decorative laminate

Abstract

To provide a decorative plate having a realistic feeling and a high-class impression and having a design property with high texture, and to provide a simple method of producing the decorative plate.SOLUTION: A decorative plate includes a first region and a second region having different refractive indices on its surface. A height difference between the first region and the second region is 1 μm or less. A refractive index (n1) of a resin included in the surface of the first region and a refractive index (n2) of a resin included in the surface of the second region satisfy a relationship of n1<n2.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This invention relates to decorative panels and methods for manufacturing decorative panels. [Background technology]

[0002] For interior and exterior building materials, such as cabinets for furniture and kitchen products, countertops used for various counters and desks, doors, and other residential building materials, thermosetting resin decorative laminates such as high-pressure melamine resin decorative laminates, low-pressure melamine resin decorative laminates, diallyl phthalate (DAP) resin decorative laminates, polyester decorative laminates, guanamine resin decorative laminates, and phenolic resin decorative laminates are used because they have excellent properties in terms of scratch resistance, impact resistance, heat resistance, and stain resistance.

[0003] With the increasing consumer preference for luxury goods in recent years, these thermosetting resin decorative panels are increasingly desired to have a realistic appearance (hereinafter simply referred to as "realism") and a sense of luxury that closely resembles the surface irregularities of real wood, stone, fabric, leather, and other materials, particularly surface irregularities that are synchronized with the pattern. Methods to improve realism and a sense of luxury have long been employed to enhance realism by imparting irregularities to at least the surface layer of the decorative panel. For example, embossing using embossing plates, molded sheets, or transfer sheets with a pattern transfer layer laminated on the molded surface of a molded sheet in a releaseable manner has been employed for a long time. However, improving realism through embossing requires a separate process of making an embossing plate and forming a resin layer to create the irregularities through embossing. Furthermore, the manufacturing process becomes longer due to the need for both embossing plate making and embossing. Furthermore, the uneven surface can lead to contamination problems, such as dirt accumulating in the recesses. Additionally, when embossing is used to add realism and a sense of luxury to patterns such as wood grain, it is necessary to adjust the position of the wood grain pattern and the embossed area, i.e., to align them. However, this alignment is difficult, and the yield of good products decreases.

[0004] As a method to solve the problems of the length of the manufacturing process, the difficulty of registration, and the decrease in yield associated with such embossing, and to impart an uneven shape to the surface of a decorative panel, for example, Patent Document 1 proposes a decorative panel with excellent realism and a method for manufacturing the same, which expresses a clear uneven shape that is precisely matched to the pattern of the release layer by having a release layer in the shape of a pattern in a part of the surface and a thermosetting resin layer in the remaining part of the surface that does not have the release layer. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2016-182808 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0006] However, even with the decorative panel and its manufacturing method disclosed in Patent Document 1, the problem remained that it was not possible to achieve both the appearance of surface irregularities synchronized with the pattern and the appearance of stain resistance due to the accumulation of contaminants in the recesses.

[0007] This invention was made under such circumstances, and aims to provide a decorative panel with excellent stain resistance, a sense of realism and luxury due to the appearance of surface irregularities synchronized with the pattern, and a simple method for manufacturing the decorative panel. [Means for solving the problem]

[0008] As a result of diligent research to solve the aforementioned problems, the present inventors have found that the aforementioned problems can be solved by an invention relating to a decorative panel having the following configuration.

[0009] The present invention aims to provide [1] to

[17] . [1] A method for manufacturing decorative laminates, comprising the following steps (1) to (5). (1) A step of forming a release layer on a part of one side of a releasable support, and forming a primer layer on the side of the releasable support where the release layer is formed and at least on a portion without the release layer, to obtain Sheet (1). (2) A step of obtaining a laminate (A) by stacking a substrate (1) impregnated with an uncured thermosetting resin on the release layer side of the Sheet (1).

[0010] (3) A step of heat-pressing the laminate (A) with mirror plates sandwiching both sides thereof, causing a part of the uncured thermosetting resin to penetrate into the primer layer of the transfer sheet and curing the uncured thermosetting resin. (4) A step of taking out the laminate (A) from between the mirror plates. (5) A step of peeling and removing the releasable support from the laminate (A) to obtain a decorative board having a first region with the release layer in the plane and a second region without the release layer in the plane.

[0011] [2] The method for manufacturing a decorative board according to [1], further including a step of forming a decorative layer on the primer layer of the Sheet (1) in the step (1). [3] The method for manufacturing a decorative board according to [1] or [2], wherein the substrate (1) is a substrate formed on a core layer. [4] The method for manufacturing a decorative board according to any one of [1] to [3], wherein on the surface having the first region and the second region of the decorative board, the difference in elevation between the first region and the second region is within 1 μm.

[0012] [5] The method for manufacturing a decorative board according to any one of [1] to [4], wherein the refractive index (n1) of the resin contained on the surface of the first region and the refractive index (n2) of the resin contained on the surface of the second region satisfy the relationship n1 < n2. [6] The method for manufacturing a decorative board according to any one of [1] to [5], wherein in the step (1), as the releasable support, a releasable support having a release layer on the releasable support is used, and the release layer is formed on the release layer. [7] The method for manufacturing a decorative board according to any one of [1] to [6], wherein in the step (1), the primer layer is also formed on the release layer.

[0013] [8] The method for manufacturing a decorative board according to any one of [1] to [8], wherein the release layer is a cured product of an ionizing radiation-curable resin composition containing a reactive silicone. [9] A decorative board having a resin layer on a substrate, wherein the resin layer has a first region and a second region on the surface, the difference between the elevation of the first region and the elevation of the second region is 1 μm or less, and the refractive index (n1) of the resin contained in the surface of the first region and the refractive index (n2) of the resin contained in the surface of the second region satisfy the relationship n1 < n2.

[10] The decorative board according to [9], wherein at least one outermost surface of the decorative board includes the first region and the second region.

[0014]

[11] The decorative board according to [9] or

[10] , wherein the resin layer corresponding to the first region has a release layer from the substrate side, and the resin layer corresponding to the second region has a primer layer from the substrate side.

[12] The decorative board according to any one of [9] to

[11] , wherein the resin layer corresponding to the first region has a primer layer and a release layer in this order from the substrate side, and the resin layer corresponding to the second region has a primer layer from the substrate side.

[13] The decorative board according to any one of [9] to

[12] , having a decorative layer between the substrate and the resin layer.

[0015]

[14] The decorative board according to any one of [9] to

[13] , further including a core layer on the side of the substrate opposite to the resin layer.

[15] The decorative board according to any one of [9] to

[14] , wherein the surface of the resin layer corresponding to the first region includes a cured product of an ionizing radiation-curable monomer containing a reactive silicone.

[0016]

[16] The content of triazine residues (TA1) in the first region and the content of triazine residues (TA2) in the second region satisfy the relationship TA1 < TA2. The decorative panel according to any one of [9] to

[15] .

[17] The contact angle of water (θ1) in the first region and the contact angle of water (θ2) in the second region on at least one outermost surface of the decorative panel satisfy the relationship θ1 > θ2. The decorative panel according to any one of [9] to

[16] .

Advantages of the Invention

[0017] According to the present invention, it is possible to provide a decorative panel having excellent antifouling properties, a high-class feeling along with a realistic feeling, and a high-quality design feeling, and a simple manufacturing method of the decorative panel.

Brief Description of the Drawings

[0018] [Figure 1] It is a schematic perspective view showing the appearance of an example of the decorative panel of the present invention. [Figure 2] It is a schematic diagram showing the layer structure in a cross-sectional view of an example of the transfer sheet of the present invention. [Figure 3] It is a schematic diagram showing the layer structure in a cross-sectional view of an example of the transfer sheet of the present invention. [Figure 4] It is a schematic diagram showing the layer structure in a cross-sectional view of an example of the transfer sheet of the present invention. [Figure 5] It is a conceptual diagram of peeling and removing the peelable support. [Figure 6] It is a schematic diagram of the decorative panel.

