (pan), and place it inside the device. 2) Prepare alpha-alumina as a reference material and place it inside the apparatus. 3) Under a nitrogen atmosphere, raise the temperature from room temperature at a rate of 10°C / min to 30°C above the melting point of the film body, and then maintain the temperature for 10 minutes. 4) Cool the temperature down to 40°C at a rate of 10°C / min, then heat it again to the temperature reached in 3) under the same heating conditions as in 3). 5) The melting point temperature is obtained by reading the horizontal axis (temperature) of the endothermic peak (downward-facing peak) in the DSC curve obtained during the heating process in 4). If multiple endothermic peaks exist, the temperature obtained from the endothermic peak with the largest area is adopted.

[0028] The thickness of the film itself is, for example, 30 μm or more, and may be 40 μm or more. If the film itself is too thin, it may not be possible to secure the mechanical strength necessary for controlling the adhesion between the release film and the cured resin layer. On the other hand, the thickness of the film itself is, for example, 100 μm or less, and may be 90 μm or less.

[0029] (2) Coat layer The coating layer is positioned on the cured resin layer side of the film body and contains cured material of the curable resin α. The 60° gloss value of the coating layer is typically 30 or less. The coating layer has a first surface, which is the side facing the cured resin layer. The RSm (average length of the curved elements) of the first surface, as specified in JIS B0601:2013, is typically 0.16 mm or less.

[0030] (i) Composition of the coating layer The coating layer contains at least a cured product of the curable resin α. The coating layer may further contain a matting agent.

[0031] (Curable resin α) Examples of curable resins α include ionizing radiation-curable resins and thermosetting resins. Examples of ionizing radiation-curable resins include electron beam-curable resins and ultraviolet-curable resins. Ionizing radiation-curable resins (ionizing radiation-curable compounds) are not limited to materials that undergo a crosslinking polymerization reaction upon irradiation with ionizing radiation and change into a three-dimensional polymer structure. Examples of ionizing radiation-curable resins include prepolymers, oligomers, and monomers that have polymerizable unsaturated bonds or epoxy groups in their molecules that can be crosslinked upon irradiation with ionizing radiation. In this disclosure, only one type of ionizing radiation-curable resin may be used, or two or more types may be used. In particular, it is preferable to use at least one of a polyfunctional monomer and an oligomer as the ionizing radiation-curable resin.

[0032] Examples of ionizing radiation-curable resins include (meth)acrylate resins such as urethane (meth)acrylate, ester (meth)acrylate, and epoxy (meth)acrylate; silicon-based resins such as siloxane; ester-based resins; and epoxy-based resins. (Meth)acrylate resin refers to either an acrylate-based resin or a methacrylate-based resin.

[0033] The weight-average molecular weight of the ionizing radiation-curable resin is, for example, 500 or more and 80,000 or less, and may also be 1,000 or more and 50,000 or less. The weight-average molecular weight is a value measured using gel permeation chromatography (GPC) with polystyrene as the standard substance.

[0034] The ionizing radiation-curable resin preferably contains at least a polyfunctional monomer or oligomer having a weight-average molecular weight of 500 or more. Examples of such polyfunctional monomers or oligomers include (meth)acrylate resins such as dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, urethane(meth)acrylate, ester(meth)acrylate, and epoxy(meth)acrylate.

[0035] On the other hand, examples of thermosetting resins include acrylic polyol resins, unsaturated ester resins, urethane resins (including two-component curing polyurethanes), epoxy resins, amino alkyd resins, phenolic resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea cocondensation resins, silicon resins, and siloxane resins. Furthermore, a curing agent may be used to cure the thermosetting resin.

[0036] (Matting agent) The coating layer may or may not contain a matting agent. Using a matting agent makes it easier for irregularities to form in the coating layer, and these irregularities are transferred to the cured resin layer, thereby reducing the surface gloss of the cured resin layer.

[0037] Examples of matting agents include inorganic particles and synthetic resin particles. Examples of inorganic particles include silica, alumina, calcium carbonate, magnesium carbonate, calcium sulfate, barium sulfate, and kaolin. Examples of synthetic resin particles include acrylic beads, urethane beads, nylon beads, silicone beads, silicone rubber beads, polycarbonate beads, and polyolefin waxes (e.g., polypropylene wax, polyethylene wax).

[0038] The average particle size of the matting agent is not particularly limited, but for example, it may be 1 μm or more and 20 μm or less, 2 μm or more and 18 μm or less, or 3 μm or more and 16 μm or less. In this disclosure, the average particle size is measured by the volume-based particle size distribution D by laser diffraction scattering. 50 The content of the matting agent in the coating layer is, for example, 5 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin component of the coating layer, and may be 8 parts by mass or more and 45 parts by mass or less, or 15 parts by mass or more and 40 parts by mass or less.

[0039] (Release agent) The coating layer may or may not contain a release agent. Examples of release agents include silicone-based release agents such as silicone oil, wax-based release agents such as polyolefin wax, and fluorine-based release agents. Among these, silicone oil is preferred because it has excellent heat resistance in the heating and pressurizing process. The silicone oil may be reactive or non-reactive, but reactive silicone oil is preferred because it has even better heat resistance.

[0040] Reactive silicone oil refers to modified silicone oils in which organic groups have been introduced into the side chains or terminals, and which exhibit reactivity depending on the properties of the introduced organic groups. Specifically, examples of reactive silicone oils include modified silicone oil side chain type, modified silicone oil both-ended type, modified silicone oil single-ended type, and modified silicone oil side chain both-ended type, in which the introduced organic groups are amino-modified, epoxy-modified, mercapto-modified, carboxyl-modified, carbinol-modified, phenol-modified, methacrylic-modified, heterofunctional group-modified, etc. These reactive silicone oils can be used individually or in mixtures of two or more types.

[0041] Non-reactive silicone oils are not particularly limited as long as they do not have reactive functional groups such as amino groups, epoxy groups, mercapto groups, carboxyl groups, hydroxyl groups, (meth)acryloyl groups, or allyl groups. Examples of non-reactive silicone oils include silicone oils made from polysiloxane, as well as polyether-modified silicone oils, aralkyl-modified silicone oils, fluoroalkyl-modified silicone oils, long-chain alkyl-modified silicone oils, higher fatty acid ester-modified silicone oils, higher fatty acid amide-modified silicone oils, and phenyl-modified silicone oils. These non-reactive silicone oils can be used individually or in combination of two or more types.

[0042] The amount of release agent in the coating layer is, for example, 1 part by mass or more and 10 parts by mass or less per 100 parts by mass of the total solid content of the coating layer, and may be 2 parts by mass or more and 9 parts by mass or less, or 3 parts by mass or more and 8 parts by mass or less.

[0043] (ii) Gloss value of the coating layer The 60° gloss value of the coating layer is usually 30 or less. That is, the first surface of the coating layer is not flat but has a predetermined uneven shape. The 60° gloss value of the coating layer may be 26 or less, or 23 or less. The 60° gloss value of the coating layer can be adjusted, for example, by the content of the matting agent. For example, increasing the content of the matting agent will decrease the 60° gloss value of the coating layer. The 85° gloss value of the coating layer is not particularly limited, but may be 50 or less, 40 or less, or 35 or less.

[0044] The 60° gloss and 85° gloss values ​​of the coating layer are determined by measuring the surface (first surface) of the coating layer after peeling off the release film from the resin-impregnated decorative laminate containing the release film. The 60° gloss and 85° gloss values ​​of the coating layer are the 60° specular gloss and 85° specular gloss measured in accordance with Method 3 of JIS Z 8741:1997, and are determined as the average value of measurements taken at 10 arbitrary locations. When performing the above measurement, care should be taken to ensure that the cured resin layer present on the first surface of the coating layer (for example, the cured resin layer 32 in Figure 2) is not included in the measurement area. Also, when performing the above measurement, black paper (Tencolor, manufactured by Oji F-Tex) should be used. <400> The peeled release film is placed on a black A4 sheet with the first side facing upwards, and the measurement is taken in that state. The 60° gloss and 85° gloss values ​​of the coating layer can be adjusted, for example, by the particle size of the matting agent, the content of the matting agent, and the thickness of the coating layer.

[0045] (iii) Contact angle of the coating layer with pure water The pure water contact angle on the first surface of the coating layer is not particularly limited, but for example, it may be 68.0° or more, 70.0° or more, 75.0° or more, or 80.0° or more. If the pure water contact angle is too small, the adhesion between the coating layer and the cured resin layer may become excessively high, making it difficult to peel the release film from the cured resin layer. On the other hand, the pure water contact angle on the first surface of the coating layer may be 92.0° or less, or 88.0° or less. If the pure water contact angle is too large, the adhesion between the coating layer and the cured resin layer may become excessively low, making it difficult to remove the cured resin layer on the release layer.

[0046] The pure water contact angle on the first surface of the coating layer is determined by measuring the first surface of the coating layer after peeling off the release film from the resin-impregnated decorative laminate containing the release film. Specifically, the pure water contact angle is the value obtained by measuring it using the following method.

[0047] Specifically, the release film is placed on a horizontal surface so that the first surface of the coating layer is facing upwards. Next, a water droplet (pure water, 2.0 μL) is dropped onto the coating layer from a direction perpendicular to the horizontal plane. At this time, the water droplet is not dropped onto the cured resin layer present on the first surface, but rather so that the entire water droplet is in contact with the first surface where there is no cured resin layer. After dropping the water droplet, wait for 10 seconds and measure the contact angle between the coating layer and the pure water using a contact angle meter. Perform the above measurement at 10 arbitrary locations and take the average value as the pure water contact angle on the first surface of the coating layer.

