Decorative paper for resin-impregnated decorative laminates, melamine decorative laminates, and method for manufacturing melamine decorative laminates.

Abstract

To provide decorative paper for resin-impregnated decorative laminates and a melamine decorative laminate which can achieve high solidity and designability.SOLUTION: Decorative paper for resin-impregnated decorative laminates has base paper, a pattern layer provided on the base paper, a liquid repellent layer provided on the pattern layer, and a filler layer provided between the base paper and the pattern layer or between the pattern layer and the liquid repellent layer. There is also provided a melamine decorative laminate prepared with such a decorative paper for resin-impregnated decorative laminates, wherein the melamine decorative laminate has: the decorative paper for resin-impregnated decorative laminates; and a transfer layer that is provided, through an adhesion layer, in a region free of a liquid repellent layer on a pattern layer provided in the decorative paper for resin-impregnated decorative laminates.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] This disclosure relates to decorative paper for resin-impregnated decorative laminates, melamine decorative laminates, and a method for manufacturing melamine decorative laminates. [Background technology]

[0002] Conventionally, for example, a transfer sheet has been proposed in which a transfer layer and an adhesion layer are laminated in that order on one side of a base layer, and the transfer layer contains a cured product of an ionizing radiation-curable resin (for example, Patent Document 1). In the transfer sheet described in Patent Document 1, a transfer sheet is laminated onto a laminate in which a base paper and an uncured melamine resin layer are laminated, and then heated and pressurized (thermal transfer) is performed to cure the uncured melamine resin layer and produce a melamine decorative laminate. Furthermore, the laminate to be laminated with the transfer sheet may include a base paper, a pattern layer, and a liquid-repellent layer that provides a gloss difference in harmony with the pattern of the pattern layer (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2019-64132 [Patent Document 2] Japanese Patent Publication No. 2018-176484 [Overview of the project] [Problems that the invention aims to solve]

[0004] Since the laminate formed by laminating the aforementioned transfer sheet is made of a fibrous sheet material such as paper with good liquid absorption that can be impregnated with resin, a highly permeable and porous base paper is used for the laminate. As a result, the liquid-repellent layer placed on top of the base paper may seep into the base paper and fail to repel the transfer layer transferred from the transfer sheet, potentially reducing the three-dimensional effect and design quality due to the gloss of the liquid-repellent layer. This disclosure focuses on the points mentioned above and aims to provide decorative paper for resin-impregnated decorative laminates, melamine decorative laminates, and a method for manufacturing melamine decorative laminates that can achieve a high level of three-dimensionality and design. [Means for solving the problem]

[0005] To solve the above-mentioned problems, a decorative paper for resin-impregnated decorative boards according to one aspect of the present disclosure comprises a base paper, a pattern layer provided on the base paper, a liquid-repellent layer provided on the pattern layer, and a sealing layer provided between the base paper and the pattern layer or between the pattern layer and the liquid-repellent layer.

[0006] Furthermore, a melamine decorative laminate according to another aspect of the present disclosure comprises the above-mentioned decorative paper for resin-impregnated decorative laminates and a transfer layer provided via an adhesive layer in a region on the pattern layer of the decorative paper for resin-impregnated decorative laminates where a liquid-repellent layer is not formed.

[0007] Furthermore, in another embodiment of the present disclosure, a method for manufacturing a melamine decorative laminate involves forming a transfer sheet on one surface of a base layer by forming a transfer layer and an adhesion layer in that order, using an uncured ionizing radiation-curable resin; immersing the resin-impregnated decorative paper for decorative laminates in an aqueous melamine resin solution; laminating the transfer sheet onto the liquid-repellent side of the immersed resin-impregnated decorative paper to form a laminate; applying pressure and heat to the laminate to cure the uncured aqueous melamine resin solution contained in the base paper; peeling the base layer of the transfer sheet from the resin-impregnated decorative paper; transferring the portion of the transfer layer of the transfer sheet that is in contact with layers other than the liquid-repellent layer of the resin-impregnated decorative paper to the resin-impregnated decorative laminate; and irradiating the resin-impregnated decorative laminate with ionizing radiation to cure the ionizing radiation-curable resin of the transfer layer transferred to the resin-impregnated decorative laminate. [Effects of the Invention]