Modes for Carrying Out the Invention

[0019] 〔Decorative Panel〕 The decorative panel of the present invention has a resin layer on a substrate. The resin layer has a first region and a second region on the surface. The difference between the elevation of the first region and the elevation of the second region is 1 μm or less. The refractive index (n1) of the resin contained on the surface of the first region and the refractive index (n2) of the resin contained on the surface of the second region satisfy the relationship n1 < n2. It is a decorative panel.

[0020] There are no particular restrictions on the shape of the decorative panel of the present invention, and it can be appropriately selected as desired. For example, it may be flat, curved, or have corners or other non-flat shapes. Figure 1 shows a flat decorative panel, but the shape of the decorative panel of the present invention is not limited to this. Considering the ease of manufacturing and applications of the decorative panel, a flat shape is preferred.

[0021] <Resin layer> The decorative panel of the present invention has a resin layer, and the resin layer must have a first region and a second region on its surface. The elevations of the first and second regions vary depending on the layers they comprise, as will be described later. However, in order to ensure sufficient stain resistance on the surface of the decorative panel, it is important that the elevations of the first and second regions are visually substantially the same (i.e., there is virtually no difference in elevation between the two regions). Here, "visually being substantially the same in elevation between the first and second regions" means that the difference in elevation between the first and second regions must be 1 μm or less.

[0022] In this specification, "elevation" refers to the thickness direction of the decorative material, and in Figure 6, it refers to the z-direction. A high (or low) elevation at a specific location (a specific surface, a specific position, etc.) means that the z-coordinate value, which is the thickness direction at that location, is relatively large (or small). In Figure 6, the higher a location is in the figure, the higher its elevation; the lower a location is in the figure, the lower its elevation.

[0023] The difference in elevation between the two regions, the first region and the second region, improves the accumulation of dirt in the concave portions of the surface, enhances antifouling properties, and to prevent the physical three-dimensional sense (or unevenness) caused by the elevation difference between the two regions from inhibiting the manifestation of the three-dimensional sense based on the refractive index difference between the two regions described below, the difference in elevation between the two regions is preferably 0.8 μm or less, which is the maximum wavelength of visible light, more preferably 0.6 μm or less, and even more preferably 0.4 μm or less, which is the minimum wavelength of visible light. There is no particular limitation on the lower limit value, and 0 μm is most preferable. However, when it is difficult to make the difference in elevation between the two regions exactly 0 μm, within a range that does not complicate the manufacturing process or material selection or increase the manufacturing cost, it is sufficient that the elevation difference (i.e., unevenness) between the two regions is visually not substantially felt and sufficient antifouling properties can be ensured. Although it also depends on the planar shape (pattern pattern) of the two regions, the decorative layer, or both of them, generally, if the elevation difference between the two regions is 0.3 μm, it is sufficient. Here, "substantially" means that it is below the visually distinguishable threshold value. The difference in elevation between the elevation of the first region and the elevation of the second region can be determined, for example, by the method described in the examples.

[0024] The refractive index (n1) of the resin contained on the surface of the first region is different from the refractive index (n2) of the resin contained on the surface of the second region. n1 and n2 vary depending on the resin contained on the surface of the first region and the resin contained on the surface of the second region, and their absolute values can be adjusted as appropriate. In order to impart a high design quality with a three-dimensional sense due to the fact that, based on the principle mechanism described below, due to the difference in light reflectance between the regions on the surface, a concavo-convex shape can be visually recognized even though the physical elevation difference is substantially 0, it is necessary to satisfy the relationship n1 < n2.

[0025] That is, when the refractive index of the resin contained on the surface of the first region is n1, the refractive index of the resin contained on the surface of the second region is n2, and the refractive index of air is n0, the light reflectance R1 of the surface of the first region is, when the incident angle of light from the air to the surface of the first region is φ0, R1 P =tan 2 {φ0 - sin-1 (n0sinφ0 / n1)} / tan 2 {φ0+sin -1 (n0sinφ0 / n1)} [Equation 1’] R1 S =sin 2 (φ0 - sin -1 (n0sinφ0 / n1)) / sin 2 (φ0 + sin -1 (n0sinφ0 / n1)) [Equation 1’’] It becomes as follows. Here, R1 P and R1 S are the reflectance for the P - polarized component and the reflectance for the S - polarized component, respectively.

[0026] (Although these equations are well - known in the optical field, for example, refer to pages 20 - 29 of "Science Library Physics = 9 Optics", first edition second printing issued on September 30, 1980, published by Science Co., Ltd.) Similarly, when the incident angle of light from the air to the surface of the second region is φ0, the reflectance R2 of the light on the surface of the second region for the P - polarized component and the S - polarized component, respectively, is R2 P =tan 2 {φ0 - sin -1 (n0sinφ0 / n2)} / tan 2 {φ0 + sin -1 (n0sinφ0 / n2)} [Equation 2’] R2 S =sin 2 (φ0 - sin -1 (n0sinφ0 / n2)) / sin 2 (φ0 + sin -1 (n0sinφ0 / n2)) [Equation 2’’] It becomes as follows.

[0027] Incidentally, to facilitate the understanding of the principle and simplify the equations, consider the case where the incident angle of light to each of the regions 21 and 22 is φ0≒0 degrees, that is, almost normal incidence (in the sense that light is incident from the direction of the normal N to the surface of the decorative panel 3). In this case, the distinction between P - polarized light and S - polarized light also disappears, and [Equation 1’] - [Equation 2’’] can be approximated in the following simple form.

[0028] The reflectance R1 of the light on the surface of the first region is R1=(n1 - n0) / (n1 + n0) [Equation 1’’’] The reflectance R2 of the light on the surface of the second region is R2=(n2 - n0) / (n2 + n0) [Equation 2’’’] Since the refractive index of air is approximately 1, when approximated as n0 = 1, [Equation 1’’’] and [Equation 2’’’] further become The reflectance R1 of the light on the surface of the first region is R1=(n1 - 1) / (n1 + 1) [Equation 1] The reflectance R2 of the light on the surface of the second region is R2=(n2 - 1) / (n2 + 1) [Equation 2] And can be approximated

[0029] As is apparent from [Equation 1’’’] and [Equation 2’’’], or [Equation 1] and [Equation 2], If n1 < n2, then R1 < R2 [Equation 3] It becomes

[0030] As is apparent from [Equation 3], when the refractive index n1 of the resin contained in the surface of the first region is made smaller (relatively) than the refractive index n2 of the resin contained in the surface of the second region, when illuminated at the same light incident angle and observed in the same line-of-sight direction, (relatively), the reflectance R1 of the light on the surface of the first region is smaller than the reflectance R2 of the light on the surface of the second region. Therefore, the second region becomes relatively brighter than the first region, resulting in a difference in brightness and gloss, and a three-dimensional effect is manifested

[0031] To more strongly manifest a three-dimensional effect and impart a sense of reality and luxury, it is preferable to increase the difference between n1 and n2. It is preferable that the difference between n1 and n2 is 0.02 or more, more preferably 0.03 or more, and still more preferably 0.05 or more. From the viewpoints of easy availability of the resin contained in the surface of the first region and the resin contained in the surface of the second region and maintaining the strength of a practical decorative material, it is preferable that it is 0.20 or less, more preferably 0.18 or less, and still more preferably 0.16 or less n1 and n2 can be determined, for example, by the method described in the examples

[0032] In the present invention, "plan view" means viewing the decorative panel of the present invention in a planar direction from the side (surface side) having the first region and the second region. A typical example of a "plan view" is when the line of sight coincides with the normal direction N of the surface of the decorative panel, as explained with reference to Figures 1 and 2. However, the "plan view" in the present invention is not limited to this form and also includes any case in which the decorative panel of the present invention is viewed from the side (surface) having the resin layer consisting of the first region 21 and the second region 22 in the originally assumed line of sight. Furthermore, in the present invention, "cross-sectional view" means viewing a cross section parallel to the normal direction N of the surface of the decorative panel of the present invention from the normal direction N and a direction perpendicular to the cross section, as shown in Figure 1, and also includes any case in which it is viewed from a direction in which at least the cross-sectional shape of the decorative panel of the present invention can be seen.