[0048] (iv) Surface roughness of the coating layer The coating layer has a first surface, which is the side facing the cured resin layer. The surface roughness (RSm, Rsk, Ra) of the first surface is measured on the surface (first surface) of the coating layer after peeling off the release film from the resin-impregnated decorative laminate containing the release film, in accordance with JIS B 0601:2013. Details of the method for measuring the surface roughness of the first surface will be described in detail in the examples below. As described later, care should be taken when measuring the surface roughness to ensure that the cured resin layer present on the first surface of the coating layer (for example, the cured resin layer 32 in Figure 2) is not included in the measurement area.

[0049] (RSm) The RSm (average length of curve elements) of the first surface is usually 0.16 mm or less. The RSm of the first surface may also be 0.15 mm or less. If the RSm of the first surface is too large, the adhesion between the coating layer and the cured resin layer will be poor, and it may become difficult to properly remove the cured resin layer from the release layer. On the other hand, the RSm of the first surface may be, for example, 0.01 mm or more, and may also be 0.03 mm or more. RSm (average length of curve elements) is a lateral parameter of the contour curve and is the average length of the contour curve elements in the reference length. The smaller the RSm, the more protrusions are included in the reference length. RSm can be adjusted, for example, by the particle size of the matting agent, the content of the matting agent, and the thickness of the coating layer. For example, reducing the particle size of the matting agent will reduce RSm.

[0050] (Rsk) A small Rsk (skewness) of the first surface is preferable. This is because the contact area between the coating layer and the cured resin layer increases, improving the adhesion between the coating layer and the cured resin layer. When the Rsk (skewness) is large, the downward convex shape of the coating layer 42 becomes relatively sharp, as shown in Figure 4(a). In contrast, when the Rsk (skewness) is small, the downward convex shape of the coating layer 42 becomes relatively rounded, as shown in Figure 4(b). Comparing Figure 4(a) and Figure 4(b), in the case of Figure 4(b) (when the Rsk of the first surface is small), the contact area between the coating layer 42 and the cured resin layer 30 increases, and the adhesion between the two improves. The Rsk (skewness) of the first surface is not particularly limited, but for example it can be 2.0 or less, or 1.5 or less. On the other hand, the Rsk (skewness) of the first surface can be, for example, 0.1 or more.

[0051] (Ra) The arithmetic mean roughness (Ra) of the first surface is not particularly limited, but may be, for example, 0.20 μm or more, 0.30 μm or more, or 0.40 μm or more. On the other hand, the arithmetic mean roughness of the first surface may be, for example, 1.80 μm or less, or 1.60 μm or less. The arithmetic mean roughness (Ra) is the average value of the height difference from the average surface in the contour curve at a reference length. The larger the value of the arithmetic mean roughness (Ra), the greater the height difference between the convex and concave parts on the first surface.

[0052] (v) Surface shape of the coating layer The first surface of the coating layer typically has an uneven surface. For example, if the coating layer contains a matting agent, the first surface has an uneven surface derived from the matting agent. On the other hand, the first surface of the coating layer may also have a wrinkled structure. For example, as shown in Figure 5, the wrinkled structure w may typically have irregular wrinkles. The irregular wrinkles shown in Figure 5 have a convex structure w1 composed of a plurality of protrusions and a concave structure w2 surrounded by a plurality of protrusions.

[0053] Furthermore, as shown in Figure 5, it is preferable that the protrusions have linear protrusions. "Linear protrusion" means that the ratio of the length to the width of the protrusion (length / width) is 3 or more, preferably 5 or more, and more preferably 10 or more. Also shown in Figure 5 is that the first surface of the coating layer has irregular wrinkles; the irregular wrinkles have a convex structure w1 composed of a plurality of curved linear protrusions; and the irregular wrinkles have a concave structure w2 that meanders as if surrounded by a plurality of curved linear protrusions.

[0054] The wrinkle structure shown in Figure 5 can be formed, for example, by the following method: (1) a first curing treatment by irradiation with light with a wavelength between 320 nm and 400 nm, (2) a second curing treatment by irradiation with light with a wavelength between 100 nm and 200 nm, and (3) a third curing treatment by electron beam irradiation, in this order to obtain the desired wrinkle structure.

[0055] In the first curing treatment, the curable resin composition is given an appropriate viscosity. The wavelength of light used in the first curing treatment can be irradiated using an ultraviolet irradiation device that uses, for example, 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, or an LED light as the light source.

[0056] In the second curing treatment, the energy of ultraviolet light penetrates only to the surface and does not reach the layers below it. As a result, only the surface of the coated layer begins to harden, and only the surface undergoes hardening shrinkage, forming a wrinkled structure. The wavelength light used in the second curing treatment is preferably "excimer light," which includes light in the ultraviolet wavelength range from excited state dimers, i.e., excimers, formed by the discharge of noble gases such as Ar, Kr, Xe, and Ne, halide gases of noble gases such as F, Cl, I, and Br, or mixed gases.

[0057] In the third curing treatment, electron beam irradiation can be used to promote curing from the slower-curing near-surface portion to the deeper portions in the depth direction, while maintaining the wrinkle structure formed on the surface of the coated layer. The electron beam irradiation conditions used in the third curing treatment are not particularly limited as long as the desired wrinkle structure can be obtained.

[0058] (vi) Coat layer The thickness of the coating layer is not particularly limited, but for example, it may be 1 μm or more and 30 μm or less, 3 μm or more and 20 μm or less, or 5 μm or more and 15 μm or less.

[0059] (3) Release film The release film has the film body and coating layer described above. Furthermore, as shown in Figure 6, the release film 40 may have a primer layer 43 between the film body 41 and the coating layer 42. Providing the primer layer 43 improves the adhesion between the film body 41 and the coating layer 42.

[0060] The primer layer typically contains a resin. The resin may be a cured product of curable resin β. Examples of curable resin β include thermosetting resins. The thermosetting resin is the same as the thermosetting resin in curable resin α described above. The thickness of the primer layer is not particularly limited, but is, for example, 1 μm or more and 10 μm or less.

[0061] The thickness of the release film is, for example, 30 μm or more, and may be 40 μm or more. If the release film is too thin, it may not be possible to secure the mechanical strength necessary for controlling the adhesion between the release film and the cured resin layer. On the other hand, the thickness of the release film is, for example, 130 μm or less, and may be 120 μm or less.

[0062] 2. Cured resin layer The cured resin layer is positioned between the decorative sheet and the release film. Furthermore, the cured resin layer is positioned so as to overlap with the design layer and release layer of the decorative sheet when viewed in the thickness direction. The cured resin layer also contains a cured product of the curable resin Y. In this disclosure, the precursor layer (the layer before curing) of the cured resin layer may be referred to as the curable resin layer.

[0063] Examples of curable resins Y include thermosetting resins. Examples of thermosetting resins include melamine resins (melamine resin precursors), melamine-urea cocondensation resins, unsaturated polyester resins, polyurethane resins (including two-component curable polyurethanes), epoxy resins, amino-alkyd resins, phenolic resins, urea resins, diallyl phthalate resins, guanamine resins, silicon resins, and polysiloxane resins.

[0064] As shown in Figure 1, the thickness of the cured resin layer 30 may be greater than the thickness of the release layer 3. The thickness of the cured resin layer 30 is not particularly limited, but may be, for example, 1 μm or more and 500 μm or less, or 10 μm or more and 300 μm or less. Also, the thickness T1 of the cured resin layer 30 present on the release layer 3 may be, for example, 0.5 μm or more and 45 μm or less, 2 μm or more and 35 μm or less, or 3 μm or more and 30 μm or less. The thickness T1 corresponds to, for example, the difference between the thickness of the cured resin layer 31 and the thickness of the release layer 3, as shown in Figure 2.

[0065] As shown in Figure 1, when the release film 40 is peeled off from the resin-impregnated decorative panel 50 containing the release film, a resin-impregnated decorative panel 100 is obtained, as shown in Figure 2, which has a release layer 3 having a pattern shape and a cured resin layer 31 arranged between the patterns of the release layer 3.

[0066] A low 60° gloss value is preferable for the cured resin layer, as this allows for a texture closer to that of the real thing. The 60° gloss value of the cured resin layer is, for example, 16 or less, but may also be 14 or less, or 12 or less. On the other hand, the 60° gloss value of the cured resin layer is not particularly limited, but is, for example, 2 or more. Also, the 60° gloss value of the cured resin layer may be greater than the 60° gloss value of the release layer. The difference between the 60° gloss value of the cured resin layer and the 60° gloss value of the release layer is, for example, 1.0 or more, or 3.0 or more. Also, the ratio of the 60° gloss value of the cured resin layer to the 60° gloss value of the release layer is, for example, 1.2 or more, or 1.5 or more. Furthermore, a low 85° gloss value is preferable for the cured resin layer, as this allows for a texture closer to that of the real thing even when the cured resin layer is observed from a wide angle. The 85° gloss value of the cured resin layer is, for example, 45 or less, but may also be 35 or less, or 20 or less. The 60° gloss and 85° gloss values ​​of the cured resin layer are the 60° specular gloss and 85° specular gloss measured in accordance with Method 3 of JIS Z 8741:1997, and are determined as the average value of measurements taken at any 10 locations.

[0067] 3. Decorative sheet As shown in Figure 7, the decorative sheet 10 consists of a porous base material 1, a design layer 2, and a release layer 3 having a pattern shape, in the thickness direction D T In this order, they are present.

[0068] (1) Release layer In this disclosure, the release layer is positioned on the side opposite to the porous substrate of the design layer and has a patterned shape. In regions where the design layer is present on the porous substrate, at least a portion of the release layer is positioned on the side opposite to the porous substrate of the design layer, and in regions where the design layer is not present on the porous substrate, the porous substrate and the release layer may be in contact.

[0069] (i) Resin components The release layer contains a resin component. Typically, the resin component is a cured product (crosslinked structure) of a curable resin X. Alternatively, the resin component may be a thermoplastic resin. Among these, it is preferable that the release layer contains a cured product of a curable resin X, as this provides a release layer with good abrasion resistance. Furthermore, the inclusion of a cured product of a curable resin X in the release layer improves its release properties from the cured resin layer.