[0008] According to aspects of this disclosure, it is possible to provide decorative paper for resin-impregnated decorative laminates and melamine decorative laminates that can achieve a high degree of three-dimensionality and design quality, as well as a method for manufacturing melamine decorative laminates. [Brief explanation of the drawing]

[0009] [Figure 1] It is a cross-sectional view showing a configuration example of decorative paper for a resin-impregnated decorative board according to an embodiment of the present disclosure. [Figure 2] It is a cross-sectional view showing a configuration example of a melamine decorative board according to an embodiment of the present disclosure. [Figure 3A] It is a diagram for explaining a method for manufacturing a melamine decorative board according to the present disclosure, and is a cross-sectional view showing a transfer sheet before transfer and decorative paper for a resin-impregnated decorative board. [Figure 3B] It is a diagram for explaining a method for manufacturing a melamine decorative board according to the present disclosure, and is a cross-sectional view showing a transfer sheet and decorative paper for a resin-impregnated decorative board during transfer. [Figure 3C] It is a diagram for explaining a method for manufacturing a melamine decorative board according to the present disclosure, and is a cross-sectional view showing a transfer sheet after transfer and a melamine decorative board

Embodiments for Carrying Out the Invention

[0010] Next, embodiments of the present disclosure will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thicknesses of each layer, etc. are different from the actual ones. Further, the embodiments shown below are examples of configurations for embodying the technical idea of the present disclosure, and the technical idea of the present disclosure is not specified to be the following in terms of the material, shape, and structure of the components. The technical idea of the present disclosure can be variously modified within the technical scope defined by the claims described in the claims.

[0011] 1. Embodiments of the Present Disclosure (1.1) Basic Configuration of Decorative Paper for Resin-Impregnated Decorative Board Hereinafter, the configuration of the decorative paper 1 for a resin-impregnated decorative board according to the present disclosure will be described with reference to FIG. 1. The figure is a cross-sectional view showing a configuration example of the decorative paper 1 for a resin-impregnated decorative board. As shown in Fig. 1, the decorative paper 1 for resin-impregnated decorative board includes a base paper 11, a pattern layer 13 provided on the base paper 11, and a liquid-repellent layer 14 provided on the pattern layer 13. Further, the decorative paper 1 for resin-impregnated decorative board includes a blocking layer 12 provided between the base paper 11 and the pattern layer 13 or between the pattern layer 13 and the liquid-repellent layer 14. For the decorative paper 1 for resin-impregnated decorative board, for example, since the glossy liquid-repellent layer 14 is formed in a pattern synchronized with the pattern of the pattern layer 13, the pattern of the pattern layer 13 is expressed three-dimensionally and has high design quality. In this embodiment, the decorative paper 1 for resin-impregnated decorative board in which the blocking layer 12 is provided between the base paper 11 and the pattern layer 13 will be described. Hereinafter, the structure of each layer will be described.

[0012] <Base paper> The base paper 11 may be a fibrous sheet-like body such as paper with good water absorption that can be impregnated with resin later. For example, tissue paper, titanium paper, high-quality paper, bleached or unbleached kraft paper, etc. can be used. Among them, titanium paper, which is excellent in both printing suitability and resin impregnation suitability, is most preferable. Also, when it is desired to utilize the texture of the surface of the adherend (not shown) to which the decorative paper 1 for resin-impregnated decorative board is attached, so-called transparent paper having the property of becoming transparent by resin impregnation can also be used as the base paper 11. There is no particular restriction on the thickness of the base paper 11, but generally, the basis weight is 20 g / m 2 to 200 g / m 2 Those within the following range are used.