[0033] In order to obtain a high-quality design with a realistic and luxurious feel, the decorative panel of the present invention preferably has at least one outermost surface that includes the first region and the second region, and more preferably the outermost surface of the main surface of the decorative panel that is viewed by the viewer includes the first region and the second region.

[0034] The resin layer corresponding to the first region preferably has a release layer described later, starting from the substrate side, in order to obtain a high-quality design that has both realism and a sense of luxury, and preferably has the primer layer and release layer described later, starting from the substrate side. In order to obtain a high-quality design with a realistic and luxurious feel, it is preferable that the resin layer corresponding to the second region has a primer layer, as described later, on the substrate side.

[0035] The area of ​​the first region (S1) and the area of ​​the second region (S2) on at least one of the outermost surfaces of the decorative panel can be adjusted as appropriate according to the desired design. In order to obtain a high-quality design that has both a realistic feel and a sense of luxury, the total ratio of S1 and S2 to the outermost surface is preferably 80% or more, more preferably 90% or more, and it is even more preferable that the outermost surface consists substantially only of the first region and the second region.

[0036] The area ratio value of the area of ​​the first region (S1) and the area of ​​the second region (S2) [(S1) / (S2)] can be adjusted as appropriate according to the desired design aesthetic, but it is preferably 10 / 90 or more and 90 / 10 or less, more preferably 20 / 80 or more and 80 / 20 or less, and even more preferably 30 / 70 or more and 70 / 30 or less.

[0037] (first area) The first region preferably has a release layer on the outermost surface of the resin layer. This release layer facilitates the removal of the mold release support described later, and further prevents the uncured thermosetting resin impregnated into the substrate (1) described later from seeping into the first region. As a result, the first region has a different resin composition from the second region described later, and the n1 <n2とすることができる。

[0038] (Exfoliation layer) In the decorative panel of the present invention, the release layer preferably contains a cured product of an ionizing radiation-curable resin composition containing reactive silicone. The inclusion of reactive silicone makes it difficult for the uncured thermosetting resin impregnated into the substrate (1) to penetrate into the release layer in the first region, thus allowing for the production of a decorative panel with a realistic and luxurious feel and high-quality design using a simple manufacturing method, which is preferable.

[0039] Ionizing radiation-curable resin compositions are resin compositions that crosslink and harden upon irradiation with ionizing radiation. Ionizing radiation-curable resin compositions contain compounds having ionizing radiation-curable functional groups. Here, ionizing radiation-curable functional groups are groups that crosslink and harden upon irradiation with ionizing radiation, and preferred examples include functional groups having ethylenic double bonds such as (meth)acryloyl groups, vinyl groups, and allyl groups. Ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or crosslinking molecules, and usually ultraviolet (UV) or electron beams (EB) are used, but other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams are also included.

[0040] Specifically, the ionizing radiation-curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation-curable resins. It is preferable to use an ionizing radiation-curable resin containing reactive silicone. Furthermore, it is even more preferable to use a combination of an ionizing radiation-curable resin containing reactive silicone and another ionizing radiation-curable resin containing reactive silicone.

[0041] As polymerizable monomers, (meth)acrylate monomers having a radical polymerizable unsaturated group in the molecule are preferred, and among these, polyfunctional (meth)acrylate monomers are preferred. Here, "(meth)acrylate" means "acrylate or methacrylate". Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least one (meth)acryloyl group as such functional group. From the viewpoint of obtaining a higher texture and superior surface properties, acrylate monomers having an acryloyl group are preferred.

[0042] From the viewpoint of obtaining a higher quality aesthetic design and superior surface properties, the number of functional groups is preferably 2 or more, preferably 8 or less as the upper limit, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less. These polyfunctional (meth)acrylates may be used individually or in combination of multiple types.

[0043] Preferred polymerizable monomers include difunctional (meth)acrylates such as ethylene glycol di(meth)acrylate, bisphenol A tetraethoxydiaacrylate, bisphenol A tetrapropoxydiaacrylate, and 1,6-hexanediol diacrylate; and trifunctional or more (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate. In particular, from the viewpoint of obtaining a higher texture and superior surface properties, dipentaerythritol-based polymerizable monomers such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferred, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are more preferred, and the combined use of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate is especially preferred.

[0044] Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule, and having at least one (meth)acryloyl group as such functional group. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, polycaprolactone urethane (meth)acrylate oligomers, polycaprolactone diol urethane (meth)acrylate, and the like.

[0045] From the viewpoint of obtaining a higher quality aesthetic design and superior surface properties, the number of functional groups in these polymerizable oligomers is preferably 2 or more, preferably 8 or less as the upper limit, more preferably 6 or less, even more preferably 4 or less, and particularly preferably 3 or less.

[0046] The weight-average molecular weight of these polymerizable oligomers is preferably 500 or more, more preferably 1,000 or more, with an upper limit of preferably 80,000 or less, and more preferably 50,000 or less, considering the viewpoint of obtaining a higher texture and superior surface properties, as well as the ease of forming a second cured layer. In this specification, the weight-average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

[0047] Examples of reactive silicones include those with a polysiloxane structure as their basic structure, and further having at least one reactive functional group. Ionizing radiation-curable functional groups are preferred as the reactive functional group. The reactive silicone is preferably a modified silicone oil in which an organic group is introduced to at least one of its side chains and / or terminals, and more preferably a modified silicone oil in which an organic group is introduced to both terminals. From the viewpoint of obtaining a design with a higher texture, the organic groups that are preferred include reactive functional groups such as (meth)acrylic groups, amino groups, epoxy groups, mercapto groups, carbinol groups, phenol groups, and carboxyl groups, and non-reactive functional groups such as polyether groups, aralkyl groups, fluoroalkyl groups, alkyl groups, fatty acid amide groups, and phenyl groups. Among these, reactive functional groups are preferred, and (meth)acrylic groups are particularly preferred, i.e., (meth)acrylic modified silicone oil is particularly preferred. Furthermore, these organic groups may have substituents such as nitrogen atoms, sulfur atoms, hydroxyl groups, and alkyl groups.

[0048] The reactive silicone content is preferably 0.1 to 5% by mass, more preferably 0.5 to 3% by mass, and even more preferably 0.8 to 2% by mass, relative to the total amount of resin components forming the release layer. When the reactive silicone content is within the above range, the effect of adding reactive silicone can be efficiently obtained.

[0049] When the ionizing radiation-curable resin composition is of the ultraviolet curing type, it is preferable that the ionizing radiation-curable resin composition contains a photopolymerization initiator.

[0050] The release layer preferably contains an inorganic filler. The inclusion of an inorganic filler creates a visual contrast in light and shadow, resulting in a higher-quality aesthetic finish. Examples of inorganic fillers include particles made from inorganic materials such as oxides (aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, zinc oxide, zirconia oxide, etc.), hydroxides (aluminum hydroxide, magnesium hydroxide, calcium hydroxide, etc.), carbonates (magnesium carbonate, calcium carbonate, etc.), sulfates (calcium sulfate, barium sulfate, etc.), and silicates (magnesium silicate, aluminum silicate, calcium silicate, aluminosilicate, etc.). Among these, oxides (aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, zinc oxide, etc.) are preferred, and silica is particularly preferred.

