Decorative sheet for melamine decorative laminate, melamine decorative laminate, and method for manufacturing melamine decorative laminate.

Abstract

To provide a decorative sheet for melamine decorative laminates that can suppress the occurrence of curling. [Solution] The material has a first surface and a second surface which is the surface opposite to the first surface, and is made of a base material selected from paper base material and fiber base material, A decorative layer and a first resin layer are arranged on the first surface side of the substrate, The substrate has a second resin layer disposed on the second surface side, The first resin layer is arranged in a pattern on the first surface side, The second resin layer is arranged in a pattern on the second surface side, Decorative sheet for melamine laminate.

Description

[Technical Field]

[0001] This disclosure relates to decorative sheets for melamine decorative laminates, melamine decorative laminates, and methods for manufacturing melamine decorative laminates. [Background technology]

[0002] Conventionally, decorative laminates have been used for surfaces such as tables, counters, walls, and floors. These laminates are made by impregnating a porous substrate, such as titanium paper, with an uncured melamine resin solution, and then curing the impregnated resin solution by heat pressing. Such melamine decorative laminates, which are impregnated and cured with melamine resin, exhibit physical properties such as high strength and heat resistance.

[0003] Decorative laminates are required to have a design that conveys a sense of luxury, and for example, the aesthetic appearance of the surface of the decorative laminate is adjusted by creating an uneven or textured surface. As decorative panels with adjusted surface design, decorative panels with an embossed surface, using embossed panels with a textured surface, have been proposed (see, for example, Patent Documents 1 and 2).

[0004] However, the decorative panels described in Patent Documents 1 and 2 have the problem that an embossing plate is required for each pattern in order to adjust the surface design, which is costly and difficult to manufacture. In addition, decorative panels with an embossed surface have the problem that it is difficult to match the uneven shape with the underlying pattern, making it difficult to give them a high level of design.

[0005] On the other hand, as a decorative laminate that adjusts the surface design without embossing, melamine decorative laminates have been proposed in Patent Document 3. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Publication No. 2015-193209 [Patent Document 2] Japanese Patent Publication No. 2017-87544 [Patent Document 3] International Publication No. 2016 / 148091 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0007] The melamine decorative laminate described in Patent Document 3 comprises a paper-based substrate, a release layer containing a cured product of an ionizing radiation-curable resin provided on a part of the surface of the paper-based substrate, and a surface layer containing a cured product of melamine resin provided on the remaining part of the surface of the paper-based substrate (the part of the surface of the paper-based substrate where the release layer is not provided). The melamine decorative laminate described in Patent Document 3 is manufactured by a method that includes the steps of providing a release layer on a part of the surface of the paper-based substrate, impregnating the paper-based substrate with an uncured product of melamine resin and covering the release layer with the uncured product of melamine resin, then heating to heat-cur the uncured product of melamine resin, and peeling off the cured resin film covering the release layer. The melamine decorative laminate described in Patent Document 3 does not use an embossed plate, thus resolving the problems described in Patent Documents 1 and 2. However, the melamine decorative laminate described in Patent Document 3 frequently suffered from the problem of the paper-based substrate curling during the manufacturing process, which reduced the manufacturing efficiency of the decorative laminate.

[0008] This disclosure aims to provide a decorative sheet for melamine decorative laminates that can suppress the occurrence of curling. Furthermore, this disclosure aims to provide a melamine decorative laminate using the aforementioned decorative sheet and a method for manufacturing a melamine decorative laminate. [Means for solving the problem]

[0009] The inventors of this invention have diligently investigated the cause of curling in decorative sheets for melamine decorative laminates. A decorative sheet for melamine decorative laminates is made into a melamine decorative laminate through a process that involves impregnating a substrate with melamine resin. In the process of impregnating the substrate with melamine resin, the melamine resin is impregnated from both the first and second surfaces of the substrate. The inventors have discovered that curling occurs in the substrate during the process of impregnating it with melamine resin, causing the decorative sheet to curl. Conventional decorative sheets for melamine decorative laminates have a resin layer placed on only one side of the substrate to avoid hindering the impregnation of the substrate with melamine resin. The inventors have discovered that when a resin layer is placed on only one side of the substrate, a significant difference in the degree to which the melamine resin-containing composition is impregnated occurs between the side of the substrate with the resin layer and the side without the resin layer, resulting in curling. As a result of diligent research, the inventors found that although the impregnation of the melamine resin into the substrate is reduced, by deliberately forming a resin layer on the opposite side of the substrate, it is possible to improve the balance of the degree to which the melamine resin-containing composition impregnates both sides of the substrate, thereby suppressing curling of the substrate and the decorative sheet for melamine decorative laminates.

[0010] This disclosure provides the following [1] to [3]. [1] Having a first surface and a second surface which is the surface opposite to the first surface, the substrate is selected from paper substrates and fiber substrates, A decorative layer and a first resin layer are arranged on the first surface side of the substrate, The substrate has a second resin layer disposed on the second surface side, The first resin layer is arranged in a pattern on the first surface side, The second resin layer is arranged in a pattern on the second surface side, Decorative sheet for melamine laminate. [2][1] A decorative sheet for melamine decorative laminates, The decorative sheet has a third resin layer containing melamine resin, which is disposed on the first surface side of the base material of the decorative sheet in an area where the first resin layer is not disposed. Melamine decorative laminate. [3] A method for manufacturing melamine decorative laminate, comprising the following steps 1 to 4 in order. Step 1: A step of immersing the decorative sheet for melamine decorative board described in [1] in a curable resin composition containing an uncured melamine resin. By Step 1, the curable resin composition is impregnated into the base material of the decorative sheet, and a layer containing the curable resin composition is formed on the entire surface on the first surface side of the base material of the decorative sheet, thereby obtaining a laminate α. Step 2: A step of obtaining a laminate β by disposing a release film on the layer side of the laminate α containing the curable resin composition. Step 3: A step of forming a third resin layer by curing the curable resin composition in the layer containing the curable resin composition of the laminate β by heating and pressurizing. Step 4: When removing the release film from the laminate β, removing the third resin layer on the first resin layer of the third resin layer together with the release film, and leaving the third resin layer formed at a location having no first resin layer.