[0070] Examples of curable resin X include ionizing radiation-curable resins and thermosetting resins. The details regarding curable resin X are the same as those described for curable resin α above.

[0071] (ii) matting agent The release layer may contain a matting agent. Using a matting agent can result in a low-gloss release layer. The matting agent is the same as the one used in the coating layer described above. The amount of matting agent in the release layer is, for example, 5 parts by mass or more and 20 parts by mass or less, 8 parts by mass or more and 18 parts by mass or less, or 10 parts by mass or more and 15 parts by mass or less, per 100 parts by mass of the total solid content of the release layer.

[0072] (iii) Release agent The release layer may contain a release agent. Adding a release agent improves the release properties. The release agent is the same as the one used in the coating layer described above. The amount of release agent in the release layer is, for example, 1 part by mass or more and 10 parts by mass or less, 2 parts by mass or more and 9 parts by mass or less, or 3 parts by mass or more and 8 parts by mass or less, per 100 parts by mass of the total solid content of the release layer.

[0073] Furthermore, the release layer may be colorless or colored. In the latter case, it is preferable that the release layer contains a coloring agent. The same coloring agent used in the design layer described later can be used. In addition, the release layer may contain additives such as ultraviolet absorbers, infrared absorbers, light stabilizers, polymerization inhibitors, crosslinking agents, antistatic agents, antioxidants, leveling agents, coupling agents, plasticizers, defoaming agents, fillers, thermal radical generators, and aluminum chelating agents, as needed. Adding an ultraviolet absorber or a light stabilizer can improve the weather resistance of the release layer.

[0074] (iv) Release layer The pure water contact angle of the release layer is not particularly limited, but for example, it may be 85° or more and 130° or less, or 90° or more and 125° or less. The pure water contact angle of the release layer is determined by measuring the surface of the release layer exposed by peeling off the release film from the resin-impregnated decorative board containing the release film. Specifically, the pure water contact angle of the release layer is the value obtained by measuring it using the following method.

[0075] Specifically, the resin-impregnated decorative panel is placed on a horizontal surface so that the release layer exposed by peeling off the release film is on the top surface. Next, a water droplet (pure water, 2.0 μL) is dropped onto the release layer from a direction perpendicular to the horizontal surface. At this time, the water droplet is not dropped at the boundary between the cured resin layer and the release layer, but is dropped so that the entire droplet is in contact with the release layer. After dropping the water droplet, wait for 1 second and measure the contact angle between the release layer and the pure water using a contact angle meter. Perform the above measurement at any 10 locations and the average value is taken as the pure water contact angle of the release layer.

[0076] The pure water contact angle can be adjusted by the amount of release agent and the thickness of the release layer. For example, increasing the amount of release agent can increase the pure water contact angle. For example, increasing the thickness of the release layer can also increase the pure water contact angle.

[0077] The Spc (arithmetic mean curvature of the peak) of the release layer is not particularly limited, but for example, 10 mm -1Above, 140 mm -1 Below, and 15 mm -1 Above, 120 mm -1 May be below, and 20 mm -1 Above, 100 mm -1 May be below. The Spc of the release layer can be obtained by measuring the surface of the release layer exposed by peeling off the release film from the resin-impregnated decorative board including the release film.

[0078] Spc (arithmetic mean curvature of peak points) is one of the three-dimensional surface texture parameters defined in ISO 25178, and is the average curvature (average sharpness) of the tip of the peak, which is obtained from the arithmetic mean value of the radii of curvature of the peak points (peak vertices) classified as mountains (convex parts) in the surface image included in the reference area. Therefore, Spc (arithmetic mean curvature of peak points) is the reciprocal of the radius (mm) -1 ). The larger the value of Spc (arithmetic mean curvature of peak points), the larger the curvature of the tip of the peak (convex part) (the radius of curvature of its reciprocal is smaller, and the shape of the tip is sharper). On the other hand, the smaller the value of Spc (arithmetic mean curvature of peak points), the smaller the curvature of the peak point (top of the protrusion) (the radius of curvature of its reciprocal is larger, and the shape of the tip is blunter).

[0079] The Spc (arithmetic mean curvature of peak points) of the release layer is the average value of the measured values obtained by using a laser microscope manufactured by Keyence Corporation and selecting the measurement part so that all of the measurement parts enter the release layer, and measuring at 10 arbitrary locations under the following conditions with respect to the surface of the release layer. (Measurement conditions) Objective lens: 5x Laser wavelength: 661 nm Measured area area of each point: 500 μm × 500 μm

[0080] Spc can be adjusted, for example, by the particle size of the matting agent. Specifically, Spc can be increased by increasing the particle size of the matting agent. Also, Spc can be increased by increasing the content of the matting agent.

[0081] The 60° gloss value of the release layer is not particularly limited, but for example, it may be 10 or less, 8 or less, or 7.5 or less. When the 60° gloss value of the release layer is adjusted to a low value, the release layer functions as a matte area. The 60° gloss value of the release layer may be, for example, 1.0 or more, 2.0 or more, or 3.0 or more.

[0082] The 60° gloss value of the release layer can be determined by measuring the surface of the release layer exposed by peeling off the release film from the resin-impregnated decorative laminate containing the release film. The 60° gloss value of the release layer is the 60° specular gloss measured according to Method 3 of JIS Z 8741:1997, and is determined as the average value of measurements taken at 10 arbitrary locations. The 60° gloss value of the release layer can be adjusted by the particle size of the matting agent, the content of the matting agent, and the thickness of the release layer.

[0083] Furthermore, as shown in Figure 8, it is preferable that the release layer 3 is arranged in accordance with the pattern of the design layer 2. "In accordance with" means that the shapes and positions of the two patterns in question are roughly the same. Specifically, it means that the shapes and positions of the release layer pattern and at least some of the patterns constituting the design layer's pattern are consistent to an extent that does not impair realism and a sense of luxury. In Figure 8, the design layer 2 has pattern layers y1 and y2, and the release layer 3 is in accordance with pattern layer y1. By arranging the release layer pattern in accordance with the design layer's pattern, a high level of texture can be obtained. On the other hand, the release layer does not necessarily have to be arranged in accordance with the design layer's pattern.

[0084] The thickness of the release layer is not particularly limited, but for example, it may be 0.1 μm or more and 20 μm or less, 0.3 μm or more and 10 μm or less, or 0.5 μm or more and 8 μm or less. The thickness of the release layer refers to the thickness of the portion that does not penetrate to the design layer side and protrudes from the side of the design layer 2 opposite to the porous substrate. Also, when viewing the decorative sheet from the thickness direction, if the area of ​​the release layer is S1 and the area of ​​the porous substrate is S2, the ratio of S1 to S2 (S1 / S2) may be, for example, 5% or more and may be 10% or more. On the other hand, S1 / S2 may be, for example, 80% or less, 70% or less, or 60% or less.

[0085] The method for forming the release layer is not particularly limited, but one example is to coat a release layer forming ink containing a curable resin X onto the surface opposite to the porous substrate of the design layer and cure it. For example, if the release layer forming ink contains an electron beam curable resin as the curable resin X, a cured product of the electron beam curable resin is usually obtained by irradiating it with an electron beam. Examples of electron beam sources include various electron beam accelerators such as Cockcroftwald type, Van de Graft type, resonant transformer type, insulated core transformer type, linear type, Dynamitron type, and high-frequency type. The energy of the electron beam is, for example, 100kV or more and 1000kV or less, and may also be 100kV or more and 300kV or less. The irradiation dose of the electron beam is, for example, 2Mrad or more and 15Mrad or less.

[0086] (2) Design layer The design layer in this disclosure is disposed on one surface of the porous substrate. The design layer preferably has a pattern.

[0087] Examples of patterns in the design layer include organic patterns, inorganic patterns, and abstract patterns. Organic patterns are those derived from the life activities of living things such as plants and animals. Inorganic patterns are those that do not fall under the category of organic patterns. Abstract patterns are those that interpret a subject (for example, a form existing in nature) abstractly and do not represent a clear shape. Examples of organic patterns include wood grain patterns, leather patterns, floral patterns, and botanical patterns. Examples of inorganic patterns include stone patterns, concrete patterns, sand patterns, fabric patterns, metal patterns, tile patterns, and brick patterns. Examples of abstract patterns include wavering patterns (for example, wavering ink patterns), smoke patterns, and marble patterns.

[0088] The design layer, for example, has a pattern layer. The design layer may also have a solid layer on the porous substrate side of the pattern layer. In this disclosure, the pattern layer means a layer formed partially (particularly in a pattern) on one surface of the porous substrate. The solid layer means a layer formed over the entire surface of one surface of the porous substrate.

[0089] The design layer contains, for example, a coloring agent and a resin component. Examples of coloring agents include inorganic pigments such as carbon black, titanium white, zinc oxide, reddish-brown, Prussian blue, and cadmium red; organic pigments such as azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, and dioxazine pigments; metallic powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium dioxide-coated mica and bismuth oxide; fluorescent pigments; and phosphorescent pigments. Dyes may also be used as coloring agents.

[0090] Examples of resin components include (meth)acrylic resins, ester urethane resins, acrylamide resins, ethylene oxide resins, N-vinylpyrrolidone resins, ester resins, amide resins, vinyl acetate resins, vinyl chloride resins, urethane (meth)acrylic resins, natural rubber, and synthetic rubber. Among these, (meth)acrylic resins and urethane (meth)acrylic resins are preferred.

[0091] The design layer preferably contains a resin having one or more polar groups, such as a hydroxyl group, an amino group, and a carboxyl group, as a resin component. The inclusion of a resin having the above polar groups improves the impregnation of the curable resin Y into the porous substrate.