[0051] From the viewpoint of obtaining a higher quality aesthetic, the average particle size of the inorganic filler is preferably 0.3 μm or more and 20 μm or less, more preferably 0.5 μm or more and 10 μm or less. In this specification, the average particle size of the filler is a value measured by laser diffraction scattering.

[0052] These inorganic fillers are preferably surface-treated. Examples of surface treatment agents for the inorganic fillers include alkoxysilanes and silane coupling agents having reactive groups such as (meth)acryloyloxy groups, epoxy groups, vinyl groups, styryl groups, amino groups, isocyanate groups, ureido groups, sulfide groups, and mercapto groups. From the viewpoint of obtaining a higher quality aesthetic, silane coupling agents having (meth)acryloyloxy groups, epoxy groups, vinyl groups, and amino groups, i.e., (meth)acryloyloxy-based silane coupling agents, epoxy-based silane coupling agents, vinyl-based silane coupling agents, and amino-based silane coupling agents are preferred. These surface treatment agents may be used individually or in combination of several types.

[0053] Preferred alkoxysilanes include trialkoxysilanes such as methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, decyltrimethoxysilane, and dodecyltrimethoxysilane. Furthermore, preferred (meth)acryloyloxy silane coupling agents include 3-(meth)acryloyloxypropylmethyldimethoxysilane, 3-(meth)acryloyloxypropyltrimethoxysilane, 3-(meth)acryloyloxypropylmethyldiethoxysilane, and 3-(meth)acryloyloxypropyltriethoxysilane. Preferred epoxy silane coupling agents include diethoxy(glycidyloxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyl Liethoxysilane is a preferred example, vinyltrimethoxysilane and vinyltriethoxysilane are preferred vinyl silane coupling agents, and N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, and N-phenyl-3-aminopropyltrimethoxysilane are preferred amino silane coupling agents.

[0054] Among the above, from the viewpoint of obtaining a design with a higher texture, surface-treated silica particles, obtained by surface-treating silica particles with a silane coupling agent, are preferred as the inorganic filler. They have a high affinity with silicone-based release agents, which are preferably used in the release layer, and the synergistic effect between the reactive silicone and the inorganic filler provides a particularly excellent improvement in design with a high texture.

[0055] The inorganic filler content is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 20 to 35 parts by mass, per 100 parts by mass of the resin component forming the release layer. When the inorganic filler content is within the above range, the effect of adding the inorganic filler can be efficiently obtained.

[0056] The release layer further includes an uncured resin composition containing weathering agents such as ultraviolet absorbers and light stabilizers, and various additives as desired, such as ultraviolet blockers, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, defoamers, antiblocking agents, lubricants, solvents, and other various additives. These weathering agents and other additives may be used alone or in combination of two or more kinds.

[0057] As the ultraviolet absorber, an ultraviolet absorber generally used for decorative boards can be used without particular limitation, and examples thereof include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers, hydroxyphenyltriazine-based ultraviolet absorbers, and the like. As the light stabilizer, an ultraviolet absorber generally used for decorative boards can be used without particular limitation, and examples thereof include hindered amine light stabilizers such as piperidinyl sebacate-based light stabilizers. From the viewpoint of improving the strength of the first cured product layer, these weathering agents may have a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, vinyl group, allyl group, etc. in the molecule.

[0058] The thickness of the release layer is not particularly limited as long as the difference in elevation between the elevation of the first region and the elevation of the second region can be 1 μm or less, and is usually about 0.1 to 20 μm. From the viewpoint of more easily obtaining a high-quality design texture, it is preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

[0059] (Second region) The second region preferably has a primer layer on the outermost surface of the resin layer. With this primer layer, the uncured thermosetting resin impregnated in the base material (1) described later will penetrate into the second region. As a result, the second region has a resin composition different from that of the first region, and it is preferable that n1 < n2 as described above.

[0060] (Primer layer) In the decorative board of the present invention, the primer layer has the role of adjusting the refractive index, and is also preferable for improving the adhesion of each layer as described later. In the first region 21, the primer layer 12 may have the primer layer 12 and the release layer 11 in this order from the side of the base material 16 as shown in FIG. 6 to be described later. Thereby, it is preferable because the adhesion of the decorative layer (1) 13 to be described later is increased by the release layer 11.

[0061] Examples of the resin material for forming the primer layer include urethane resin, polyester resin, acrylic resin, acrylic urethane resin, vinyl chloride-vinyl acetate copolymer resin, and the like. Further, from the viewpoint of efficiently obtaining excellent adhesion, the thickness of the primer layer is usually about 0.1 μm to 15 μm, preferably 0.3 μm to 10 μm, and more preferably 0.5 μm to 5 μm.

[0062] As described above, due to the relationship of n1 < n2, although the physical height difference between the two regions is substantially 0, the second region reflects more external light compared to the first region. Therefore, the first region appears relatively dark, visually expressing the appearance of a concave portion, and the second region appears relatively bright, visually expressing the appearance of a convex portion. Without creating unevenness on the surface of the decorative board like embossing as in Patent Document 1 described above, the decorative board of the present invention can express the design of the visual appearance of the surface uneven shape.

[0063] In the decorative panel of the present invention, there are no particular limitations on the pattern exhibited by the first region, but examples include wood grain pore patterns, recessed patterns on the surface of marble slabs (for example, recesses in travertine marble patterns), stone patterns that mimic the surface of rocks such as cleavage planes of granite slabs, recessed areas of fabric patterns (textures) that mimic the texture of cloth or cloth, wrinkled recesses in leather patterns that express the grain of leather, tile patterns or brickwork patterns, hairline recesses, grooved recesses, matte recesses, sandy recesses, and recesses in the shape of letters, symbols, or geometric patterns, as well as patterns such as marquetry and patchwork that combine these. Furthermore, as a pattern that combines these, examples include recesses in patterns of artificial stone, such as artificial marble, which is made by mixing crushed stone such as marble with white cement, hardening it, and polishing it to a finish that resembles marble.

[0064] There are no particular restrictions on the width of the first region, and it can be determined appropriately according to the desired design. The average value is approximately 0.1 to 10 mm, and especially when a wood grain pattern is adopted, it is preferably 0.05 to 2 mm, and more preferably 0.1 to 1 mm, from the viewpoint of obtaining a design with a higher texture. The average value of the width of the first region is the average of the measured maximum width of any 10 first regions.

[0065] Furthermore, there are no particular restrictions on the length of the first region, and it can be appropriately determined according to the desired design. The average length is approximately 1 to 300 mm, and especially when a wood grain pattern is adopted, it is preferably 2 to 50 mm, and more preferably 3 to 45 mm, from the viewpoint of obtaining a design with a higher texture. The average value of the length of the first region is the average of the measured lengths of any 10 first regions.

[0066] The arithmetic surface roughness Ra of the outermost surface of the first and second regions is not particularly limited, but considering that it is easier to visually perceive the recessed shape and obtain a design with a higher texture, it is preferably 0.2 to 0.6 μm, more preferably 0.3 to 0.5 μm. In this specification, the arithmetic surface roughness Ra is the arithmetic mean roughness of JIS B0601:2013 with a cutoff value of 0.8 mm, and the arithmetic surface roughness Ra is measured at any ten locations on the outermost surface and the average value is used.