Advantages of the Invention

[0011] According to the present disclosure, it is possible to provide a decorative sheet for melamine decorative board that suppresses the occurrence of curling, and a melamine decorative board and a method for manufacturing a melamine decorative board using the same.

Brief Description of the Drawings

[0012] [Figure 1] It is a cross-sectional view showing an embodiment of the decorative sheet for melamine decorative board of the present disclosure. [Figure 2] It is a cross-sectional view showing one step of the method for manufacturing a melamine decorative board of the present disclosure. [Figure 3] It is a cross-sectional view showing one step of the method for manufacturing a melamine decorative board of the present disclosure. [Figure 4] It is a cross-sectional view showing an embodiment of the melamine decorative board of the present disclosure.

Modes for Carrying Out the Invention

[0014] Figure 1 is a cross-sectional view showing an embodiment of the decorative sheet 100 for melamine decorative laminates according to the present disclosure. The decorative sheet 100 in Figure 1 has a base material 10 selected from paper base material and fiber base material. The base material 10 has a first surface (P1) and a second surface (P2) which is the surface opposite to the first surface. In Figure 1, the first surface (P1) corresponds to the surface of the base material, and the second surface (P2) corresponds to the back surface of the base material. Furthermore, the decorative sheet 100 in Figure 1 has a decorative layer 20 and a first resin layer 30 arranged on the first surface side of the base material 10, and a second resin layer 40 arranged on the second surface side of the base material 10. In Figure 1, the decorative layer 20 has a first decorative layer 21 and a second decorative layer 22. Furthermore, in Figure 1, the first resin layer 30 is arranged in a pattern on the first surface side, and the second resin layer 40 is arranged in a pattern on the second surface side.

[0015] <Base material> The base material can be selected from paper base materials and fiber base materials, with paper base materials being preferred. Because paper and fiber substrates are easily impregnated with melamine resin, the pencil hardness of the surface of melamine decorative laminates can be increased, making the surface of the laminate more resistant to scratches. The substrate has a first surface and a second surface which is the surface opposite to the first surface. The first and second surfaces of the substrate refer to the front and back surfaces of the substrate, not the sides of the substrate.

[0016] Examples of paper substrates include kraft paper, titanium paper, linter paper, resin-impregnated paper, tissue paper, and Japanese paper. Examples of fiber substrates 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. Furthermore, the fiber substrate may be a nonwoven fabric or a woven fabric.

[0017] There are no particular restrictions on the thickness of the substrate, and it can be appropriately selected according to the desired performance. To improve mechanical properties and handling, a thickness of 10 μm to 150 μm is preferred, 20 μm to 120 μm is more preferred, and 30 μm to 100 μm is even more preferred. When using paper as the base material, the basis weight should be 20 g / m² to ensure good mechanical properties and handling. 2 More than 150g / m 2 The following is preferable: 30 / m 2 More than 100g / m 2 The following are preferable.

[0018] The substrate may have one or both sides treated for easy adhesion, or may have an easy-adhesion layer on one or both sides, in order to improve adhesion with the layer formed on the substrate. Methods for easy adhesion treatment include physical surface treatment and chemical surface treatment.

[0019] <Decorative layer> The decorative layer may be formed in a pattern on a portion of the substrate or on the entire surface of the substrate. In regions where the substrate has a first resin layer, it is preferable to place the decorative layer between the substrate and the first resin layer. Examples of decorative layers include wood grain patterns, stone patterns, fabric patterns, leather patterns, geometric patterns, letters, symbols, line drawings, abstract patterns, solid colors, solid color gradients, and multi-color patterns, and combinations of these may also be used.

[0020] The decorative layer may be formed from a single layer or from two or more layers. For example, the decorative layer may be a combination of a first decorative layer and a second decorative layer.

[0021] The first decorative layer is preferably formed in an arbitrary pattern on the first surface side of the base material. The arbitrary pattern can be changed depending on the overall design to be applied. For example, if the overall design is a wood grain pattern, the first decorative layer is preferably formed by creating one or more patterns selected from vessels, autumn wood, and knots. Vessels are cylindrical cells that serve as pathways for water, and the arrangement of minute vessels makes it appear to the human eye as if a dark-colored pattern is being formed. Autumn wood refers to the part that is formed from summer to autumn, with a narrow grain and a dark color. Knots are traces of branches incorporated into the trunk, and are roughly circular or oval in shape, with a darker color than the surrounding tissue. When the overall design is a pattern of stone such as travertine, it is preferable that the first decorative layer be a recessed pattern. When the overall design is a tile pattern or brick pattern, it is preferable that the first decorative layer be a grout pattern. It is preferable that the pattern of the first decorative layer be synchronized with the pattern of the first resin layer. By synchronizing the pattern of the first decorative layer with the pattern of the first resin layer, the area having the first decorative layer and the first resin layer appears more recessed, making it easier to improve the visual three-dimensionality.

[0022] In this specification, "synchronization" is not limited to perfect alignment when the decorative sheet is viewed from above, but allows for an error that does not impair realism and a sense of luxury. For example, when the total area of ​​the first decorative layer when the decorative sheet is viewed from above is set to 100, the area of ​​the first resin layer that synchronizes with the first decorative layer is preferably 90 or more, more preferably 95 or more, even more preferably 97 or more, and even more preferably 99 or more.

[0023] The second decorative layer is preferably formed in an arbitrary pattern on the first surface side of the base material. The arbitrary pattern can be changed depending on the overall design to be applied. The pattern of the second decorative layer is preferably complementary to the pattern of the first decorative layer. For example, when applying a wood grain pattern to the entire piece, it is preferable that the second decorative layer be a wood grain pattern (excluding the pore groove pattern and / or knot pattern). When applying a stone pattern such as travertine to the entire piece, it is preferable that the second decorative layer be a pattern excluding the recessed areas. When applying a tile or brick pattern to the entire piece, it is preferable that the second decorative layer be a tile or brick portion.