[0092] Resins containing polar groups contain one or more of the following polar groups: a hydroxyl group (-OH), an amino group (-NH2), or a carboxyl group (-COOH). These polar groups may be ionized and stabilized by the influence of the solvent and other functional groups, for example. Therefore, the above "hydroxyl group (-OH)" may be in the ionized state "-O - This concept includes the above "amino group (-NH2)", and the ionized state is "-NH3". + The concept includes "carboxyl group (-COOH)", and the ionized state is "-COOH - This is a concept that includes "[...]."

[0093] Examples of resins having one or more polar groups such as hydroxyl groups (-OH), amino groups (-NH2), and carboxyl groups (-COOH) include aqueous proteins such as casein, cellulose, cellulose derivatives such as acetylcellulose, nitrated cotton, hydroxypropylcellulose, and carboxymethylcellulose, polyvinyl alcohol, polyvinyl alcohol derivatives such as polyvinyl butyral resin, amino resins such as melamine resin, (meth)acrylic acid resins, phenolic resins, acrylic polyols, and natural polymers (e.g., polynucleotides, polypeptides, polysaccharides).

[0094] The design layer preferably contains one or more of the following polar group-containing resins: casein, melamine resin, polyvinyl alcohol, polyvinyl alcohol derivatives, cellulose, and cellulose derivatives, and more preferably casein. As the casein, α-casein, β-casein, γ-casein, or mixtures thereof can be used. In addition, derivatives such as sodium caseinate and ammonium caseinate can be used alone or in combination as the casein.

[0095] The proportion of the resin having polar groups described above to the resin components contained in the design layer is, for example, 20% by mass or more, may be 30% by mass or more, may be 40% by mass or more, or may be 50% by mass or more. On the other hand, the above proportion of the resin having polar groups is, for example, 100% by mass or less, or 90% by mass or less. If the content of the resin having polar groups is within the above range, the penetration of the ink in the release layer into the porous substrate can be further suppressed without hindering the penetration of the curable resin Y into the porous substrate.

[0096] The design layer may contain additives such as fillers (e.g., silica), extender pigments (e.g., organic beads), neutralizing agents, and surfactants, as needed. The thickness of the design layer is not particularly limited, but is, for example, 0.1 μm or more and 20 μm or less.

[0097] One method for forming a design layer is a coating method using an ink for forming a design layer that contains a colorant, a binder resin, and a solvent (or dispersion medium). For example, a design layer can be obtained by coating one side of a porous substrate with the ink for forming a design layer and drying it.

[0098] (3) Porous base material The porous substrate in this disclosure is a substrate into which a curable resin Y is impregnated during the manufacture of a resin-impregnated decorative panel. Examples of porous substrates include permeable fibrous substrates. Examples of permeable fibrous substrates include paper, synthetic paper, nonwoven fabrics, and woven fabrics. Examples of the above-mentioned paper include titanium paper, tissue paper, kraft paper, linter paper, cardboard, gypsum board paper, fine paper, coated paper, parchment paper, and Japanese paper. In addition, vinyl wallpaper raw material (paper dry-laminated with polyvinyl chloride resin) can also be used as a fibrous substrate. Other examples of fibrous substrates include nonwoven or woven fabrics containing inorganic fibers such as glass fibers, asbestos, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers. Further examples of fibrous substrates include nonwoven or woven fabrics containing synthetic resin fibers such as polyester, vinylon, polyethylene, and polypropylene. Among these porous substrates, titanium paper, tissue paper, kraft paper, coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, and Japanese paper are preferred in terms of their impregnation properties with the curable resin Y. In particular, titanium paper is preferred as a porous substrate because it has excellent impregnation properties with the curable resin Y and also has excellent opacity.

[0099] Porous substrates may be colored. For example, a colored porous substrate can be obtained by incorporating a coloring agent during the manufacturing stage of the porous substrate. For example, if the porous substrate is paper, colored paper can be obtained by incorporating a coloring agent during the papermaking stage. Examples of coloring agents include inorganic pigments such as titanium dioxide, carbon black, and iron oxide, organic pigments such as phthalocyanine blue, and various dyes. The amount of coloring agent added is set appropriately according to the desired color. Furthermore, the porous substrate may contain various additives as needed, such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers.

[0100] The basis weight of the porous substrate is not particularly limited, but for example, 40 g / m² 2 More than 150g / m 2The following applies: The thickness of the porous substrate is not particularly limited, but is, for example, 50 μm or more and 170 μm or less. For example, to improve the adhesion of the ink forming the design layer, the surface of the porous substrate facing the design layer may be subjected to corona treatment.

[0101] 4. Core substrate In this disclosure, the core substrate is placed on the porous substrate side of the decorative sheet (the side of the decorative sheet located on the porous substrate side with respect to the design layer). By providing the core substrate, the mechanical strength of the resin-impregnated decorative panel can be increased. Examples of the core substrate include phenol resin-impregnated paper. Phenolic resin-impregnated paper is, for example, paper obtained by impregnating kraft paper, which is the core paper, with phenol resin and drying it. The core substrate may also contain a cured product of a curable resin Y.

[0102] 5. Resin-impregnated decorative laminate containing release film The resin-impregnated decorative panel including a release film in this disclosure has the core substrate, decorative sheet, cured resin layer, and release film in this order in the thickness direction. Also, as shown in Figure 2, the resin-impregnated decorative panel 100 is obtained by peeling off the release film 40 from the resin-impregnated decorative panel 50 including the release film. The resin-impregnated decorative panel 100 can express a gloss-matt finish due to the difference in gloss between the release layer 3 and the cured resin layer 31. Also, as shown in Figure 9, the resin-impregnated decorative panel 100 has a thickness direction D T From this perspective, the region where the release layer 3 exists may be designated as a matte region, and the region where the cured resin layer 31 exists (the region where the release layer 3 does not exist) may be designated as a gloss region.

[0103] In a 90° tensile test to peel the release film from a resin-impregnated decorative laminate containing the release film, the integral mean load when the release film is pulled at a speed of 100 mm / min is not particularly limited, but is preferably between 0.1 N and 3.0 N. Details of the 90° tensile test are described in the examples.

[0104] Resin-impregnated decorative panels are used, for example, by being placed on the surface of a substrate. Examples of substrates include wood-based materials, resin-based materials, metal-based materials, and ceramic-based materials. Examples of wood-based materials include wood veneer, wood plywood, particleboard, and wood fiberboard. Examples of wood used in wood-based materials include cedar, cypress, pine, and lauan. Examples of resins used in resin-based materials include vinyl chloride resin, (meth)acrylic resin, ester resin, styrene resin, olefin resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), phenolic resin, cellulose resin, carbonate resin, melamine resin, and rubber. Examples of metals used in metal-based materials include iron and aluminum. The material of the ceramic-based material may be ceramics such as glass and porcelain, non-cement ceramic materials such as gypsum, or non-ceramic ceramic materials such as ALC (autoclaved lightweight concrete).

[0105] Applications of resin-impregnated decorative panels include, for example, building materials and furniture. Building materials may be interior or exterior materials. Examples of building materials include walls, floors, ceilings, doors, and shelves. Examples of furniture include tables, desks, and cabinets.

[0106] B. Release Film As shown in Figure 2, the release film 40 in this disclosure comprises a core substrate 20, a decorative sheet 10, and a cured resin layer 31, with the thickness direction D T In this context, the resin-impregnated decorative sheet 100 is used in the manufacture of the decorative sheet 10 having the following characteristics in this order. The decorative sheet 10 has a thickness direction D TIn this invention, the core substrate 20 side is in order to have a porous substrate 1, a design layer 2, and a release layer 3 having a pattern shape. The decorative sheet 10 and the cured resin layer 31 also contain a cured product of a curable resin Y. The cured resin layer 31 is also arranged between the patterns of the release layer 3. In this disclosure, the release film 40 has a film body 41 and a coating layer 42 arranged on the cured resin layer 31 side of the film body 41. The coating layer 42 contains a cured product of a curable resin α, and the 60° gloss value of the coating layer 42 is within a predetermined range. Furthermore, the coating layer 42 has a first surface S1 which is the surface on the cured resin layer 31 side, and the RSm (average length of the curved elements) of the first surface S1 is within a predetermined range.

[0107] According to this disclosure, the release film has a predetermined coating layer, thereby achieving both improved aesthetics through reduced gloss and ease of removal of the cured resin layer on the release layer. Details of the release film are the same as those described in "A. Resin-impregnated decorative panel including release film" above. Since the coating layer in the release film contains a curable resin, the surface gloss (e.g., 60° gloss value) and surface roughness (e.g., RSm) do not change significantly before and after the heat and pressure processing described later.

[0108] C. Method for manufacturing resin-impregnated decorative panels The method for manufacturing a resin-impregnated decorative laminate in this disclosure comprises a preparation step, a laminate formation step, a heating and pressing step, and a peeling step, which will be described later. In this disclosure, the release film comprises a film body and a coating layer disposed on the side of the film body that is on the cured resin layer side. The coating layer contains a cured product of a curable resin α, and the 60° gloss value of the coating layer is within a predetermined range. Furthermore, the coating layer has a first surface which is the surface on the cured resin layer side, and the RSm (average length of the curved element) of the first surface is within a predetermined range.

[0109] According to this disclosure, by using a release film having a predetermined coating layer, it is possible to achieve both improved aesthetics through reduced gloss and ease of removal of the cured resin layer on the release layer, thereby enabling the efficient manufacture of resin-impregnated decorative panels that express a gloss-matte aesthetic.

[0110] 1. Preparation process The preparation step in this disclosure, as shown in Figure 10(a), involves a porous substrate 1, a design layer 2, and a release layer 3 having a pattern shape, in the thickness direction D T The next step is to prepare a decorative sheet 10 having the following characteristics in this order. Details of the decorative sheet are the same as those described in "A. Resin-impregnated decorative board including release film" above.