[0067] <Decorative layer> The decorative panel of the present invention preferably has a decorative layer in order to express a higher quality of design and to accommodate a variety of designs. The decorative panel of the present invention preferably has a decorative layer between the base material and the resin layer. The decorative layer may be, for example, a colored layer that covers the entire surface (a so-called solid colored layer), a patterned layer formed by various patterns, or a combination of these. For example, when coloring and concealing the base color of a substrate, a solid colored layer can be used to conceal the color while achieving a higher quality aesthetic. Furthermore, a combination of a solid colored layer and a patterned layer can be used to express a wider range of aesthetic possibilities. On the other hand, when the base pattern of the adherend is to be utilized, only a patterned layer can be provided without a solid colored layer. The decorative layer is preferably located between the substrate and the resin layer.

[0068] When a decorative layer has a patterned layer, the patterns exhibited by the decorative layer include the patterns exemplified by the patterns exhibited by the first region, such as wood grain patterns, marble patterns (e.g., travertine marble patterns), stone patterns that mimic the surface of rocks such as the cleavage surface of granite slabs, fabric patterns that mimic the texture of cloth or cloth, leather patterns that express the grain of leather, tile patterns, brickwork patterns, hairline patterns, serrated grooves, pear-skin texture, sand texture, letters, symbols, geometric patterns, patterns that combine these, such as marquetry and patchwork, and other patterns like those of the artificial marble mentioned above.

[0069] Among these patterns, considering the characteristics of the decorative laminate of the present invention, which possesses a high-quality design, the wood grain pore pattern is preferred as the pattern. When adopting the wood grain pore pattern, if a second pattern area is created that matches the darker pore groove portion in the wood grain pore pattern of the decorative layer, and a first area is placed directly above it, the pore groove portion will coincide with the first area, and the pore groove portion will appear darker visually. As a result, even though there is virtually no difference in elevation between the two areas and the surface of the decorative laminate is substantially flat, the pore groove portion will appear as a recess visually.

[0070] For example, in the decorative panel 3 shown in Figure 6, there is a first region 21 that is synchronized with the pattern of the decorative layer (1) 13, and the primer layer 12 and the release layer 11 are provided in this order directly above the decorative layer (1) 13. In addition, there is a second region 22 that is synchronized with the pattern of the decorative layer (2), and the primer layer 12 is provided directly above the decorative layer (2) 14. This configuration allows the pattern of the decorative layer to exhibit a visually pleasing design with a textured surface, while maintaining excellent stain resistance due to the virtually zero physical elevation difference between the first and second regions resulting from the difference in refractive index. In particular, by synchronizing the decorative layer with the first and second regions, a sense of realism similar to that of genuine wood, along with a luxurious feel, can be achieved, resulting in a decorative panel with a high-quality design.

[0071] The thickness of the decorative layer can be appropriately selected according to the desired pattern, but from the viewpoint of coloring and concealing the base color of the substrate and obtaining a higher quality design, 0.5 to 20 μm is preferred, 1 μm to 10 μm is more preferred, and 2 to 5 μm is even more preferred.

[0072] <Base material> The base material used in the decorative panel of the present invention is impregnated with an uncured thermosetting resin, as described below. The base material has the role of holding the release layer, the primer layer, and preferably the decorative layer. There are no particular restrictions on the base material, and it can be appropriately selected according to the desired performance. From the viewpoint of ease of handling, paper base materials, fiber base materials, resin base materials, etc. are preferred, and from the viewpoint of obtaining a decorative panel with superior mechanical properties, paper base materials and fiber base materials with liquid permeability are more preferred, and paper base materials are even more preferred.

[0073] Examples of paper substrates include kraft paper, titanium paper, linter paper, resin-impregnated paper, tissue paper, and Japanese paper. Examples of fiber substrates include nonwoven fabrics and woven fabrics, and include fiber substrates composed of inorganic fibers such as glass fibers, alumina fibers, silica fibers, and carbon fibers, fiber substrates composed of organic fibers of various synthetic resins such as polyester resin, acrylic resin, polyethylene resin, and polypropylene resin, and composites thereof.

[0074] The thickness of the substrate is not particularly limited and can be appropriately selected according to the desired performance. It can hold the required amount of uncured thermosetting resin, and from the viewpoint of ensuring mechanical properties and ease of handling, it is usually about 10 to 200 μm, preferably 20 to 150 μm, and more preferably 30 to 120 μm. Also, when using a paper substrate, from the same viewpoint, its basis weight is usually 20 to 150 g / m². 2 Approximately, preferably 30-100 g / m 2 That is the case.

[0075] A preferred embodiment of the decorative panel of the present invention is a thermosetting resin decorative panel obtained by pressure molding or heat-pressure molding using a paper substrate or fiber substrate impregnated with liquid uncured material of a thermosetting resin as a base material. The thermosetting resin must be able to penetrate the primer layer and preferably be a resin that can integrate with the curable resin forming the primer layer. This configuration results in a refractive index difference between the first and second regions of the decorative panel of the present invention, leading to high design aesthetics and improved mechanical strength.

[0076] As the curable resin to be impregnated into the base material, from the viewpoint of obtaining a more textured design property of the decorative board of the present invention and improving the mechanical strength, for example, melamine resin, urea resin, melamine-urea resin, guanamine resin, diallyl phthalate resin, polyester resin, phenolic resin, epoxy resin, amino alkyd resin, silicone resin, polysiloxane resin, etc. are preferably mentioned. Thermosetting resins such as melamine resin, urea resin, melamine-urea resin, guanamine resin, sulfonamide resin, etc. are preferred. Among them, melamine resin, melamine-urea resin, and phenolic resin are preferred, and particularly melamine resin is preferred.

[0077] When using melamine resin as the curable resin, the uncured product of the melamine resin hardly penetrates into the peeling layer on the outermost surface of the first region, and the uncured product of the melamine resin easily penetrates into the primer layer on the outermost surface of the second region. Therefore, a difference in the content of components derived from the uncured product of the melamine resin occurs between the first region and the second region. This difference in content causes a difference in refractive index between the two regions.

[0078] The difference in the content of components derived from the uncured product of this melamine resin can be evaluated by the content of triazine residues present in the skeleton of the melamine resin. The content of triazine residues (TA1) in the first region and the content of triazine residues (TA2) in the second region preferably satisfy the relationship TA1 < TA2.

[0079] It is preferable that the contact angle of water (θ1) in the first region and the contact angle of water (θ2) in the second region on at least one outermost surface of the decorative board satisfy the relationship θ1 > θ2. Since the outermost surface of the second region is a peeling layer and is preferably a cured product containing reactive silicone, it is preferable that the contact angle with water is smaller than that of the first region, and it is preferable to satisfy the relationship θ1 > θ2. For improving the design property, θ2 - θ1 is preferably 10 degrees or more and 70 degrees or less.

[0080] The substrate can be subjected to surface treatments such as physical surface treatments like oxidation or embossing, or chemical surface treatments, on one or both sides, in order to improve interlayer adhesion between the substrate and other layers, or to strengthen adhesion to various adherends. Oxidation methods include, for example, corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, and ozone-ultraviolet treatment, while surface texture creation methods include, for example, sandblasting and solvent treatment. These surface treatments are appropriately selected depending on the type of substrate, but generally, corona discharge treatment is preferred in terms of surface treatment effectiveness and ease of operation. Furthermore, to improve interlayer adhesion between the substrate and other layers, and to strengthen adhesion with various adherends, the substrate may be subjected to treatments such as forming a primer layer or a backside primer layer.

[0081] <Core Layer> The core layer is a layer that reinforces the decorative panel of the present invention, and is optionally provided on the side of the base material opposite to the resin layer. Depending on the type and application of the decorative panel, various materials and materials constituting various layers can be used for the core layer, but in particular, when the decorative panel is a thermosetting resin decorative panel, it is preferable that the core layer be formed from a thermosetting resin impregnated sheet. When a fiber base material or paper base material impregnated with thermosetting resin is used as the base material, a thermosetting resin decorative panel with superior mechanical properties can be obtained by combining it with a core layer formed from a thermosetting resin impregnated sheet.