[0024] The decorative layer can be formed, for example, by printing using a decorative layer ink containing a colorant and a binder resin.

[0025] Examples of colorants for the decorative layer include inorganic pigments such as carbon black, iron black, titanium white, antimony white, lead yellow, titanium yellow, reddish-brown, cadmium red, ultramarine, and cobalt blue; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; or dyes. It is preferable that the colorant for the first decorative layer does not contain a luminous pigment. There are no particular restrictions on the binder resin for the decorative layer. Examples include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluororesins, silicone resins, cellulose derivatives, and rubber resins.

[0026] The thickness of the decorative layer can be appropriately adjusted within a range of 0.1 μm to 20 μm, taking into consideration the desired design.

[0027] <First resin layer> The first resin layer is formed in a pattern on the first surface side of the substrate. In regions where the substrate has a decorative layer, it is preferable to place the first resin layer on the decorative layer. In regions where the substrate does not have a decorative layer, the substrate and the first resin layer may be in contact.

[0028] The pattern of the first resin layer is arbitrary. Examples of patterns for the first resin layer include wood grain patterns, stone patterns, fabric patterns, leather patterns, geometric patterns, letters, symbols, line drawings, abstract patterns, etc., and combinations of these may also be used. The pattern of the first resin layer does not have to be synchronized with the pattern of the decorative layer, but as mentioned above, it is preferable that the pattern of the first resin layer be synchronized with the pattern of the first decorative layer.

[0029] The first resin layer is preferably composed mainly of resin. The term "main component" means 50% by mass or more of the total amount constituting the first resin layer, preferably 60% by mass or more, and more preferably 70% by mass or more.

[0030] Examples of resins for the first resin layer include thermosetting resins, ionizing radiation-curable resins, and thermoplastic resins. Among these, a curable resin is preferred in order to obtain good mechanical strength. Furthermore, in step 4 described later, an ionizing radiation-curable resin is preferred among curable resins in order to facilitate the removal of the third resin layer on the first resin layer. The first resin layer preferably has penetration-resistant properties. Penetration-resistant properties mean the ability to suppress the penetration of compositions containing uncured melamine resin. For this reason, the resin of the first resin layer is preferably a curable resin, and more preferably an ionizing radiation-curable resin.

[0031] In this specification, when the term "curable resin" is used, it means a cured product obtained by curing an uncured curable resin. Similarly, when the term "thermosetting resin" is used, it means a cured product obtained by curing an uncured thermosetting resin, and when the term "ionizing radiation curable resin" is used, it means a cured product obtained by curing an uncured ionizing radiation curable resin. Furthermore, in this specification, when a curable resin composition, a thermosetting resin composition, or an ionizing radiation-curable resin composition is referred to, unless otherwise specified, it means a composition that includes uncured resin material.

[0032] The amount of curable resin in the first resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 90% by mass or more, and even more preferably 100% by mass, relative to the total amount of resin in the first resin layer. By including the curable resin in the above proportion in the first resin layer, the third resin layer on the first resin layer can be easily removed in step 4, which will be described later.

[0033] Examples of thermosetting resins include melamine resin, urea resin, melamine-urea resin, guanamine resin, diallyl phthalate resin, polyester resin, phenolic resin, epoxy resin, aminoalkyd resin, silicon resin, and polysiloxane resin.

[0034] Ionizing radiation-curable resins are resins that crosslink and harden upon irradiation with ionizing radiation, and possess ionizing radiation-curable functional groups. 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 it also includes other electromagnetic waves such as X-rays and gamma rays, and charged particle beams such as alpha rays and ion beams.

[0035] Specifically, the ionizing radiation-curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that are commonly used as ionizing radiation-curable resins. The polymerizable monomers and polymerizable oligomers may be used individually or in mixtures of two or more types.

[0036] 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. From the viewpoint of obtaining a higher quality aesthetic design and superior surface properties, the number of functional groups is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, with an upper limit of preferably 8 or less, and more preferably 6 or less. These polyfunctional (meth)acrylates may be used individually or in combination of multiple types.

[0037] 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.

[0038] 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.

[0039] From the viewpoint of obtaining a higher quality aesthetic design and superior surface properties, the number of functional groups in the polymerizable oligomer is preferably 2 or more, more preferably 3 or more, with an upper limit of preferably 8 or less, and more preferably 6 or less.

[0040] The weight-average molecular weight of the polymerizable oligomer is preferably 700 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. In this specification, the weight-average molecular weight is the average molecular weight measured by GPC analysis and converted to standard polystyrene.

[0041] The first resin layer preferably contains a release agent or a matting agent, and more preferably contains both a release agent and a matting agent.

[0042] The inclusion of a release agent in the first resin layer makes it easier to remove the third resin layer on the first resin layer in step 4, which will be described later. 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. Examples of silicone-based mold release agents include those with a polysiloxane structure as their basic structure, and among these, modified silicone oils in which organic groups are introduced to at least one of the side chains and terminals are preferred, and modified silicone oils in which organic groups are introduced to both terminals are more preferred.

[0043] The release agent content is preferably 0.1 parts by mass to 5 parts by mass, more preferably 0.5 parts by mass to 3 parts by mass, and even more preferably 1 part by mass to 2 parts by mass, per 100 parts by mass of the resin component of the first resin layer. When the release agent content is within the above range, the effect of adding the release agent can be efficiently obtained.

[0044] The first resin layer preferably contains a matting agent. By including a matting agent in the first resin layer, the surface of the first resin layer is roughened, making it easier to improve the gloss-matt finish of the melamine decorative laminate.

[0045] Examples of matting agents include organic fillers and inorganic fillers. Inorganic fillers are preferred because they easily provide good abrasion resistance.

[0046] Examples of organic fillers include particles of acrylic, styrene, and silicone. 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.