[0111] 2. Laminate formation process The laminate formation process in this disclosure, as shown in Figure 10(d), involves (i) a core substrate 20, a decorative sheet 10, a curable resin layer 30a containing a curable resin Y, and a release film 40, in the thickness direction D T The process involves forming a laminate 52 having the following characteristics in this order: (ii) the surface of the decorative sheet 10 facing the porous substrate 1 is arranged to face the core substrate 20, and (iii) the decorative sheet 10 is impregnated with a curable resin Y.

[0112] The method for forming the laminate is not particularly limited. For example, as shown in Figures 10(b) and (c), first, a curable resin layer 30a containing the curable resin Y is formed by impregnating the decorative sheet 10 with the curable resin Y (Figure 10(b)), covering the design layer 2 and the release layer 3, thereby obtaining a precursor laminate 51 (Figure 10(c)). Next, as shown in Figure 10(d), a release film 40 is placed on the side of the precursor laminate 51 facing the curable resin layer 30a, and a core substrate 20 is placed on the side of the precursor laminate 51 facing the porous substrate 1. This yields a laminate 52. Details of the core substrate 20, curable resin Y, and release film 40 are the same as those described in "A. Resin-impregnated decorative board including release film" above.

[0113] In the laminate formation process, for example, a decorative sheet is immersed in a curable resin composition containing curable resin Y. After immersion, drying is preferable. At this time, a portion of the curable resin may be cured, leaving it in a semi-cured state. The curable resin composition is a curable resin composition containing curable resin Y. The proportion of curable resin Y in the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The curable resin composition may contain solvents such as water, alcohol, or organic solvents.

[0114] Another example of a method for forming a laminate is to place a core substrate opposite to a porous substrate in a decorative sheet, impregnate the core substrate and the porous substrate with a curable resin Y, cover the design layer and the release layer, and form a curable resin layer containing the curable resin Y, and then place a release film on the side of the curable resin layer.

[0115] 3. Heating and pressurizing process The heating and pressurizing step in this disclosure, as shown in Figure 10(e), is a step in which the laminate 52 is heated and pressurized to cure the curable resin Y, forming a cured resin layer 30 from the curable resin layer 30a, and obtaining a cured laminate 53. The cured laminate 53 corresponds to the resin-impregnated decorative board containing the release film as described above.

[0116] The heating temperature is not particularly limited, but for example, it is between 90°C and 160°C. The heating time is also not particularly limited, but for example, it is between 30 seconds and 30 minutes.

[0117] 4. Peeling process The peeling step in this disclosure involves peeling the release film 40 from the cured laminate 53, as shown in Figure 10(f), in the thickness direction D T This process involves removing the hardened resin layer 30 positioned in a location overlapping with the release layer 3, while leaving the hardened resin layer 30 (hardened resin layer 31) positioned between the patterns of the release layer 3. This results in a resin-impregnated decorative panel 100.

[0118] 5. Resin-impregnated decorative laminate The resin-impregnated decorative laminate obtained through the processes described above is the same as described in "A. Resin-impregnated decorative laminate containing release film" above.

[0119] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure. [Examples]

[0120] [Preparation of release film] Release films 1-9 (RF1-9) were prepared using the following method.

[0121] (Preparation of Release Film 1) A composition was prepared containing 100 parts by mass of an ionizing radiation-curable monomer (acrylate monomer) and 20 parts by mass of a matting agent (silica particles, average particle size: 6 μm). The prepared composition was applied to the corona-treated surface of a 50 μm thick PET film (film body, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.), and cured by irradiation with an electron beam of 5 Mrad at an accelerating voltage of 165 kV to form a coating layer (8 μm thick). This obtained a release film 1 having a film body and a coating layer.

[0122] (Production of Release Film 2) A composition was prepared containing 100 parts by mass of an ionizing radiation-curable monomer (acrylate monomer) and 15 parts by mass of a matting agent (silica particles, average particle size: 6 μm). The prepared composition was applied to the corona-treated surface of a 50 μm thick PET film (film body, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.), and cured by irradiation with an electron beam of 5 Mrad at an accelerating voltage of 165 kV to form a coating layer (8 μm thick). This obtained a release film 2 having a film body and a coating layer.

[0123] (Production of Release Film 3) A composition was prepared containing 100 parts by mass of an ionizing radiation-curable monomer (acrylate monomer) and 15 parts by mass of a matting agent (silica particles, average particle size: 12 μm). The prepared composition was applied to the corona-treated surface of a 50 μm thick PET film (film body, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.), and cured by irradiation with an electron beam of 5 Mrad at an accelerating voltage of 165 kV to form a coating layer (8 μm thick). This obtained a release film 3 having a film body and a coating layer.

[0124] (Production of Release Film 4) A composition containing 100 parts by mass of thermosetting resin (acrylic polyol resin), 50 parts by mass of curing agent (hexamethylene diisocyanate), and 40 parts by mass of matting agent (silica particles, average particle size: 4 μm) was diluted with an appropriate amount of solvent (ethyl acetate and butyl acetate) to prepare a coating solution. The prepared coating solution was applied to the corona-treated surface of a 50 μm thick PET film (film body, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.) and cured at 50°C for 24 hours to form a coating layer (5 μm thick). This obtained a release film 4 having a film body and a coating layer.

[0125] (Production of Release Film 5) A mixture was obtained by mixing 30 parts by mass of a trifunctional urethane acrylate oligomer, 30 parts by mass of a trifunctional acrylate monomer, and 40 parts by mass of a difunctional acrylate monomer. To the obtained mixture, 3 parts by mass of a wrinkle-forming stabilizer (silica, average particle size: 3 μm) and 0.8 parts by mass of a photopolymerization initiator (benzophenone-based) were added to prepare a composition for forming a coating layer. The prepared composition was applied to form a coating layer. The coating layer was irradiated with ultraviolet light using a UV irradiation device consisting of LEDs (LED-UV irradiation, wavelength 395 nm, maximum illuminance 0.6 W / cm²). 2 , cumulative light intensity 30~100 mJ / cm 2Pre-curing was performed. Next, ultraviolet light was irradiated using an excimer light irradiation device (excimer irradiation, wavelength 172 nm (Xe2), ultraviolet power density 30 mW / cm²). 2 , integrated light intensity 5~100 mJ / cm 2 (Nitrogen atmosphere). Furthermore, an electron beam was irradiated (acceleration voltage 100-150kV, irradiation dose 30-100kGy) to form a coating layer (thickness 7μm) having a wrinkled structure. This yielded a release film 5 having the film body and the coating layer.

[0126] (Preparation of Release Film 6) A composition containing 100 parts by mass of thermosetting resin (acrylic polyol resin), 50 parts by mass of curing agent (hexamethylene diisocyanate), and 45 parts by mass of filler (silica particles, average particle size: 3 μm) was diluted with an appropriate amount of solvent (ethyl acetate and butyl acetate) to prepare a primer coating solution. The prepared coating solution was applied to the corona-treated surface of a 50 μm thick PET film (film body, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.) to form a primer layer (3 μm thick). Next, a composition containing 100 parts by mass of ionizing radiation-curable monomer (acrylate monomer) and 20 parts by mass of matting agent (silica particles, average particle size: 6 μm) was prepared. The prepared composition was applied onto the primer layer and cured by irradiation with an electron beam of 5 Mrad at an accelerating voltage of 165 kV to form a coat layer (8 μm thick). This obtained a release film 6 having a film body, a primer layer, and a coat layer.

[0127] (Production of Release Film 7) A composition was prepared containing 100 parts by mass of an ionizing radiation-curable monomer (acrylate monomer) and 10 parts by mass of a matting agent (silica particles, average particle size: 6 μm). The prepared composition was applied to the corona-treated surface of a 50 μm thick PET film (film body, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.), and cured by irradiation with an electron beam of 5 Mrad at an accelerating voltage of 165 kV to form a coating layer (8 μm thick). This obtained a release film 7 having a film body and a coating layer.

[0128] (Production of Release Film 8) A composition was prepared containing 100 parts by mass of an ionizing radiation-curable monomer (acrylate monomer) and 12 parts by mass of a matting agent (silica particles, average particle size: 12 μm). The prepared composition was applied to the corona-treated surface of a 50 μm thick PET film (film body, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.), and cured by irradiation with an electron beam of 5 Mrad at an accelerating voltage of 165 kV to form a coating layer (thickness 5 μm). This obtained a release film 8 having a film body and a coating layer.

[0129] (Production of Release Film 9) A 50μm thick PET film (film itself, CosmoShine® A4160 manufactured by Toyobo Co., Ltd.) was prepared as release film 9.

[0130] [evaluation] (Surface gloss) The surface gloss of the first surface of release films 1-9 was evaluated using 60° gloss and 85° gloss values. Specifically, the release films were placed on a horizontal surface with the first surface facing upwards, and the 60° gloss value (60° specular gloss) and 85° gloss value (60° specular gloss) were measured using a gloss meter ("Microtrigloss (Cat. No. 4563)", manufactured by BYK Gardner) in accordance with Method 3 of JIS Z 8741:1997. Black paper (Tencolor, manufactured by Oji F-Tex) was used for measurement. <400> The release film was placed on a black A4 sheet with the first side facing upwards, and measurements were taken in that state. The above measurements were performed at 10 arbitrary locations, and the average values ​​were taken as the 60° gloss value and the 85° gloss value. The results are shown in Tables 1 to 3.