[0082] Examples of core layers include fiber substrates and paper substrates impregnated with an uncured resin composition containing liquid uncured thermosetting resin. The type of fiber substrate or paper substrate used for the core layer is not particularly limited as long as it is one of the examples provided for the fiber substrate or paper substrate; the basis weight is preferably 100 to 300 g / m². 2 , comfortably 150~250g / m 2Furthermore, the thermosetting resin can preferably be the same as those exemplified as thermosetting resins that can be impregnated into the substrate in the state of a liquid, uncured resin composition, and the liquid, uncured resin compositions of the various thermosetting resins described above are also preferred. Among these thermosetting resins, phenolic resin is preferred, and as the core layer, phenolic resin-impregnated paper, which is commonly used as core paper for melamine resin decorative laminates and the like, is preferred.

[0083] Phenolic resin-impregnated paper, for example, has a basis weight of 150-250 g / m². 2 Preferably, the kraft paper used is manufactured by impregnating it with phenolic resin to an impregnation rate of approximately 20-60% and then drying it at approximately 100-140°C.

[0084] <Layer configuration> The configuration of the decorative panel of the present invention will be described below with reference to Figures 1 and 6. Figure 1 is a schematic perspective view showing the appearance of the decorative panel 3 of the present invention. The decorative panel 3 of the present invention has a first region 21 and a second region 22 on its outermost surface. Figure 6 is a schematic diagram showing the layer structure in a cross-sectional view of an example of the decorative panel of the present invention.

[0085] The first region 21 comprises, in this order from the outermost surface 5, a release layer 11, optionally a primer layer 12, optionally a decorative layer (1) 13, a substrate 16, and optionally a core layer 18. The second region 22 comprises, in this order from the outermost surface 5, a primer layer 12, optionally a decorative layer (2) 14, a substrate 16, and optionally a core layer 18.

[0086] (Uses of decorative panels) The decorative panel of the present invention is a decorative panel that possesses excellent stain resistance, while simultaneously having a realistic and luxurious feel, resulting in a high-quality design. Therefore, the decorative panel of the present invention can be used as is or after undergoing predetermined molding processes for various applications. For example, it can be laminated onto a base material such as a flat plate, curved plate, or sheet (or film) of various materials and used as interior and exterior building materials, such as countertops for furniture and kitchen cabinets, various counters and desks, and doors for residential buildings.

[0087] Examples of substrates include wood components used as sheet materials or three-dimensional articles, such as wood veneers, plywood, particleboard, and wood fiberboards like MDF (medium-density fiberboard) made from various types of wood such as cedar, cypress, pine, and lauan; metal components used as sheet materials, steel plates, three-dimensional articles, or sheets, such as iron and aluminum; ceramic components used as sheet materials or three-dimensional articles, such as glass, ceramics, non-cement ceramic materials like gypsum, and non-ceramic ceramic materials like ALC (autoclaved lightweight concrete) boards; and resin components used as sheet materials, three-dimensional articles, or sheets, such as acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride resin, cellulose resin, and rubber. These components can be used individually or in combination of multiple types.

[0088] (Manufacturing method for decorative panels) The method for manufacturing decorative panels of the present invention will be explained with reference to Figures 2 to 5.

[0089] The method for manufacturing decorative laminates of the present invention requires the following steps (1) to (5). (1) A step of forming a release layer on a part of one side of a release support, and forming a primer layer on the side of the release support on which the release layer is formed, and on at least the portion that does not have a release layer, to obtain a sheet (1). (2) A step of obtaining a laminate (A) by stacking a substrate (1) impregnated with an uncured thermosetting resin on the release layer side of the sheet (1).

[0090] (3) A step of heat-pressing the laminate (A) with both sides sandwiched between mirror plates, thereby impregnating a portion of the uncured thermosetting resin into the primer layer of the transfer sheet and curing the uncured thermosetting resin. (4) The step of removing the laminate (A) from between the mirror plates. (5) A step of peeling off the release support from the laminate (A) to obtain a decorative panel having a first region having the release layer in its surface and a second region not having the release layer in its surface.

[0091] <Release support containing a release support substrate> As shown in Figure 2, the release support 4 must include the release support 2 in order to obtain a higher quality aesthetic. The release support 2 preferably includes a release support base material 15. Examples of release support base material 15 include sheets of various resins such as polyester resins like polyethylene terephthalate and polybutylene terephthalate; polyolefin resins like polyethylene and polypropylene; and acrylic resins.

[0092] The thickness of the release support 4 is usually about 20 to 200 μm, preferably 30 to 100 μm, in order to obtain excellent mechanical strength.

[0093] The release support 2, which includes the release support substrate 15, may further have a release layer 17 as shown in Figure 4. <Release layer> The release layer preferably contains a release agent along with the curable resin. Including a release agent is preferable because it makes it easier to peel and remove the release support from the decorative panel. This reduces the likelihood of unevenness on the outermost surface of the resin layer formed by peeling, and reduces the elevation difference between the first and second regions described later, resulting in a design with a higher texture.

[0094] Examples of release agents include fluorine-based release agents and silicone-based release agents, and from the viewpoint of obtaining a higher quality aesthetic, silicone-based release agents are preferred. As a silicone-based release agent, the same type of reactive silicone used in the release layer can be used.

[0095] The release agent content is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and even more preferably 1 to 2 parts by mass, per 100 parts by mass of the curable resin forming the release layer. When the release agent content is within the above range, the effect of adding the release agent can be efficiently obtained. The release layer is an uncured resin composition containing, similar to the release layer, various additives as desired, such as inorganic fillers, UV absorbers, light stabilizers and other weathering agents, and other additives such as UV shielding agents, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion enhancers, leveling agents, thixotropic agents, coupling agents, plasticizers, defoaming agents, antiblocking agents, lubricants, and solvents. These weathering agents and other additives may be used individually or in combination.

[0096] The thickness of the release layer is not particularly limited as long as it is a thickness that exhibits the above-mentioned function, and is usually about 0.1 to 20 μm. From the viewpoint of more easily obtaining a high-quality design, it is preferably 0.5 to 10 μm, and more preferably 1 to 5 μm.

[0097] <(1) Process> In step (1), as shown in Figure 2, an ink used to form a release layer is applied to the release support 2 to form the desired release layer 11. If the release support 2 includes the release support substrate 15, it is preferable to form the release layer 11 on the release support substrate 15. The ink used to form the release layer is applied by known methods such as gravure printing, bar coating, roll coating, reverse roll coating, and comma coating, preferably by gravure printing.

[0098] The ink used to form the release layer preferably contains an ionizing radiation-curable resin composition containing a reactive silicone and a solvent. The solvent is not particularly limited as long as it dissolves the solute and does not hinder coating. As solvents, ketone solvents such as methyl ethyl ketone and acetone; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; ether solvents such as diethyl ether, tetrahydrofuran, and 1,4-dioxane; and alcohol solvents such as methanol, ethanol, and propanol can be used alone or in combination.

[0099] The uncured resin layer formed by the application of the aforementioned ink can be cured by irradiation with ionizing radiation such as electron beams or ultraviolet rays. When using electron beams as the ionizing radiation, the acceleration voltage can be appropriately selected depending on the resin used and the thickness of the layer, but it is generally preferable to cure the uncured resin layer with an acceleration voltage of approximately 70 to 300 kV. The irradiation dose is preferably the amount at which the crosslinking density of the ionizing radiation-curable resin saturates, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

[0100] There are no particular restrictions on the electron source; for example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graft type, resonant transformer type, insulated core transformer type, or linear type, dynamitron type, and high-frequency type can be used. Furthermore, when using ultraviolet radiation as ionizing radiation, the radiation emitted must include ultraviolet light with wavelengths of 190 to 380 nm. There are no particular restrictions on the ultraviolet source; for example, high-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, and carbon arc lamps can be used.