[0047] The average particle size of the inorganic filler is preferably 0.3 μm to 10 μm, more preferably 0.5 μm to 7 μm, even more preferably 1 μm to 5 μm, and even more preferably 2 μm to 4 μm. In this specification, the average particle size is a value measured by laser diffraction scattering. The matting agent content is preferably 5 to 40 parts by mass, and more preferably 10 to 35 parts by mass, per 100 parts by mass of the resin component of the first resin layer.

[0048] The thickness t1 of the first resin layer is not particularly limited, but is usually around 0.1 μm to 20.0 μm. From the viewpoint of more easily obtaining a high-quality design, it is preferably 0.5 μm to 10.0 μm, and more preferably 1.0 μm to 5.0 μm.

[0049] In this specification, the thickness of each layer is preferably calculated as the average value of 20 thicknesses. The thickness can be calculated, for example, from cross-sectional photographs of a decorative sheet for melamine decorative laminates and cross-sectional photographs of melamine decorative laminates. It is preferable that the 20 locations for calculating the average value are selected in a way that avoids any bias in location.

[0050] The first resin layer may contain colorants and luminous pigments to adjust the surface design.

[0051] When S1 is defined as the area ratio of the first resin layer to the total area of ​​the first surface of the substrate, it is preferable that S1 be 75% or less. By setting S1 to 75% or less, it is possible to impregnate the substrate with melamine resin and increase the strength of the melamine decorative laminate. It is more preferable that S1 be 65% or less, and even more preferable that it be 60% or less. If S1 is too small, it becomes difficult to achieve a good aesthetic appearance on the surface of the melamine decorative laminate. For this reason, S1 is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more.

[0052] <Second resin layer> The second resin layer is formed in a pattern on the second surface side of the substrate. As described above, although the impregnation of the melamine resin into the substrate is reduced, the decorative sheet for melamine decorative laminates of this disclosure makes it possible to suppress curling of the substrate and the decorative sheet for melamine decorative laminates by deliberately forming a resin layer on the opposite side of the substrate. The second resin layer preferably has penetration-resistant properties. Penetration-resistant properties mean the ability to suppress the penetration of compositions containing uncured melamine resin. For this reason, the resin of the second resin layer is preferably a curable resin, and more preferably an ionizing radiation-curable resin.

[0053] The pattern of the second resin layer is arbitrary. Examples of patterns for the second resin layer include wood grain patterns, stone patterns, fabric patterns, leather patterns, geometric patterns, letters, symbols, line drawings, abstract patterns, etc., and combinations of these may also be used. In melamine decorative laminates, the second resin layer is located on the back side of the base material. That is, in melamine decorative laminates, the second resin layer is usually difficult for people to see, so the second resin layer may be formed with a random pattern that lacks aesthetic appeal.

[0054] The second resin layer is preferably composed mainly of resin. The term "main component" means at least 50% by mass of the total amount constituting the second resin layer, preferably at least 60% by mass, and more preferably at least 70% by mass.

[0055] Examples of resins for the second resin layer include thermosetting resins, curable resins such as ionizing radiation-curable resins, and thermoplastic resins. Among these, curable resins are preferred, and ionizing radiation-curable resins are more preferred, in order to obtain good mechanical strength. An example of the curable resin for the second resin layer is the same as that for the curable resin for the first resin layer.

[0056] The second resin layer may or may not contain a matting agent, but it is preferable that it does not contain a matting agent. The second resin layer may or may not contain a release agent, but it is preferable not to contain a release agent in order to improve the adhesion of the reinforcing layer.

[0057] The thickness t2 of the second resin layer is not particularly limited, but is usually around 0.1 μm to 20.0 μm. From the viewpoint of more easily obtaining a high-quality design, it is preferably 0.5 μm to 10.0 μm, and more preferably 1.0 μm to 5.0 μm.

[0058] When defining the area ratio S2 of the second resin layer to the total area of the second surface of the base material, it is preferable that S2 is 70% or less. By setting S2 to 70% or less, it becomes easier to impregnate the base material with melamine resin, and it becomes easier to increase the strength of the melamine decorative board. More preferably, S2 is 60% or less, still more preferably 40% or less, and even more preferably 30% or less. If S2 is too small, it may be difficult to suppress the curl of the decorative sheet. Therefore, preferably, S2 is 3% or more, more preferably 5% or more, still more preferably 7% or more, and even more preferably 10% or more.

[0059] <Relationship between S1 and S2> For the decorative sheet for a melamine decorative board of the present disclosure, it is preferable that S1, which represents the area ratio of the first resin layer to the total area of the first surface of the base material, and S2, which represents the area ratio of the second resin layer to the total area of the second surface of the base material, are in a predetermined relationship.

[0060] For the decorative sheet for a melamine decorative board of the present disclosure, preferably, S1 / S2 is 0.25 or more and 4.00 or less, more preferably 0.33 or more and 3.75 or less, and still more preferably 0.40 or more and 3.50 or less. By setting S1 / S2 within the above range, it becomes easier to suppress the curl of the decorative sheet.

[0061] <0了000285>For the decorative sheet for a melamine decorative board of the present disclosure, preferably, S1 > S2. By setting S1 > S2, it is possible to improve the surface design property of the melamine decorative board and easily suppress the curl of the decorative sheet for the melamine decorative board.

[0062] For the decorative sheet for a melamine decorative board of the present disclosure, preferably, S1 + S2 is 80% or less. By setting S1 + S2 to be 80% or less, it becomes easier to impregnate the base material with melamine resin, and it becomes easier to increase the strength of the melamine decorative board. More preferably, S1 + S2 is 70% or less, and still more preferably 65% or less. If S1 + S2 is too small, it becomes difficult to improve the design property of the surface of the melamine decorative board. Therefore, S1 + S2 is preferably 10% or more, more preferably 20% or more, and even more preferably 30% or more.