[0131] (Surface roughness) The surface roughness (Ra, RSm, and Rsk) of the first surface of release films 1-9 was measured. Specifically, based on JIS B 0601:2013 (ISO 4287:1997, Amd.1:2009), the surface roughness (Ra, RSm, and Rsk) was measured using a "SurfCorder SE800" surface roughness measuring instrument manufactured by Kosaka Laboratory. A differential transformer type detector was used, with a measuring force of 0.75 mN. The stylus had a tip radius of 2 μm ± 25% and an apex angle of 60°, and was made of diamond. The skid had a radius of curvature of 40 mm (in the measurement direction) and was made of sapphire. The measurement conditions were a vertical magnification of 2000x (resolution: 10 nm, detection range: ±300 μm) and a measurement speed of 0.5 mm / s. Furthermore, the cutoff value λc (λc contour curve filter) was set to 0.8 mm, and the cutoff value λs (λs contour curve filter) was set to 2.5 μm, with the cutoff filter characteristics set to a Gaussian filter. The data interval was processed for each cutoff length λc (divided into 1600 equal parts per cutoff length), and surface roughness data was calculated for each cutoff length λc (obtaining 5 values). The average value of these 5 values ​​was adopted as the numerical value for that measurement. The above measurements were performed at 10 locations, and the average values ​​of Ra, RSm, and Rsk were obtained, respectively. The results are shown in Tables 1 to 3.

[0132] (Surface wettability) The surface wettability of the first surface of release films 1-9 was evaluated using the pure water contact angle. Specifically, the release films were placed on a horizontal surface with the first surface facing upwards. Next, a water droplet (pure water, 2.0 μL) was dropped onto the first surface from a direction perpendicular to the horizontal plane. After dropping the water droplet, a 10-second wait was made, and the contact angle between the first surface and the pure water was measured using a contact angle meter (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd.). The above measurement was performed at 10 arbitrary locations, and the average value was taken as the pure water contact angle. The results are shown in Tables 1-3.

[0133] [Examples 1-6, Comparative Examples 1-3] (Production of decorative sheets) As a porous substrate, a paper-based substrate (basis weight 80g / m²) 2A titanium base paper for building materials (PM-77P, manufactured by KJ Specialty Paper Co., Ltd.) was prepared. Using a gravure printing method with the printing inks listed below, a design layer (pattern layer) with a thickness of 2 μm was partially laminated onto the paper substrate to create a wood grain pattern. Furthermore, the release layer-forming ink listed below was laminated on top of the pattern layer in a manner consistent with the pattern layer, and then an 8 μm thick release layer was formed by irradiating with an electron beam at an accelerating voltage of 165 kV for 3 Mrad. In this way, a decorative sheet was manufactured in which the porous substrate, design layer, and release layer were laminated in this order.

[0134] <Printing Ink> • Pigments (azo, quinacridone, carbon black, etc.) 10 parts by mass Casein / acrylic resin 10 parts by mass ·Water 70 parts by mass • Dipropyl glycol 5 parts by mass • Isopropyl alcohol 5 parts by mass

[0135] <Ink for forming a release layer> • Ionizing radiation-curable monomer (Toagosei Co., Ltd., Aronics M-400) 48 parts by mass • Reactive silicone (Shin-Etsu Chemical Co., Ltd., X-22-164B) 4 parts by mass (6.7 parts by mass per 100 parts by mass of total solids) • Silane coupling treated silica (particle size 2 μm) 8 parts by mass (13.3 parts by mass per 100 parts by mass of total solids) • Methyl ethyl ketone 40 parts by mass

[0136] (Manufacturing of melamine decorative laminates) The prepared decorative sheet was impregnated with a liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, Nikaredin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol, using an impregnation device until the uncured melamine resin composition reached 80 g / m². 2 The impregnated decorative sheet (precursor laminate) was manufactured by impregnating it to the ratio specified (when dry) and then drying it.

[0137] The impregnated decorative sheet was manufactured by impregnating kraft paper with a phenolic resin solution, with a basis weight of 245 g / m². 2 A core substrate consisting of three sheets of phenol resin-impregnated core paper (obtained by impregnating core craft paper with a liquid, uncured resin composition made of phenol resin) was laminated onto the impregnated decorative sheet, and then release films 1 to 9 were laminated onto the impregnated decorative sheet, thereby obtaining nine types of laminates. In this process, the coated layer side of release films 1 to 8, or the corona-treated side of release film 9, was laminated facing the impregnated decorative sheet.

[0138] The resulting laminate is sandwiched between two mirrored plates and pressed using a hot press machine at a pressure of 100 kg / cm². 2 The uncured melamine resin composition was heat-molded at a molding temperature of 150°C for 25 minutes to form a cured resin layer containing melamine resin. This produced a cured laminate (resin-impregnated decorative panel including release film). The systems using release films 1 to 6 correspond to Examples 1 to 6, and the systems using release films 7 to 9 correspond to Comparative Examples 1 to 3.

[0139] (Surface gloss) The release films were peeled off from the cured laminates (resin-impregnated decorative panels including release films) obtained in Examples 1-6 and Comparative Examples 1-3. The surface gloss of the peeled release films 1-9 (release films 1-9 after pressing) and the surface gloss of the cured resin layer in the resin-impregnated decorative panel were evaluated using 60° gloss and 85° gloss values. For measuring the surface gloss of the peeled release films, the peeled release films were placed on a horizontal surface with the first surface facing upwards, and the 60° gloss values ​​(60° specular gloss) and 85° gloss values ​​(60° specular gloss) were measured using a gloss meter ("Microtrigloss (Cat. No. 4563)", manufactured by BYK Gardner) in accordance with Method 3 of JIS Z 8741:1997. During measurement, black paper (Tencolor, manufactured by Oji F-Tex) was used. <400> The release film was placed on a black A4 sheet with the first surface facing upwards, and measurements were taken in that state. Care was taken to ensure that the cured resin layer present on the first surface of the coating layer (for example, the cured resin layer 32 in Figure 2) was not included in the measurement area. The above measurements were performed at 10 arbitrary locations, and the average values ​​were taken as the 60° gloss value and the 85° gloss value. The results are shown in Tables 1 to 3.

[0140] On the other hand, in measuring the surface gloss of the cured resin layer in resin-impregnated decorative laminates, the resin-impregnated decorative laminate was placed on a horizontal surface with the cured resin layer facing upwards, and the 60° gloss value (60° specular gloss) and 85° gloss value (60° specular gloss) were measured using a gloss meter ("Microtrigloss (Cat. No. 4563)", manufactured by BYK Gardner) in accordance with Method 3 of JIS Z 8741:1997. The above measurements were performed at 10 arbitrary locations, and the average values ​​were taken as the 60° gloss value and 85° gloss value. The results are shown in Tables 1 to 3.

[0141] (Surface roughness) The release films were peeled off from the cured laminates (resin-impregnated decorative panels including release films) obtained in Examples 1-6 and Comparative Examples 1-3, and the surface roughness (Ra, RSm, and Rsk) of the first surface of the peeled release films 1-9 (release films 1-9 after pressing) was measured. Specifically, the surface roughness (Ra, RSm, and Rsk) was measured using a "SurfCorder SE800" surface roughness measuring instrument manufactured by Kosaka Laboratory, based on JIS B 0601:2013 (ISO 4287:1997, Amd. 1:2009). A differential transformer type detector was used as the detector, and the measuring force was set to 0.75 mN. The stylus had a tip radius of 2 μm ± 25% and an apex angle of 60°, and was made of diamond. The skid had a radius of curvature of 40 mm (in the measurement direction) and was made of sapphire. The measurement conditions were set to a vertical magnification of 2000x (resolution: 10nm, detection range: ±300μm) and a measurement speed of 0.5mm / s. The cutoff value λc (λc contour curve filter) was set to 0.8mm, the cutoff value λs (λs contour curve filter) to 2.5μm, and the cutoff filter characteristics were set to a Gaussian filter. The data interval was processed for each cutoff length λc (divided into 1600 equal parts per cutoff length), and surface roughness data was calculated for each cutoff length λc (obtaining 5 values). The average of these 5 values ​​was adopted as the numerical value for that measurement. During measurement, care was taken to ensure that the cured resin layer present on the first surface of the coating layer (for example, cured resin layer 32 in Figure 2) was not included in the measurement area. The results are shown in Tables 1 to 3.

[0142] (90° tensile test) The release film was peeled from the cured laminates (resin-impregnated decorative panels including the release film) obtained in Examples 1-6 and Comparative Examples 1-3 by a 90° tensile test. Figure 11(a) is a top view showing the test apparatus for the 90° tensile test in this disclosure, and Figure 11(b) is a cross-sectional view AA of Figure 11(a). As shown in Figures 11(a) and (b), the test apparatus has a base, a floor placed on the base, a pair of walls extending from the floor, and four rollers fixed to the pair of walls. The dimensions of each component are as shown in Figures 11(a) and (b). As shown in Figure 11(c), the release film was pulled in a direction 90° with respect to the direction of travel of the resin-impregnated decorative panel, and the release film was peeled from the cured laminate (resin-impregnated decorative panel including the release film), and the integral mean load and maximum point load were determined.

[0143] Specifically, a cured laminate (resin-impregnated decorative panel including a release film) was cut to a size of 25 mm in width and 150 mm in length to obtain a sample. Next, the release film and resin-impregnated decorative panel were peeled off from the edge of the sample to a position of approximately 30 mm (position A) and placed in the test apparatus. Then, the release film from which the resin-impregnated decorative panel had been peeled off was fixed and pulled at a speed of 100 mm / min in a direction 90° to the direction of travel of the resin-impregnated decorative panel, from position A to position B (75 mm). As shown in Figure 12, the integral average load (average of integral values) and the maximum point load were determined from position C (25 mm from position A) to position B. The results are shown in Tables 1 to 3.

[0144] (Design aspects of resin-impregnated decorative panels) The release film was peeled off from the cured laminates (resin-impregnated decorative laminates including the release film) obtained in Examples 1-6 and Comparative Examples 1-3 to prepare resin-impregnated decorative laminates. On the other hand, a reference sample A, which is a veneer decorative laminate, and a reference sample B, which is a melamine decorative laminate with a normal wood grain pattern (melamine decorative laminate without a release layer), were prepared.