[0013] <Blocking layer> The blocking layer 12 is a layer for suppressing the penetration of the liquid-repellent layer 14 provided above the base paper 11 into the base paper 11, repelling the transfer layer 25 transferred from the transfer sheet 3 (details will be described later), and preventing the loss of the three-dimensional effect and design quality due to the gloss of the liquid-repellent layer 14. The sealing layer 12 can be made of one or more resin materials selected from inks such as nitrose-based resins, urethane-based resins, and acrylic-based resins, or coating resins such as thermosetting resins and ionizing radiation-curable resins. By using these materials, the liquid-repellent layer 14 is prevented from seeping into layers below the liquid-repellent layer 14, such as the base paper 11, thereby further improving the design of the decorative paper 1 for resin-impregnated decorative boards.

[0014] The sealing layer 12 may contain additives such as titanium dioxide, urethane resin, silica, pigment, nitrocellulose, carbon black, hydrated fine silica, and zinc oxide. Including such additives further suppresses the penetration of the liquid-repellent layer into the base paper, thereby further improving the design of the decorative paper 1 for resin-impregnated decorative panels. In addition, the inclusion of additives in the sealing layer 12 can improve the opacity of the adherend.

[0015] If an additive is added to the sealing layer 12, the amount of the additive should be greater than 0% by mass relative to the resin material constituting the sealing layer 12, preferably between 20% by mass and 70% by mass, and more preferably between 40% by mass and 50% by mass. When the amount of the additive is within this range, the effect of the additive can be fully realized. Furthermore, when titanium dioxide and other additives are included as additives, it is preferable that the other additives are added in an amount of 100% by mass or less relative to the titanium dioxide, and more preferably 80% by mass or less. This prevents a decrease in the opacity of the adherend due to an increase in the amount of additives other than titanium dioxide, which would reduce the amount of titanium dioxide added.

[0016] <Pattern layer> The pattern layer 13 is a layer for improving the design of the decorative paper 1 for resin-impregnated decorative boards by adding patterns and colors. There are no particular restrictions on the type of pattern that makes up the pattern layer 13; for example, it can be any desired pattern such as wood grain, stone pattern, fabric pattern, abstract pattern, geometric figure, letters, symbols, or a combination of two or more of these.

[0017] The pattern layer 13 can be created using a standard printing method with a standard printing ink that does not have liquid-repellent properties. There are no particular restrictions on the type of printing ink, and oil-based inks may be used, but it is preferable to use water-based inks considering their suitability for resin impregnation. This is because water-based inks have better compatibility with the aqueous solution of the impregnation resin compared to oil-based inks, allowing for rapid and uniform impregnation in the subsequent impregnation process, and also enabling the development of superior strength through integration with the impregnation resin.

[0018] While there are no particular restrictions on the type of water-based ink, it is most desirable to use one whose binder resin is primarily composed of casein or emulsion resin. These binder resins have the property of becoming poorly soluble in water after the drying process following ink printing, and are therefore less likely to redissolve in the aqueous solution of the impregnating resin during the subsequent resin impregnation process. This prevents damage to the image pattern and eliminates the risk of contamination of the impregnating resin.

[0019] Examples of emulsion resins include acrylic, vinyl acetate, styrene, and urethane types, while examples of latex resins include styrene-butadiene, acrylonitrile-butadiene, and methyl methacrylate-butadiene types.

[0020] In addition to casein and emulsion resin, other water-soluble resins such as polyvinyl alcohol and polyacrylamide, or water-soluble polymers such as polysaccharides and cellulose derivatives may be used in combination to improve the stability of the ink.

[0021] There are no particular restrictions on the method of forming the pattern layer 13; for example, any printing method such as gravure printing, offset printing, screen printing, flexographic printing, letterpress printing, or inkjet printing can be used. Furthermore, a solid ink layer may be provided for the purpose of coloring the base. In this case, in addition to the various printing methods described above, any coating method such as roll coating, gravure coating, rod coating, knife coating, air knife coating, spray coating, lip coating, or die coating can be used to apply the solid ink layer.