[0063] <Relationship between t1 and t2> For the decorative sheet for a melamine decorative board of the present disclosure, it is preferable that the thickness t1 of the first resin layer and the thickness t2 of the second resin layer satisfy 0.5 ≦ t1 / t2 ≦ 1.5, more preferably 0.7 ≦ t1 / t2 ≦ 1.3, and even more preferably 0.9 ≦ t1 / t2 ≦ 1.1. By setting t1 / t2 within the above range, it becomes easier to exhibit the effect of setting S1 and S2 in a predetermined relationship.

[0064] For the decorative sheet for a melamine decorative board of the present disclosure, the total light transmittance defined in JIS K7361-1:1997 is preferably 10% or less, more preferably 5% or less, and even more preferably 1% or less.

[0065] <Manufacturing method of decorative sheet for melamine decorative board> The decorative sheet for a melamine decorative board of the present disclosure can be manufactured, for example, by a process including the following (1) to (3). The order of the steps (1) to (3) is not particularly limited, but (2) is preferably performed after (1). (1) A step of applying and drying ink for a decorative layer on the first surface side of a base material to form a decorative layer. ' (2) A step of applying and drying ink for a first resin layer on the first surface side of a base material to form a first resin layer. (3) A step of applying and drying ink for a second resin layer on the second surface side of a base material to form a second resin layer.

[0066] [Manufacturing method of melamine decorative board] The manufacturing method of the melamine decorative board of the present disclosure sequentially performs the following steps 1 to 4. Step 1: A step of immersing the decorative sheet for melamine decorative laminate described above in a curable resin composition containing uncured melamine resin. Step 1 impregnates the substrate of the decorative sheet with the curable resin composition and forms a layer containing the curable resin composition on the entire surface of the first side of the substrate of the decorative sheet, thereby obtaining a laminate α. Step 2: A step to obtain a laminate β by placing a release film on the layer side of the laminate α containing the curable resin composition. Step 3: A step of forming a third resin layer by heating and pressurizing the laminate β to cure the curable resin composition of the layer containing the curable resin composition. Step 4: When peeling off the release film from the laminate β, the third resin layer on the first resin layer of the third resin layer is removed together with the release film, while leaving the third resin layer formed in the area where the first resin layer is not present.

[0067] <Process 1> Step 1 is a step of immersing a decorative sheet for melamine decorative laminates according to the present disclosure in a curable resin composition containing uncured melamine resin.

[0068] In step 1, it is preferable to immerse the decorative sheet in the curable resin composition and then dry it. At this time, a portion of the curable resin composition may be cured, leaving the curable resin composition in a semi-cured state. Step 1 impregnates the base material of the decorative sheet with a curable resin composition, and a layer 210 containing the curable resin composition is formed on the entire surface of the first side of the base material of the decorative sheet, resulting in a laminate α(110) (Figure 2).

[0069] In step 1, it is preferable that the "thickness of the first resin layer" and the "thickness of the layer containing the curable resin composition in the region that does not have the first resin layer" satisfy the following relationship. [Thickness of the first resin layer] < [Thickness of the layer containing the curable resin composition in the region that does not have the first resin layer]

[0070] In the conventional method for manufacturing a melamine resin board, after step 1, the decorative sheet for the melamine decorative board curls, resulting in a decrease in the manufacturing efficiency of the melamine resin board. On the other hand, in the method for manufacturing a melamine resin board according to the present disclosure, curling of the decorative sheet for the melamine decorative board can be suppressed after step 1, so that the melamine resin board can be efficiently manufactured.

[0071] The curable resin composition is a curable resin composition containing an uncured melamine resin, and is preferably a thermosetting resin composition containing an uncured melamine resin. The proportion of the uncured melamine resin in the curable resin composition is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. The curable resin composition preferably does not contain a matting agent in order to achieve a good gloss matte effect.

[0072] The curable resin composition may contain water, alcohol, an organic solvent, etc. as a solvent. In the conventional manufacturing method, when the curable resin composition contains a solvent, the decorative sheet for the melamine decorative board is likely to curl after step 1. However, in the method for manufacturing a melamine resin board according to the present disclosure, even if the curable resin composition contains a solvent, curling can be easily suppressed.

[0073] <Step 2> Step 2 is a step of obtaining a laminate β (120) by disposing a release film (80) on the layer side containing the curable resin composition of the laminate α (see FIG. 3).

[0074] The release film 80 has a role of removing the third resin layer on the first resin layer among the third resin layers obtained by curing the layer containing the curable resin composition in step 4 described later. As the release film, when the adhesive force between the release film and the third resin layer is A1 and the adhesive force between the third resin layer and the first resin layer is A2, a release film that satisfies A1 > A2 is used. Further, as the release film, when the adhesive force between the release film and the third resin layer is A1 and the adhesive force between the third resin layer and the base material or the decorative layer is A3, a release film that satisfies A1 < A3 is used.

[0075] Examples of the release film 80 include a single layer of a plastic film made of polyester resin such as polyethylene terephthalate or polybutylene terephthalate; polyolefin resin such as polyethylene or polypropylene; or an acrylic resin; or a release layer formed on such a plastic film.

[0076] If the melamine decorative laminate has a reinforcing layer, it is preferable in step 2 to place the reinforcing layer 90 on the side of the laminate β that has the second resin layer (Figure 3). By adding a reinforcing layer, the mechanical strength of the resulting melamine decorative laminate can be increased.

[0077] Examples of reinforcing layers include thermosetting resin-impregnated sheets, which are made by impregnating a fibrous base material or a paper base material with a thermosetting resin. Examples of fibrous or paper substrates for the reinforcing layer include those similar to those exemplified as substrates for decorative sheets used in melamine decorative laminates. The thermosetting resin can be any resin that can impregnate the substrate in its thermosetting resin composition state, and phenolic resin is preferred. Specifically, phenolic resin-impregnated paper is preferred as the reinforcing layer. Phenolic resin-impregnated paper, for example, has a basis weight of 150 g / m². 2 More than 250g / m 2 This product can be manufactured by impregnating the following kraft paper with phenolic resin to an impregnation rate of 20% to 60%, and then drying it at a temperature of 100°C to 140°C.