[0101] Furthermore, step (1) requires forming a primer layer on the side of the release support where the release layer is formed, and at least on the portion where the release layer is not present. As shown in Figure 2, it is not necessary to form the primer layer 12 on the release layer 11, and as shown in Figure 3, the primer layer 12 may also be formed on the release layer 11. In the decorative layer formation step described later, forming the decorative layer on the primer layer and then forming the decorative layer on the primer layer makes the formation of the decorative layer easier than forming the decorative layer directly on the release layer. For this reason, it is preferable to form the primer layer on the release layer as well.

[0102] The primer layer can be formed in the same manner as the release layer, except that a resin material is used to form the primer layer instead of the ink used to form the release layer. This makes it possible to obtain a sheet (1) 4 with a release layer and a primer layer formed on a release support, as shown in Figures 2 and 3.

[0103] <(2) Process> In step (2), a laminate (A) is obtained by stacking a substrate 16 impregnated with the uncured thermosetting resin on the release layer side of sheet (1) 4 shown in Figure 2. To impregnate a substrate having liquid permeability, the aforementioned uncured liquid thermosetting resin composition is prepared, and the uncured thermosetting resin composition is impregnated into the substrate. The impregnated uncured thermosetting resin composition is then heated at an appropriate time to cure through reactions such as crosslinking and polymerization, thereby becoming a cured thermosetting resin product. The substrate (1) may be a substrate formed on the core layer.

[0104] <(3) Process> In step (3), the laminate (A) is heat-pressed with both sides sandwiched between mirror plates, thereby impregnating a portion of the uncured thermosetting resin into the primer layer of the transfer sheet and curing the uncured thermosetting resin.

[0105] The pressure of the hot press is 10 kg / cm². 2 More than 300kg / cm2 It is preferably the following, 50 kg / cm 2 or more, and more preferably 200 kg / cm 2 or less, still more preferably 80 kg / cm 2 or more, and still more preferably 150 kg / cm 2 or less. By performing hot pressing within this range, the uncured thermosetting resin penetrates into the primer layer, and the penetration of the uncured thermosetting resin into the release layer is suppressed, so that a decorative board satisfying the relationship of n1 < n2 can be obtained, which is preferable.

[0106] For obtaining excellent mechanical strength, the molding temperature is preferably 10°C or more and 300°C or less, more preferably 80°C or more and 200°C or less, and still more preferably 100°C or more and 180°C or less. The hot pressing time can be appropriately adjusted according to the thickness of the laminate (A) and the type of the uncured thermosetting resin. For obtaining excellent mechanical strength, it is preferably 1 minute or more and 60 minutes or less, more preferably 5 minutes or more and 30 minutes or less, and still more preferably 8 minutes or more and 20 minutes or less.

[0107] <(4) Step> In the step (4), the laminate (A) is taken out from between the mirror finish plates.

[0108] <(5) Step> In the step (5), the release support is peeled off and removed from the laminate (A), and a decorative board having a first region with the release layer in the plane and a second region without the release layer in the plane is obtained. As shown in FIG. 5, the release support 2 which is a part of the sheet (1) 4 is peeled off and removed from the laminate (A) (illustrated by an arrow), thereby obtaining a decorative board 3. Thereby, the outermost surfaces of the first region and the second region are formed. [[ID=3l]]

[0109] <Step of forming a decorative layer> After forming the primer layer in the step (1), a step of further forming a decorative layer may be included. The decorative layer is formed by applying an ink used to form the decorative layer onto the release layer and the primer layer, or onto the primer layer, to provide a desired colored layer or patterned layer. The ink is applied by known methods such as gravure printing, bar coating, roll coating, reverse roll coating, and comma coating, preferably by gravure printing.

[0110] When the decorative layer has a wood grain pore pattern, the pore groove portion of the pattern of the decorative layer is designated as the first region, and the region other than the first region is designated as the second region. As a result, the pore groove portion appears darker visually, and the decorative panel of the present invention has a more realistic feel closer to real wood and a sense of luxury, resulting in a decorative panel with a high-quality design.

[0111] Any of the known methods exemplified above for applying the ink to the decorative layer may be adopted. Furthermore, the method for curing the ink of the decorative layer may be selected according to the type of curable resin contained in the ink of the decorative layer. For example, if the uncured resin composition is a resin composition containing liquid uncured material of a thermosetting resin, it may be cured by applying a heat treatment appropriate to the thermosetting resin used.

[0112] In the decorative panel obtained by the method for manufacturing decorative panels of the present invention, it is preferable that the elevation of the first region and the elevation of the second region are substantially the same in the surface having the first region and the second region, as this improves stain resistance. Here, "visually, the elevation of the first region and the elevation of the second region are substantially the same" means that it is preferable that the difference in elevation between the elevation of the first region and the elevation of the second region is 1 μm or less. The elevations of the first region and the elevation of the second region are as described above. [Examples]

[0113] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited in any way by these examples. (Evaluation and observation methods) (1) Evaluation of three-dimensionality (design quality) The cosmetic materials obtained in the examples and comparative examples were visually evaluated by 20 randomly selected adults under fluorescent lighting to determine whether or not they had a three-dimensional appearance. The results are shown in Table 1.

[0114] A: More than 18 people answered that it has a highly three-dimensional design. B: 11 to 17 people answered that the design had a high degree of three-dimensionality. C: Six to ten people answered that the design had a high degree of three-dimensionality. D: Five or fewer people answered that the design had a high degree of three-dimensionality.

[0115] (2) Evaluation of stain resistance (ability to erase with magic marker) On the surface of the decorative laminate obtained in each example, a straight line was drawn with an oil-based marker (black), left for 5 minutes, then wiped dry, and the degree of the remaining markings on the surface of the decorative laminate was visually evaluated according to the following criteria. A: No handwriting was found. B: Although some handwriting traces were found, they were not to the extent that they would cause any practical problems. C: Handwriting was found.

[0116] (3) Measurement of the difference between the elevation of the first region and the elevation of the second region. The first and second regions of the decorative panel were identified, and the elevations of 10 points in each region of the cross-section, including the first and second regions, were measured. The average value of these measurements was taken as the elevation of each region. The difference between the elevations of the first and second regions was calculated and taken as the difference between the elevations of the first and second regions.

[0117] (4) Measurement of the refractive index (n1) of the resin contained in the surface of the first region and the refractive index (n2) of the resin contained in the surface of the second region. The first and second regions of the decorative panel were identified, and the refractive index of each region was measured using Method B (Becke method by immersion) of JIS K 7142:2014.

[0118] (Example 1) (1) Preparation of release layer ink 60 parts by mass of ionizing radiation-curable monomer (Aronix M400, manufactured by Toagosei Co., Ltd.), 0.9 parts by mass of reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.), and 40 parts by mass of methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) were stirred at a rotation speed of 2000 rpm for 1 hour using a process homogenizer PH91 (manufactured by SMT Co., Ltd.) to prepare an ink for the release layer.

[0119] (2) Preparation of release support A release layer-forming ink containing 100 parts by mass of ionizing radiation-curable monomer (Aronix® M350, manufactured by Toagosei Co., Ltd.), 2 parts by mass of reactive silicone (X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.), 8 parts by mass of silica (Silysia 450, manufactured by Fuji Silysia Chemical Co., Ltd.), and 50 parts by mass of ethyl acetate is applied to the entire surface of the easy-adhesion surface of the support (50 μm thick PET film, Lumirror® S34, manufactured by Toray Industries, Inc.) at a rate of 5 g / m². 2 A mold-release support having a release layer on the support was prepared by coating the support so that it would be (when dry), and then curing it by irradiating it with an electron beam for 5Mrad at an accelerating voltage of 165kV.