[0022] <Liquid repellent layer> The liquid-repellent layer 14 is formed in areas of the desired pattern where a matte or glossy texture is to be expressed. The liquid-repellent layer 14 may be colorless or colored. The resin used to form the liquid-repellent layer 14 is preferably a thermosetting resin having urethane bonds, such as a two-component curable urethane resin, or a curable resin such as an ionizing radiation-curable resin. Examples of curable resins that can be used include thermosetting resins such as melamine resins, epoxy resins, urea resins, phenolic resins, unsaturated polyester resins, diallyl phthalate resins, benzoguanamine resins, urethane resins, amino alkyd resins, and silicone resins, as well as ionizing radiation-curable resins such as (meth)acrylate resins and unsaturated polyester resins.

[0023] The gloss (sheen) of the liquid-repellent layer 14 can be adjusted as appropriate according to the desired design. The gloss of the liquid-repellent layer 14 can be adjusted, for example, by adding a gloss adjuster or by not adding a gloss adjuster.

[0024] Any conventionally known material can be used as a gloss modifier, but examples include inorganic materials such as silica, alumina (α-alumina, etc.), calcium carbonate, barium sulfate, kaolinite, and alumina silicate, or fine particles made of organic materials such as polycarbonate, nylon, urethane resin, acrylic resin, styrene resin, and silicone resin.

[0025] The average particle size of such gloss modifiers is preferably between 1 μm and 10 μm, and the amount added can be appropriately selected according to the desired gloss, i.e., glossiness.

[0026] It is desirable that silicone oil be added to the liquid-repellent layer 14 to impart liquid-repellent properties. As the silicone oil, unmodified silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxy-modified silicone oil, mercapto-modified silicone oil, carbinol-modified silicone oil, methacrylic-modified silicone oil, and phenol-modified silicone oil can be used. The amount of silicone oil added to the liquid-repellent layer 14 is preferably 0.01% by mass or more and 15% by mass or less relative to the resin, and more preferably 0.05% by mass or more and 10% by mass or less.

[0027] The amount of the liquid-repellent layer 14 should be appropriate to the desired design, but the amount applied after drying should be 4 g / m². 2 It is preferable that it be greater than 8 g / m 2 It is more preferable that the above conditions are met. When the amount of liquid-repellent layer 14 applied is within the above-mentioned range, a glossy liquid-repellent layer 14 is formed in large quantities or thickly, and penetration into layers below the liquid-repellent layer 14 is suppressed, improving the aesthetic appearance.

[0028] Furthermore, the liquid-repellent layer 14 may be formed from multiple layers with different planar shapes. For example, by forming a first liquid-repellent layer and a second liquid-repellent layer with different gloss properties by adding or omitting a gloss adjuster, or by varying the amount of gloss adjuster added, it is possible to create a gloss-matte finish for the liquid-repellent layer 14. There are no particular restrictions on the type of pattern formed by the first and second liquid-repellent layers; it may be in sync with or out of sync with the pattern layer 13. However, generally, syncing them results in a superior design and is preferable.

[0029] The thickness of the first and second liquid-repellent layers may be 0.5 μm or more and 100 μm or less, and preferably 1 μm or more and 30 μm or less. When the thickness of the first and second liquid-repellent layers is within this range, it is possible to suppress the absorption of thermosetting resin without it being repelled when impregnated, and it is also possible to suppress the occurrence of cracks in the first and second liquid-repellent layers when the decorative paper 1 for resin-impregnated decorative panels is wound onto a roll.

[0030] <Impregnation resin> The base paper 11, on which the sealing layer 12, pattern layer 13, and liquid-repellent layer 14 have been formed as described above, is then impregnated with resin. As the resin, any known thermosetting resin that has been conventionally used in the formation of resin-impregnated decorative panels can be used.

[0031] Examples of resins that can be used to impregnate the base paper 11 include melamine resins, epoxy resins, diallyl phthalate resins, benzoguanamine resins, urethane resins, alkyd resins, unsaturated polyester resins, phenolic resins, urea resins, and the like. These are generally impregnated into the decorative paper for resin-impregnated decorative boards in the form of an aqueous impregnation solution dissolved or dispersed in water.