[0078] <Process 3> Step 3 is a step of forming a third resin layer by heating and pressurizing the laminate β to cure the curable resin composition in the layer containing the curable resin composition.

[0079] Step 3 can be carried out, for example, by heat-pressing the laminate β with both sides of the laminate β sandwiched between mirror plates. During step 3, the curable resin composition impregnated into the substrate can also be cured.

[0080] The heating and pressurization conditions may be appropriately adjusted according to the type of thermosetting resin used, and there are no particular limitations. However, usually, the temperature condition is 100°C or higher and 200°C or lower, the pressure is 0.1 MPa or higher and 9.8 MPa or lower, and the time is 10 seconds or longer and 120 minutes or shorter.

[0081] <Step 4> In Step 4, when peeling and removing the release film from the laminate β, the third resin layer on the first resin layer among the third resin layers is removed together with the release film, and the third resin layer formed at a location without the first resin layer is left intact.

[0082] When Step 3 is carried out with the laminate β sandwiched between mirror-finished plates on both sides, it is preferable to take out the laminate β from between the mirror-finished plates before Step 4.

[0083] FIG. 4 is a cross-sectional view showing an embodiment of the melamine decorative board 500 obtained by Steps 1 to 4. In the melamine decorative board 500 of FIG. 4, the third resin layer 200 is disposed at a location without the first resin layer, while it is not disposed at a location having the first resin layer 30. Also, the thickness t1 of the first resin layer and the thickness t3 of the third resin layer are in the relationship of t1 < t3. Therefore, the melamine decorative board 500 of FIG. 4 has irregularities on the surface, and it is easy to improve the design property of the surface. Furthermore, the melamine decorative board 500 of FIG. 4 can also exhibit a gloss-matte effect between the region having the first resin layer and the region having the third resin layer. For example, due to the stress generated when removing the third resin layer on the first resin layer, the surface of the first resin layer may be matte-finished, and a gloss-matte effect may be exhibited. Also, by containing a matting agent in the first resin layer, the surface of the first resin layer can be matte-finished, and it is easy to exhibit a gloss-matte effect. Note that by matte-finishing the surface of the first resin layer, the region having the first resin layer appears to sink more, and it is easy to improve the sense of irregularities.

[0084] [Melamine Decorative Board] The melamine decorative board of the present disclosure is the decorative sheet for the melamine decorative board of the present disclosure described above, and A third resin layer containing a melamine resin, which is disposed in a region on the first surface side of the base material of the cosmetic sheet and where the first resin layer is not disposed.

[0085] In the melamine decorative board of the present disclosure, when the thickness of the first resin layer is defined as t1 and the thickness of the third resin layer is defined as t3, it is preferable that t1 < t3. By setting t1 < t3, due to the unevenness on the surface, it is easier to improve the design property of the surface.

[0086] It is preferable that t3 - t1 is 0.5 μm or more and 45.0 μm or less, more preferably 2.0 μm or more and 35.0 μm or less, and even more preferably 3.0 μm or more and 30.0 μm or less.

[0087] In the melamine decorative board of the present disclosure, the arithmetic mean roughness Ra1 of the surface of the decorative board in the region having the first resin layer and the arithmetic mean roughness Ra3 of the surface of the decorative board in the region having the third resin layer in JIS B0601:2001 preferably have a relationship of Ra1 > Ra3. By setting the relationship of Ra1 > Ra3, it is easier to exhibit a gloss-matte effect on the surface of the melamine decorative board. Also, by setting the relationship of t1 < t3 and Ra1 > Ra3, the region having the first resin layer of the melamine decorative board appears to sink more, and it is easier to improve the unevenness.

[0088] The third resin layer preferably does not substantially contain a matting agent in order to improve the gloss-matte effect. "Not substantially containing" means that it is 0.1% by mass or less of the total solid content of the third resin layer, preferably 0.01% by mass or less, and more preferably 0% by mass.

[0089] The thickness of the third resin layer is usually about 1 μm or more and 50 μm or less, preferably 3 μm or more and 40 μm or less, and more preferably 5 μm or more and 30 μm or less.

[0090] The third resin layer is preferably composed mainly of resin. The term "main component" means 50% by mass or more of the total amount constituting the third resin layer, preferably 60% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. The proportion of melamine resin to the total resin components of the third resin layer is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more.

[0091] The third resin layer may contain colorants and luminous pigments to adjust the surface design.

[0092] The melamine decorative laminate of this disclosure preferably has a reinforcing layer that covers the entire surface of the side of the decorative sheet having the second resin layer. By adding a reinforcing layer, the mechanical strength of the melamine decorative laminate can be increased. The embodiment of the reinforcing layer is as described in the embodiment of the manufacturing method of the melamine decorative laminate.

[0093] In the decorative sheet for melamine decorative laminates that constitutes the melamine decorative laminate of this disclosure, the base material is preferably a melamine resin-impregnated base material.

[0094] The melamine decorative laminate of this disclosure preferably has a total light transmittance of 10% or less, more preferably 5% or less, and even more preferably 1% or less, as specified in JIS K7361-1:1997.

[0095] <Adherent material> The melamine decorative laminate of this disclosure may be integrated with the substrate. The substrate is preferably placed on the side of the decorative sheet that has the second resin layer.

[0096] Examples of substrates include wood boards, gypsum boards, cement boards, fiber cement boards, ceramic boards, metal boards, resin boards, FRP boards, etc. These may be used individually or as a composite substrate formed by laminating two or more of these materials.

[0097] <Application> The melamine decorative laminates of this disclosure can be used, for example, as countertops for counters and desks; furniture; cabinets for kitchen products; building materials for houses such as doors; and the like.