[0145] Reference sample B was prepared using the following method: As a porous substrate, a paper-based substrate (basis weight 80 g / m²) was used. 2We prepared titanium base paper for building materials (PM-77P, manufactured by KJ Specialty Paper Co., Ltd.). Using a gravure printing method with the printing inks listed below, we partially laminated a 2 μm thick design layer (pattern layer) onto the paper substrate to create a wood grain pattern. This produced a decorative sheet having a porous substrate and a design layer. <Printing Ink> • Pigments (azo, quinacridone, carbon black, etc.) 10 parts by mass Casein / acrylic resin 10 parts by mass ·Water 70 parts by mass • Dipropyl glycol 5 parts by mass • Isopropyl alcohol 5 parts by mass The prepared decorative sheet was impregnated with a liquid uncured melamine resin composition containing 60 parts by mass of uncured melamine resin (water-soluble methylol melamine resin, Nikaredin S-260 manufactured by Nippon Carbide Industries Co., Ltd.), 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol, using an impregnation device until the uncured melamine resin composition reached 80 g / m². 2 The impregnated decorative sheet (precursor laminate) was manufactured by impregnating it to the ratio specified (when dry) and then drying it. The impregnated decorative sheet was manufactured by impregnating kraft paper with a phenolic resin solution, with a basis weight of 245 g / m². 2 A core substrate consisting of three sheets of phenol resin-impregnated core paper (obtained by impregnating core craft paper with a liquid, uncured resin composition made of phenol resin) was laminated onto the core substrate, and then a release film (Toray Lumirror S10#50) was laminated onto the impregnated decorative sheet to obtain a laminate. The obtained laminate was sandwiched between two mirror plates and pressed using a hot press machine at a pressure of 100 kg / cm². 2 The uncured melamine resin composition was heat-molded at a molding temperature of 150°C for 25 minutes to form a cured resin layer containing melamine resin. Subsequently, the release film was peeled off to prepare a resin-impregnated decorative panel (reference sample B).

[0146] The aesthetic appeal of resin-impregnated decorative laminates was scored according to the following criteria. 5 points: Equivalent to reference sample A. 4 points: Not equivalent to reference sample A, but close to reference sample A. 3. It cannot be said that it is close to either reference sample A or reference sample B. 2 points: Not equivalent to reference sample B, but close to reference sample B. 1 point: Equivalent to reference sample B.

[0147] Ten evaluators assigned scores as described above, and the average score was calculated to evaluate the aesthetic appeal of the resin-impregnated decorative laminate according to the following criteria. The results are shown in Tables 1 to 3. S: The average score is 4 points or higher. A: The average score is between 3 and 4 points. B: The average score is between 2 and 3 points. C: The average score is less than 2 points.

[0148] (Removability of the hardened resin layer) The cured laminates (resin-impregnated decorative panels including release film) obtained in Examples 1-6 and Comparative Examples 1-3 were cut to a size of 25 mm in width and 150 mm in length. Then, the release film was peeled off from the cured laminate to prepare three resin-impregnated decorative panels. Next, the prepared resin-impregnated decorative panels were observed from the release layer side, and the cured resin layer remaining on the release layer was visually confirmed. The removeability of the cured resin layer in each sample was evaluated according to the following criteria. ○: The area covered by the cured resin layer is 20% or less of the total area of ​​the release layer. △: The area covered by the cured resin layer is greater than 20% and less than or equal to 50% of the total area of ​​the release layer. ×: The area covered by the cured resin layer exceeds 50% of the total area of ​​the release layer.

[0149] Furthermore, the removeability of the hardened resin layer in three resin-impregnated decorative panels was evaluated according to the following criteria. The results are shown in Tables 1 to 3. A: Of the three items, there are 0 "X" marks and 2 or more "O" marks. B: Of the three items, there are 0 "X" marks and 1 or fewer "O" marks. C: Of the three items, one or more are marked with an "X".

[0150] (Adhesion of the coating layer) The adhesion between the film body and the coating layer of release films 1-9 was evaluated using the following procedure. First, the cured laminate (resin-impregnated decorative board including the release film) was cut to a size of 25 mm in width and 150 mm in length, and the release film was peeled off the cured laminate to prepare three samples of the release film. Next, the peeled surface (first surface) of the release film was visually inspected, and the remaining state of the coating layer on the release film was evaluated according to the following criteria. Note that if the coating layer has peeled off from the film body, the surface gloss of the film body will be visible, and unevenness in surface gloss will occur. ○: The area where the court layer remains is 95% or more of the total area of ​​the court layer. △: The area where the court layer remains is between 50% and 95% of the total area of ​​the court layer. ×: The area where the court layer remains is less than 50% of the total area of ​​the court layer.

[0151] Furthermore, based on the evaluation of the three release films, the adhesion between the film body and the coating layer was evaluated according to the following criteria. A: All three are ○ B: Of the three items, there are 0 "X" marks and 2 or fewer "O" marks. C: Of the three items, one or more are marked with an "X".

[0152] [Table 1]

[0153] [Table 2]

[0154] [Table 3]

[0155] As shown in Tables 1 and 2, in Examples 1 to 6, the aesthetic appearance of the resin-impregnated decorative laminate and the ease of removal of the cured resin layer (melamine) on the release layer were good. In other words, it was confirmed that by providing a coating layer containing cured material of a curable resin, having a 60° gloss value within a predetermined range, and having an RSm of the first surface within a predetermined range, it is possible to achieve both improved aesthetic appearance through reduced gloss and ease of removal of the cured resin layer on the release layer. Furthermore, as shown in Examples 1 to 6, it was confirmed that the integral mean load in the 90° tensile test varied greatly depending on the release film (film body).

[0156] Comparing Example 1 and Example 2, it was observed that reducing the matting agent content tended to increase the 60° gloss value of the release film. Although the RSm values ​​were similar for Example 1 and Example 2, the aesthetic appeal of the resin-impregnated decorative panel in Example 1 was better than that of the resin-impregnated decorative panel in Example 2. This is because the surface gloss (60° gloss value and 85° gloss value) in Example 1 was lower than that in Example 2, and was evaluated as having a design closer to real wood (matte). Furthermore, comparing Example 2 and Example 3, it was observed that increasing the average particle size of the matting agent tended to increase the RSm because the distance between the protrusions caused by the matting agent increased. In Example 3, the RSm was larger (the distance between the protrusions was larger) compared to Example 2, and the adhesion to the cured resin layer decreased, resulting in slightly inferior removal of the cured resin layer from the release layer. On the other hand, in Example 3, the average particle size of the matting agent was larger than in Example 2, resulting in lower surface gloss (60° gloss value and 85° gloss value) of the release film, and consequently, the aesthetic appearance of the resin-impregnated decorative panel was better. Furthermore, comparing Example 1 with Examples 2 and 3, Example 1 had lower 60° gloss value and RSm of the release film compared to Examples 2 and 3, achieving a higher level of balance between improved aesthetic appearance due to reduced gloss and ease of removal of the cured resin layer on the release layer.

[0157] Comparing Example 1 and Example 4, Example 4 produced a coating layer containing a cured thermosetting resin, but, similar to Example 1, it achieved both improved aesthetics through reduced gloss and ease of removal of the cured resin layer on the release layer. In other words, regardless of the type of curable resin, it was possible to achieve both improved aesthetics through reduced gloss and ease of removal of the cured resin layer on the release layer. Furthermore, comparing Example 1 and Example 5, Example 5 produced a coating layer with a wrinkled structure on the first surface, but, similar to or better than Example 1, it achieved both improved aesthetics through reduced gloss and ease of removal of the cured resin layer on the release layer. Specifically, in Example 5, the 60° gloss value was significantly lower than in Example 1, and the 85° gloss value was also significantly lower, resulting in excellent aesthetics resembling real wood.

[0158] On the other hand, as shown in Table 3, the aesthetic appearance of the resin-impregnated decorative panel in Comparative Example 1 was not good. This is presumed to be because the release film used in Comparative Example 1 had a high 60° gloss value, and was unable to sufficiently reduce the gloss of the cured resin layer. In Comparative Example 2, the removal of the cured resin layer from the release layer was not good. This is presumed to be because the release film used in Comparative Example 2 had a high RSm, resulting in poor adhesion to the cured resin layer, and was unable to sufficiently remove the cured resin layer from the release layer. In Comparative Example 3, the release film did not have a coating layer, and the 60° gloss value was too high, so no improvement in aesthetic appearance was obtained through reduced gloss. Furthermore, because the cured resin layer and the release film were excessively adhered, film fracture occurred in the 90° tensile test. In other words, it was difficult to properly peel the release film from the cured resin layer.

[0159] Thus, the present disclosure provides, for example, the following inventions.

[0160] [1] A resin-impregnated decorative panel including a release film, having a core substrate, a decorative sheet, a cured resin layer, and a release film in this order in the thickness direction, The decorative sheet described above has, in the thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape, in that order from the core substrate side. The above decorative sheet and the above cured resin layer include a cured product of the curable resin Y. The above release film comprises a film body and a coating layer positioned on the side of the film body that is closer to the cured resin layer. The above coating layer contains a cured product of the curable resin α. The 60° gloss value of the above coating layer is 30 or less. The above coating layer has a first surface which is the surface facing the cured resin layer, A resin-impregnated decorative laminate containing a release film, wherein the RSm (average length of curved elements) of the first surface described above, as specified in JIS B0601:2013, is 0.16 mm or less.

[0161] [2] The thickness of the film body is 40 μm or more, and the resin-impregnated decorative board includes the release film described in [1].

[0162] [3] The thickness of the film body is 100 μm or less, and the resin-impregnated decorative board includes the release film described in [1] or [2].

[0163] [4] The pure water contact angle on the first surface is 68.0° or greater and 92.0° or less, and the resin-impregnated decorative panel includes a release film as described in any of [1] to [3].