[0032] The impregnation with the thermosetting resin may be carried out from the side of the base paper 11 that has the liquid-repellent layer 14, or from the opposite side. Furthermore, the thermosetting resin may be impregnated into the base paper 11 in two separate stages, one side at a time, or both sides simultaneously. Alternatively, a resin-impregnated overlay sheet, which has been pre-impregnated and dried with resin, may be used as the base paper 11. The impregnation rate of the thermosetting resin (the ratio of the mass of the impregnated resin to the mass after impregnation) is typically 20% by mass or more and 80% by mass or less, and preferably 40% by mass or more and 70% by mass or less. In addition, in order to obtain a melamine decorative laminate 2 with excellent physical properties (details will be described later), it is important that the resin is uniformly impregnated throughout the base paper 11.

[0033] (1.2) Basic composition of melamine decorative laminate The structure of the melamine decorative laminate 2 according to this disclosure will be described below with reference to Figure 2. Figure 2 is a cross-sectional view showing one example of the structure of the melamine decorative laminate 2. As shown in Figure 2, the melamine decorative laminate 2 has a transfer layer 25 provided on the surface of the decorative paper 1 for resin-impregnated decorative laminates, and the entire decorative paper 1 for resin-impregnated decorative laminates is impregnated with melamine resin. The transfer layer 25 is provided on the surface of the decorative paper 1 for resin-impregnated decorative laminates via an adhesion layer 26. The transfer layer 25 and the adhesion layer 26 will be described below. The composition of the decorative paper 1 for resin-impregnated decorative boards has been described above, so its explanation will be omitted.

[0034] <Transfer layer> The transfer layer 25 is provided via an adhesion layer 26 in areas on the pattern layer 13 of the decorative paper 1 for resin-impregnated decorative boards where the liquid-repellent layer 14 is not formed. The transfer layer 25 is a layer formed by transferring onto the resin-impregnated decorative paper 1 used in the manufacture of the melamine decorative laminate 2. The resin constituting the transfer layer 25 can be an ionizing radiation-curable resin. As an ionizing radiation-curable resin, for example, a resin that undergoes a crosslinking polymerization reaction after transfer by irradiation with ionizing radiation, transforming into a three-dimensional polymer structure, can be used. Examples of ionizing radiation include electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or crosslinking molecules, such as ultraviolet (UV), electron beams (EB), electromagnetic waves, and charged particle beams. As an ionizing radiation-curable resin, at least one of ultraviolet-curable resins and electron beam-curable resins is preferred because they have tack-free properties, meaning the resin no longer adheres after heat drying, and after-curing properties, meaning they can be cured by irradiation with ultraviolet or electron beams even after heat-press transfer.

[0035] <Close-up layer> The adhesion layer 26 is a layer for improving the adhesion between the transfer layer 32 and the decorative paper 1 for resin-impregnated decorative panels. As the resin constituting the adhesion layer 26, for example, a thermosetting resin such as urethane resin or acrylic resin can be used. It is preferable to use a thermosetting resin that does not contain components that exhibit liquid repellency, such as silicone oil. This allows any remaining melamine resin on the liquid-repellent layer 14 of the decorative paper 1 for resin-impregnated decorative panels to adhere to the adhesion layer 26 during heat transfer, and prevents the liquid-repellent layer 14 from turning white due to the remaining melamine resin. As for resins that do not contain components that exhibit liquid repellency, resins in which the contact angle with pure water on the side of the adhesion layer 26 opposite to the transfer layer 32 is 90 degrees or less are preferred, resins in which it is 60 degrees or less are more preferred, and resins in which it is 30 degrees or less are even more preferred. The adhesive layer 26 adheres only to the pattern layer 13 of the decorative paper 1 for resin-impregnated decorative panels by heat-press transfer during the manufacturing of the melamine decorative panel 2, but does not adhere to the liquid-repellent layer 14.