[0098] This disclosure provides, for example, the following [1] to

[14] . [1] Having a first surface and a second surface which is the surface opposite to the first surface, the substrate is selected from paper substrates and fiber substrates, A decorative layer and a first resin layer are arranged on the first surface side of the substrate, The substrate has a second resin layer disposed on the second surface side, The first resin layer is arranged in a pattern on the first surface side, The second resin layer is arranged in a pattern on the second surface side, Decorative sheet for melamine laminate. [2] A decorative sheet for melamine decorative laminate according to [1], wherein S1 is defined as the area ratio of the first resin layer to the total area of ​​the first surface, and S2 is defined as the area ratio of the second resin layer to the total area of ​​the second surface, and S1 / S2 is 0.25 or more and 4.00 or less. [3] A decorative sheet for melamine decorative laminate according to [1], wherein S1 is defined as the area ratio of the first resin layer to the total area of ​​the first surface, and S2 is defined as the area ratio of the second resin layer to the total area of ​​the second surface, and S1 > S2. [4] A decorative sheet for melamine decorative laminate according to [1], wherein S1 is defined as the area ratio of the first resin layer to the total area of ​​the first surface, and S2 is defined as the area ratio of the second resin layer to the total area of ​​the second surface, and S1 + S2 is 80% or less. [5] A decorative sheet for melamine decorative laminate according to [1], wherein S1 is defined as the area ratio of the first resin layer to the total area of ​​the first surface, and S1 is 75% or less. [6] A decorative sheet for melamine decorative laminate according to [1], wherein S2 is defined as the area ratio of the second resin layer to the total area of ​​the second surface, and S2 is 70% or less. [7] The decorative sheet for a melamine decorative board according to any one of [1] to [6], wherein the first resin layer contains a matting agent. [8] The decorative sheet for a melamine decorative board according to any one of [1] to [7], wherein the first resin layer contains a release agent. [9] The decorative sheet for a melamine decorative board according to any one of claims [1] to [8], wherein the first resin layer and the second resin layer contain a curable resin.

[0099]

[10] A decorative sheet for a melamine decorative board according to any one of [1] to [9], and a third resin layer containing a melamine resin, which is disposed on the first surface side of the base material of the decorative sheet in a region where the first resin layer is not disposed. A melamine decorative board.

[11] The melamine decorative board according to

[10] , wherein when the thickness of the first resin layer is defined as t1 and the thickness of the third resin layer is defined as t3, t1 < t3. [[ID=?]]

[12] The melamine decorative board according to

[10] or

[11] , wherein the base material is a melamine resin-impregnated base material.

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

[10] to [1??], further comprising a reinforcing layer covering the entire surface on the side of the decorative sheet having the second resin layer.

[14] A method for manufacturing a melamine decorative board, comprising sequentially performing the following steps 1 to 4. Step 1: A step of immersing the decorative sheet for a melamine decorative board according to any one of [1] to [9] in a curable resin composition containing an uncured melamine resin. By step 1, the base material of the decorative sheet is impregnated with the curable resin composition, and a layer containing the curable resin composition is formed on the entire surface of the first surface side of the base material of the decorative sheet, thereby obtaining a laminate α. Step 2: A step of obtaining a laminate β by disposing a release film on the layer side of the laminate α containing the curable resin composition. Step 3: A step of forming a third resin layer by curing the curable resin composition of the layer containing the curable resin composition by heating and pressing the laminate β. It seems there is a small error in the line number in one of the items ( "12" is likely a misprint as it refers to [?] in the text). I've translated it as best as possible with the given text. If you can correct that, I can provide a more accurate translation.Step 4: When peeling off the release film from the laminate β, the third resin layer on the first resin layer of the third resin layer is removed together with the release film, while leaving the third resin layer formed in the area where the first resin layer is not present. [Examples]

[0100] Next, the present disclosure will be described in more detail by reference to examples, but the present disclosure is not limited in any way by these examples.

[0101] 1. Evaluation 1-1. Curling and moldability The decorative sheets for melamine decorative laminates in the examples and comparative examples were evaluated for curl and moldability according to the following criteria. <Evaluation Criteria> A: Products that do not exhibit curling or exhibit only very slight curling. Products that do not hinder the workability during the manufacturing of melamine decorative laminates and allow for easy production of melamine decorative laminates. B: Small curls occurred. This did not significantly hinder the workability during the manufacturing of melamine decorative laminates, and the melamine decorative laminates could be manufactured without difficulty. C: Products with significant curling. These products significantly hinder the workability during the manufacturing of melamine decorative laminates, requiring extra effort to produce them.

[0102] 1-2. Impregnation properties of melamine resin The decorative sheets for melamine decorative laminates in the examples and comparative examples were impregnated for 10 seconds in a melamine resin solution (a solution prepared by dissolving water-soluble methylolmelamine (product name: Nikarezin S-260) from Nippon Carbide Co., Ltd. in a 7:1 mixed solvent of water and isopropyl alcohol; solid content 60% by mass). The weight increase rate of the decorative sheet after impregnation was calculated using the following formula, and the impregnation properties of the melamine resin were evaluated according to the following criteria. Weight increase rate = (Weight of decorative sheet after impregnation - Weight of decorative sheet before impregnation) / Weight of decorative sheet before impregnation <Evaluation Criteria> A: Items with a weight change rate of 40% or more B: Items with a weight change rate of 35% or more but less than 40% C: Items with a weight change rate of less than 35%

[0103] 2. Manufacturing of decorative sheets and melamine decorative laminates for melamine decorative laminates. [Example 1] Paper base material (titanium paper base for building materials, product name "PM-67P" manufactured by KJ Specialty Paper Co., Ltd., basis weight: 80g / m²) 2 On the first surface of a 100 μm thick piece of wood, a 3 μm thick first decorative layer (wood grain pore portion) and a second decorative layer (wood grain surface portion) were formed by gravure printing using printing ink (DIC Graphics Co., Ltd., "Aude SPTI"). Next, the first resin layer ink described below was printed in a pattern onto the pattern of the first decorative layer, and cured by irradiation with an electron beam (pressure voltage: 165 KeV, 3 Mrad (30 kGy)) to form a first resin layer with a thickness t1 of 2.0 μm. The area ratio S1 of the first resin layer to the total area of ​​the first surface was set to 20%. Next, the second resin layer ink described below was printed in a pattern on the second surface of the paper substrate, and cured by irradiation with an electron beam (pressure voltage: 165 KeV, 3 Mrad (30 kGy)) to form a second resin layer with a thickness t2 of 2.0 μm, thereby obtaining the decorative sheet for melamine decorative laminate of Example 1. The area ratio S2 of the second resin layer to the total area of ​​the second surface was set to 10%.