[0120] (3) Preparation of the transfer sheet On the release support obtained in (2), a pattern with a constant width (30 μm) and length (50 mm) was printed using the release layer ink manufactured in (1) by gravure printing, and a release layer was formed by irradiating with an electron beam for 3 Mrad at an accelerating voltage of 165 kV to obtain sheet (1). The thickness of the release layer was 2 μm. Next, a primer layer made of acrylic urethane resin was printed onto the upper surface to a dry thickness of 1 μm, and then a wood grain decorative layer with a thickness of 3 μm was formed using pattern printing ink (Aude SPTI, manufactured by DIC Graphics Co., Ltd.). By forming a primer layer on the release layer as well, the adhesion of the pattern layer was improved.

[0121] (4) Manufacturing of decorative panels Base material (Titanium paper base for building materials, product name "PM-67P" manufactured by KJ Specialty Paper Co., Ltd., basis weight: 80g / m²) 2, with respect to a thickness of 100 μm, a liquid uncured composition of a thermosetting resin composed of 60 parts by mass of melamine formaldehyde resin, 35 parts by mass of water, and 5 parts by mass of isopropyl alcohol was impregnated using an impregnation apparatus for impregnation such that the uncured composition was in a proportion of 80 g / m 2 (when dried), and the substrate impregnated with the uncured thermosetting resin was obtained by drying.

[0122] On the substrate impregnated with this uncured thermosetting resin, two sheets of phenolic resin-impregnated core paper (manufactured by Ota Sangyo Co., Ltd., Ota Core) with a basis weight of 245 g / m 2 were laminated to create a laminate of the core layer and the substrate. On the substrate side of the laminate impregnated with the uncured thermosetting resin, the sheet (1) obtained in (3) was laminated so that the uncured thermosetting resin-impregnated substrate and the pattern layer were in contact, and laminate (A) was obtained.

[0123] The obtained laminate (A) was sandwiched between two mirror finish plates and heat molded under the conditions of a pressure of 100 kg / cm 2 at a molding temperature of 150 °C for 10 minutes to thermally cure the uncured thermosetting resin composition to form a laminate (A) containing a melamine resin. Finally, a decorative board was manufactured by peeling and removing the release support from the laminate (A). Regarding the first region and the second region, it was confirmed that the relationship was n1 < n2 and TA1 < TA2. The above evaluation was performed on the obtained decorative board, and the results are shown in Table 1.

[0124] (Comparative Example 1) Referring to JP-A-2016-182808, a decorative board was manufactured. After printing a pattern layer on the base paper for titanium paper for building materials used in the production of the decorative board in (4) of Example 1 using pattern printing ink (manufactured by DIC Graphics Co., Ltd., Audy SPTI), in the preparation of the ink for the release layer in (1) of Example 1, an ink for the release layer adjusted was used to print a melamine resin and a pattern layer with releasability to form a decorative layer, and then, in the same manner as in Example 1, it was cured by electron beam irradiation to obtain a laminate (C1). Next, (4) the uncured liquid composition of the thermosetting resin used in the manufacture of the decorative panel was impregnated into the laminate (C1) using an impregnation device, and dried to obtain a laminate (C1) impregnated with the uncured thermosetting resin.

[0125] The release support manufactured in Example 1 is laminated onto the decorative layer side of this laminate (C1) so that its release layer and decorative layer are in contact, and kraft paper impregnated with a resin liquid consisting of phenolic resin is used on the base paper side of the laminate (C1), with a basis weight of 245 g / m². 2 Two sheets of phenol resin-impregnated core paper (Ota Sangyo Co., Ltd., Ota Core) were laminated to obtain a laminate (C2). The obtained laminate (C2) was sandwiched between two mirror-finish plates and pressed at a pressure of 100 kg / cm² using a hot press machine. 2 The uncured thermosetting resin composition was then heat-molded at a molding temperature of 150°C for 10 minutes to form a laminate (C3) containing melamine resin. Finally, by peeling off the release support from the laminate (C3) along with the melamine resin and the release-compatible pattern layer within the decorative layer, a decorative panel was manufactured in which the melamine resin directly above the release-compatible pattern layer was removed, forming a recess. The above evaluation was performed on the obtained decorative panels, and the results are shown in Table 1.

[0126] (Comparative Example 2) In the preparation of the transfer sheet in (3) of Example 1, instead of the release layer ink manufactured in (1) above, A decorative panel was manufactured in the same manner as in Example 1, except that the liquid uncured composition of thermosetting resin described in (4) Manufacturing of decorative panel in Example 1 was used. The above evaluation was performed on the obtained decorative panels, and the results are shown in Table 1.

[0127] [Table 1]

[0128] Based on the results of Example 1, the decorative panel of the present invention was evaluated as having a high-quality design with a realistic and luxurious feel, compared to the decorative panels of Comparative Examples 1 and 2, which were obtained by a different manufacturing method than the present invention. Furthermore, when the second hardened layer was provided in accordance with the vascular grooves of the wood grain pattern, the decorative panel of Example 1 was evaluated as having excellent design properties. Excellent stain resistance was also evaluated. [Explanation of Symbols]

[0129] 1. Transfer sheet 2. Release-type support 3. Decorative panels 4. Sheet (1) 5. Top surface 11. Exfoliation layer 12. Primer layer 13. Decorative layer (1) 14. Decorative layer (2) 15. Release-resistant support substrate 16. Impregnated substrate 17.Release layer 18. Core Layer 21.First area 22.Second area N.Normal direction

Claims

1. A resin layer is provided on a substrate, the resin layer has a first region and a second region on its surface, the difference between the elevation of the first region and the elevation of the second region is 1 μm or less, the refractive index (n1) of the resin contained on the surface of the first region and the refractive index (n2) of the resin contained on the surface of the second region satisfy the relationship n1 < n2, A decorative panel wherein the resin layer corresponding to the first region has a release layer from the substrate side, the release layer contains a cured product of an ionizing radiation-curable resin composition containing reactive silicone, and the thickness of the release layer is 0.1 μm or more and 2 μm or less.

2. The decorative panel according to claim 1, wherein at least one of the outermost surfaces of the decorative panel includes the first region and the second region.

3. The resin layer corresponding to the second region has a primer layer from the substrate side, The decorative panel according to claim 1 or 2, wherein the primer layer comprises any of urethane resin, polyester resin, acrylic resin, acrylic urethane resin, and vinyl chloride-vinyl acetate copolymer resin.

4. The decorative panel according to any one of claims 1 to 3, wherein the resin layer corresponding to the first region has a primer layer and a release layer in that order from the substrate side, and the resin layer corresponding to the second region has a primer layer from the substrate side.

5. A decorative panel according to any one of claims 1 to 4, wherein a decorative layer is provided between the base material and the resin layer.

6. The decorative panel according to any one of claims 1 to 5, further comprising a core layer on the side of the substrate opposite to the resin layer.

7. The decorative panel according to any one of claims 1 to 6, wherein the surface of the resin layer corresponding to the first region includes a cured product of an ionizing radiation-curable monomer containing reactive silicone.

8. The decorative panel according to any one of claims 1 to 7, wherein the content of triazine residues in the first region (TA1) and the content of triazine residues in the second region (TA2) satisfy the relationship TA1 < TA2.

9. The decorative panel according to any one of claims 1 to 8, wherein the water contact angle (θ1) of the first region and the water contact angle (θ2) of the second region on at least one of the outermost surfaces of the decorative panel satisfy the relationship θ1 > θ2.

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