[0036] (1.3) Method for manufacturing melamine decorative laminate The configuration of the manufacturing method for the melamine decorative laminate 2 according to this disclosure will be described below with reference to Figures 3A, 3B, and 3C. Figures 3A, 3B, and 3C are cross-sectional process diagrams for forming the melamine decorative laminate 2. Here, we will describe the transfer sheet 3 used in forming the melamine decorative laminate 2. The transfer sheet 3 is formed by laminating a transfer layer 32 and an adhesion layer 33 in that order on one surface of a base layer 31.

[0037] The base layer 31 is the base layer of the transfer sheet 3, and a highly flexible material is used for ease of peeling after transfer. Examples of materials that can be used for the base layer 31 include polyester resins such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, and polyester thermoplastic elastomers; polyolefin resins such as polyethylene resin, polypropylene resin, polymethylpentene resin, and olefin thermoplastic elastomers; and thin paper laminated with polyolefin resin on its surface. Polyester resin is particularly preferred in terms of heat resistance and dimensional stability.

[0038] The transfer layer 32 is a layer that is transferred to the resin-impregnated decorative paper 1 used in the manufacture of the melamine decorative laminate 2. The resin constituting the transfer layer 32 is an uncured ionizing radiation-curable resin. The same material as that used for the transfer layer 25 of the melamine decorative laminate described above is used as the ionizing radiation-curable resin. The transfer layer 32 is cured after being transferred to the resin-impregnated decorative paper 1.

[0039] The adhesion layer 33 is a layer that improves the adhesion between the decorative paper 1 for resin-impregnated decorative laminates and the transfer layer 32 after transfer. The resin that makes up the adhesion layer 33 is the same material as the adhesion layer 26 of the melamine decorative laminate described above.

[0040] Next, the decorative paper 1 for resin-impregnated decorative panels, which is impregnated with aqueous melamine resin liquid, and the transfer sheet 3 are laminated together so that the liquid-repellent layer 14 side of the decorative paper 1 and the adhesive layer 33 side of the transfer sheet 3 face each other to form a laminate 40 (see Figure 3B).

[0041] Next, as shown in Figure 3B, the formed laminate 40 is sandwiched between two mirror plates 101 and 102, and the laminate 40 is subjected to pressure and heat to cure the uncured aqueous melamine resin liquid contained in the base paper 11 (thermal transfer). Through thermal transfer, a portion of the transfer layer 32 of the transfer sheet 3 is bonded to the pattern layer 13 via the adhesion layer 33. However, the portion of the pattern layer 13 that has the liquid-repellent layer 14 is not bonded to the adhesion layer 33.

[0042] Next, as shown in Figure 3C, the base material layer 31 is peeled off from the decorative paper 1 for resin-impregnated decorative laminate. When peeling the base material layer 31 off from the decorative paper 1 for resin-impregnated decorative laminate, the portions of the transfer layer 32 and the adhesion layer 33 that are bonded to the pattern layer 13 (transfer layer 32B and adhesion layer 33B) remain on the decorative paper 1 side. As a result, the surface of the transfer layer 32B on the base material layer 31 side is exposed, and a part of the surface of the melamine decorative laminate 2 is formed by the transfer layer 32B.

[0043] On the other hand, the portions of the transfer layer 32 and the adhesion layer 33 that are not bonded to the pattern layer 13, that is, the portions that are in contact with the liquid-repellent layer 14 (transfer layer 32A and adhesion layer 33A), remain on the base material layer 31 side. As a result, the liquid-repellent layer 14 is exposed, and a part of the surface of the melamine decorative laminate 2 is formed by the exposed liquid-repellent layer 14, giving the surface a design due to the difference in gloss between the areas with and without the liquid-repellent layer 14. Finally, the decorative paper 1 for resin-impregnated decorative panels, after the transfer sheet 3 has been peeled off, is irradiated with ionizing radiation to cure the radiation-curable resin of the transfer layer 32B. As a result, a melamine decorative panel 2 is completed, which has a cured transfer layer 25 arranged via an adhesion layer 26, as shown in Figure 2.