[0104] Next, a decorative sheet for melamine decorative laminates was immersed for 1 second in a curable resin composition containing the uncured melamine resin described below, and dried. This impregnated the base material of the decorative sheet with the curable resin composition, and a layer containing the curable resin composition was formed on the entire first surface of the base material of the decorative sheet, resulting in a laminate α. Next, the following release film is laminated to the layer containing the curable resin composition of laminate α, and further, a reinforcing layer (obtained by impregnating kraft paper with a liquid uncured resin composition made of phenolic resin, with a basis weight of 245 g / m²) is laid on the second resin layer side of laminate α. 2 A laminate β was obtained by laminating three sheets of phenol resin-impregnated core paper (Ota Core, manufactured by Ota Sangyo Co., Ltd.). Next, both sides of the laminate β were sandwiched between mirror plates, and using a hot press machine, heat press molding was performed at a molding temperature of 150°C and a molding pressure of 100 kg / cm 2 for 10 minutes. By the above molding, a third resin layer formed by curing the layer containing the curable resin composition was formed. Also, by the above molding, the curable resin composition impregnated into the base material was cured. After molding, the laminate β was taken out from between the two mirror plates, and by peeling the peeling film from the laminate β, the melamine decorative board of Example 1 was obtained. When peeling and removing the peeling film from the laminate β, the third resin layer on the first resin layer in the third resin layer was removed together with the peeling film, and the third resin layer formed at a location without the first resin layer was left remaining. In the melamine decorative board of Example 1, t1 was 2.0 μm and t3 was 5.0 μm.

[0105] <Ink for the first resin layer> The following respective components were stirred for 1 hour at a rotation speed of 2000 rpm using a process homogenizer (manufactured by Sumitomo Heavy Industries, Ltd., "PH91") to obtain a resin composition. · 60 parts by mass of a radiation curable resin (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, trade name "Aronix M400" manufactured by Toagosei Co., Ltd.) · 0.9 parts by mass of a silicone-based release agent (both ends methacryloyloxyalkyl-modified organopolysiloxane, trade name "X-22-164B" manufactured by Shin-Etsu Chemical Co., Ltd.) · 18 parts by mass of silane coupling-treated silica (average particle diameter 3.0 μm) <00005`01>· 40 parts by mass of methyl ethyl ketone

[0106] <Ink for the second resin layer> The following respective components were stirred for 1 hour at a rotation speed of 2000 rpm using a process homogenizer (manufactured by Sumitomo Heavy Industries, Ltd., "PH91") to obtain a resin composition. · 60 parts by mass of a radiation curable resin (A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Toagosei Co., Ltd. under the trade name "Aronics M400") • Methyl ethyl ketone 40 parts by mass

[0107] <Curable resin composition containing uncured melamine resin> Melamine formaldehyde resin: 60 parts by mass (Water-soluble methylolmelamine from Nippon Carbide Co., Ltd. (Product name: Nikarezin S-260)) ·Water: 35 parts by mass • Isopropyl alcohol: 5% mass

[0108] <Preparation of release film> A 50 μm thick polyethylene terephthalate film (product name "Cosmoshine A4610" manufactured by Toyobo Co., Ltd.) was coated with the following ionizing radiation-curable resin composition on its easily adhesive surface. The film was then cured by irradiation with an electron beam (pressure voltage: 165 KeV, 5 Mrad (50 kGy)) to form a 5 μm thick release layer, thereby obtaining a release film. <<Ionizing radiation curable resin composition>> ·Ionizing radiation curable resin: 100 parts by mass (Ethylene bottom oxide modified product of trimethylolpropane triacrylate, trade name "Arronix M350" manufactured by Toagosei Co., Ltd.) • Silicone-based release agent: 2 parts by mass (Methacryloyloxyalkyl modified organopolysiloxane at both ends, trade name "X-22-164B" manufactured by Shin-Etsu Chemical Co., Ltd.) • Silica particles: 8 parts by mass (Product name "Silysia 450" manufactured by Fuji Silysia Chemical Co., Ltd., average particle size: 5.2 μm) • Ethyl acetate: 50 parts by mass

[0109] [Examples 2-16] Except for changing S1 and S2 to the values ​​in Table 1, decorative sheets and melamine decorative laminates for Examples 2 to 16 were obtained in the same manner as in Example 1.

[0110] [Comparative Examples 1-6] Using the value in Table 1 for S1, decorative sheets and melamine decorative laminates for Comparative Examples 1 to 6 were obtained in the same manner as in Example 1, except that a second resin layer was not formed. In Comparative Examples 1 to 6, the reinforcing layer was placed on the second surface side of the substrate.

[0111] [Table 1]

[0112] As shown in Table 1, the decorative sheet for melamine laminates in the examples can suppress curling and exhibit good moldability. Furthermore, the decorative sheet for melamine laminates in the examples can be confirmed to have good melamine resin impregnation properties. [Explanation of Symbols]

[0113] 10: Base material 20: Decorative layer 21: First Decorative Layer 22: Second decorative layer 30: 1st resin layer 40: Second resin layer 100: Decorative sheet for melamine laminate 110: Laminate α 80: Release film 120: Laminate β 200: 3rd resin layer 210: Layer containing a curable resin composition 500: Melamine decorative laminate

Claims

[Claim 1] It has a first surface and a second surface which is the surface opposite to the first surface, and the substrate is selected from paper substrates and fiber substrates, A decorative layer and a first resin layer are arranged on the first surface side of the substrate, The substrate has a second resin layer disposed on the second surface side, The first resin layer is arranged in a pattern on the first surface side, The second resin layer is arranged in a pattern on the second surface side, Decorative sheet for melamine laminate.

Images