[0164] [5] The RSm (average length of the curved elements) of the first surface described above is 0.01 mm or more, and the resin-impregnated decorative panel includes a release film as described in any of [1] to [4].

[0165] [6] A resin-impregnated decorative laminate containing a release film as described in any of [1] to [5], wherein the Rsk (skewness) of the first surface described above, as specified in JIS B0601:2013, is 2.0 or less.

[0166] [7] A resin-impregnated decorative laminate containing a release film as described in any of [1] to [6], wherein the 85° gloss value of the above-mentioned coating layer is 25 or less.

[0167] [8] The above coating layer is a resin-impregnated decorative laminate containing a release film according to any one of [1] to [7], which contains a matting agent.

[0168] [9] The first surface described above is a resin-impregnated decorative panel containing a release film according to any one of [1] to [8], having a wrinkled structure.

[0169]

[10] The above-mentioned curable resin α is an ionizing radiation-curable resin or a thermosetting resin, and the resin-impregnated decorative panel includes a release film as described in any of [1] to [9].

[0170]

[11] The above-mentioned release film is a resin-impregnated decorative panel comprising a release film according to any one of [1] to

[10] , having a primer layer between the film body and the coating layer.

[0171]

[12] A resin-impregnated decorative laminate containing the above-mentioned release film, wherein in a 90° tensile test in which the release film is peeled off from the resin-impregnated decorative laminate containing the above-mentioned release film, the integral mean load when the release film is pulled at a speed of 100 mm / min is 0.1 N or more and 3.0 N or less, as described in any of [1] to

[11] .

[0172]

[13] A resin-impregnated decorative panel containing the above-mentioned release film, wherein the 60° gloss value of the cured resin layer after peeling off the release film from the resin-impregnated decorative panel containing the above-mentioned release film is 16 or less, as described in any of [1] to

[12] .

[0173]

[14] A resin-impregnated decorative panel containing a release film according to any one of [1] to

[13] , wherein the thickness of the cured resin layer between the mold release layer and the release film is 30 μm or less.

[0174]

[15] The above-mentioned release layer is a resin-impregnated decorative panel containing a release film according to any one of [1] to

[14] , which contains a cured product of a curable resin X.

[0175]

[16] The above curable resin X is an ionizing radiation-curable resin, and the resin-impregnated decorative panel includes the release film described in

[15] .

[0176]

[17] The above resin-impregnated decorative laminate is a melamine decorative laminate, a resin-impregnated decorative laminate containing a release film as described in any of [1] to

[16] .

[0177]

[18] A release film used in the manufacture of a resin-impregnated decorative panel, having a core substrate, a decorative sheet, and a cured resin layer in this order in the thickness direction, The decorative sheet described above has, in the thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape, in that order from the core substrate side. The above decorative sheet and the above cured resin layer include a cured product of the curable resin Y. The above release film comprises a film body and a coating layer positioned on the side of the film body that is closer to the cured resin layer. The above coating layer contains a cured product of the curable resin α. The 60° gloss value of the above coating layer is 30 or less. The above coating layer has a first surface which is the surface facing the cured resin layer, A release film in which the RSm (average length of curved elements) of the first surface described above is 0.16 mm or less, as specified in JIS B0601:2013.

[0178]

[19] A method for manufacturing resin-impregnated decorative laminates, A preparation step for preparing a decorative sheet having a porous substrate, a design layer, and a release layer having a pattern shape, in this order in the thickness direction, (i) a core substrate, the decorative sheet, a curable resin layer containing curable resin Y, and a release film are arranged in this order in the thickness direction, (ii) the surface of the decorative sheet facing the porous substrate is arranged to face the core substrate, and (iii) the decorative sheet is impregnated with the curable resin Y, forming a laminate; A heating and pressurizing step is performed to heat and pressurize the above laminate, thereby curing the curable resin Y and forming a cured resin layer from the curable resin layer to obtain a cured laminate. A peeling step in which the release film is peeled off from the cured laminate, thereby removing the cured resin layer positioned in the thickness direction that overlaps with the release layer, while leaving the cured resin layer positioned between the patterns of the release layer, It has, The above release film comprises a film body and a coating layer positioned on the side of the film body that is closer to the cured resin layer. The above coating layer contains a cured product of the curable resin α. The 60° gloss value of the above coating layer is 30 or less. The above coating layer has a first surface which is the surface facing the cured resin layer, A method for manufacturing a resin-impregnated decorative laminate, wherein the RSm (average length of curved elements) of the first surface described above, as specified in JIS B0601:2013, is 0.16 mm or less. [Explanation of symbols]

[0179] 1...Porous base material 2…Design layer 3…Release layer 10… Decorative sheet 20…Core substrate 30...cured resin layer 40…Release film 41... Film body 42...Court layer 43…Primer layer 100... Resin-impregnated decorative laminate

Claims

1. A resin-impregnated decorative panel including a release film, having a core substrate, a decorative sheet, a cured resin layer, and a release film in this order in the thickness direction, The decorative sheet has, in the thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape, in that order from the core substrate side. The decorative sheet and the cured resin layer include a cured product of the curable resin Y. The release film comprises a film body and a coating layer positioned on the side of the film body that is closer to the cured resin layer. The coating layer includes a cured product of the curable resin α. The 60° gloss value of the aforementioned coating layer is 30 or less. The coating layer has a first surface which is the surface facing the cured resin layer, A resin-impregnated decorative laminate containing a release film, wherein the RSm (average length of the curved element) of the first surface, as specified in JIS B0601:2013, is 0.16 mm or less.

2. A resin-impregnated decorative panel containing the release film according to claim 1, wherein the thickness of the film body is 40 μm or more.

3. A resin-impregnated decorative panel containing the release film according to claim 1, wherein the thickness of the film body is 100 μm or less.

4. The resin-impregnated decorative panel containing the release film according to claim 1, wherein the pure water contact angle on the first surface is 68.0° or more and 92.0° or less.

5. The resin-impregnated decorative panel containing the release film according to claim 1, wherein the RSm (average length of the curved elements) of the first surface is 0.01 mm or more.

6. A resin-impregnated decorative panel containing a release film according to claim 1, wherein the Rsk (skewness) of the first surface, as defined in JIS B0601:2013, is 2.0 or less.

7. A resin-impregnated decorative panel containing a release film according to claim 1, wherein the 85° gloss value of the coating layer is 25 or less.

8. The aforementioned coating layer is a resin-impregnated decorative panel containing the release film according to claim 1, which contains a matting agent.

9. The first surface is a resin-impregnated decorative panel containing the release film according to claim 1, having a wrinkled structure.

10. The resin-impregnated decorative panel according to claim 1, wherein the curable resin α is an ionizing radiation-curable resin or a thermosetting resin, and includes a release film.

11. The resin-impregnated decorative panel includes the release film according to claim 1, wherein the release film has a primer layer between the film body and the coating layer.

12. The resin-impregnated decorative panel containing the release film according to claim 1, wherein in a 90° tensile test in which the release film is peeled off from the resin-impregnated decorative panel containing the release film, the integral mean load when the release film is pulled at a speed of 100 mm / min is 0.1 N or more and 3.0 N or less.

13. The resin-impregnated decorative panel containing the release film according to claim 1, wherein the 60° gloss value of the cured resin layer after peeling off the release film from the resin-impregnated decorative panel containing the release film is 16 or less.

14. The resin-impregnated decorative panel containing the release film according to claim 1, wherein the thickness of the cured resin layer between the mold release layer and the release film is 30 μm or less.

15. The resin-impregnated decorative panel includes the release film according to claim 1, wherein the release layer contains a cured product of the curable resin X.

16. The resin-impregnated decorative panel according to claim 15, wherein the curable resin X is an ionizing radiation-curable resin.

17. The resin-impregnated decorative laminate is a melamine decorative laminate, and the resin-impregnated decorative laminate includes the release film according to claim 1.

18. A release film used in the manufacture of a resin-impregnated decorative panel, having a core substrate, a decorative sheet, and a cured resin layer in this order in the thickness direction, The decorative sheet has, in the thickness direction, a porous substrate, a design layer, and a release layer having a pattern shape, in that order from the core substrate side. The decorative sheet and the cured resin layer include a cured product of the curable resin Y. The release film comprises a film body and a coating layer positioned on the side of the film body that is closer to the cured resin layer. The coating layer includes a cured product of the curable resin α. The 60° gloss value of the aforementioned coating layer is 30 or less. The coating layer has a first surface which is the surface facing the cured resin layer, A release film in which the RSm (average length of the curved element) of the first surface, as specified in JIS B0601:2013, is 0.16 mm or less.

19. A method for manufacturing resin-impregnated decorative laminates, A preparation step for preparing a decorative sheet having a porous substrate, a design layer, and a release layer having a pattern shape, in this order in the thickness direction, A laminate forming step in which a laminate is formed having (i) a core substrate, the decorative sheet, a curable resin layer containing curable resin Y, and a release film arranged in this order in the thickness direction, (ii) the surface of the decorative sheet facing the porous substrate, and (iii) the decorative sheet impregnated with the curable resin Y, A heating and pressurizing step is performed to heat and pressurize the laminate, thereby curing the curable resin Y and forming a cured resin layer from the curable resin layer to obtain a cured laminate. A peeling step in which the release film is peeled off from the cured laminate, thereby removing the cured resin layer positioned in the thickness direction that overlaps with the release layer, while leaving the cured resin layer positioned between the patterns of the release layer, It has, The release film comprises a film body and a coating layer positioned on the side of the film body that is closer to the cured resin layer. The coating layer includes a cured product of the curable resin α. The 60° gloss value of the aforementioned coating layer is 30 or less. The coating layer has a first surface which is the surface facing the cured resin layer, A method for manufacturing a resin-impregnated decorative laminate, wherein the RSm (average length of the curved element) of the first surface, as specified in JIS B0601:2013, is 0.16 mm or less.

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