[0044] (1.4) Effects of this embodiment The resin-impregnated decorative paper 1 and melamine decorative board 2 described above have the following effects. (1) The decorative paper for resin-impregnated decorative panels comprises a base paper, a pattern layer provided on the base paper, a liquid-repellent layer provided on the pattern layer, and a sealing layer provided between the base paper and the pattern layer, or between the pattern layer and the liquid-repellent layer. By incorporating a sealing layer, the liquid-repellent layer can be prevented from seeping into the base paper, suppressing the transfer of the transfer layer onto the liquid-repellent layer when the transfer layer is transferred onto the decorative paper for resin-impregnated decorative panels, thereby preventing damage to the three-dimensional effect and design quality caused by the gloss of the liquid-repellent layer. (2) The sealing layer is preferably formed of one or more resin materials from among inks such as nitrose cotton resin, urethane resin, and acrylic resin, or coating resins such as thermosetting resin and ionizing radiation curable resin. This suppresses the liquid-repellent layer from seeping into the base paper, further improving the design quality of the decorative paper for resin-impregnated decorative panels.

[0045] (3) The sealing layer contains titanium dioxide as an additive, and it is preferable that the titanium dioxide content is 4% by mass or more and 20% by mass or less. This further suppresses the penetration of the liquid-repellent layer into the base paper, thereby improving the design quality of decorative paper for resin-impregnated decorative panels. (4) The liquid-repellent layer is formed of a thermosetting resin or an ionizing radiation-curable resin having urethane bonds, and the amount of the thermosetting resin or ionizing radiation-curable resin applied after drying is 4 g / m². 2 More than 18g / m 2 The following is preferable: Decorative paper for resin-impregnated decorative panels according to any one of claims 1 to 3.

[0046] (5) The melamine decorative laminate comprises the resin-impregnated decorative paper described above, and a transfer layer provided via an adhesive layer in areas on the pattern layer of the resin-impregnated decorative paper where a liquid-repellent layer is not formed. As a result, even with resin-impregnated melamine decorative laminates, it is possible to obtain resin-impregnated melamine decorative laminates in which the surface is formed by both a liquid-repellent layer and a transfer layer that can express gloss, three-dimensionality, and design characteristics.

[0047] (6) Melamine decorative laminate is formed by forming a transfer sheet on one surface of a base layer in that order, forming a transfer layer and an adhesion layer on one surface of a base layer, immersing the resin-impregnated decorative paper for decorative laminates described above in an aqueous melamine resin solution, laminating the transfer sheet onto the liquid-repellent side of the immersed resin-impregnated decorative paper for decorative laminates to form a laminate, applying pressure and heat to the laminate to cure the uncured aqueous melamine resin solution contained in the base paper, peeling the base layer of the transfer sheet from the resin-impregnated decorative paper for decorative laminates, transferring the portion of the transfer layer of the transfer sheet that is in contact with the layers other than the liquid-repellent layer of the resin-impregnated decorative paper for decorative laminates to the resin-impregnated decorative paper, and irradiating the resin-impregnated decorative paper for decorative laminates with ionizing radiation to cure the ionizing radiation-curable resin of the transfer layer transferred to the resin-impregnated decorative paper for decorative laminates. As a result, even with resin-impregnated melamine decorative laminates, it is possible to obtain resin-impregnated melamine decorative laminates in which the surface is formed by both a liquid-repellent layer and a transfer layer that can express gloss, three-dimensionality, and design characteristics. (7) Preferably, the transfer layer of the transfer sheet is formed of an uncured ionizing radiation-curable resin. This suppresses cracking in the transfer layer when transferring it from the transfer sheet to the decorative paper for resin-impregnated decorative laminates, making it possible to obtain melamine decorative laminates with a high level of design appeal. [Examples]

[0048] Examples and comparative examples of embodiments of this disclosure will be described below. However, this disclosure is not limited to the following embodiments.

[0049] <Example 1> (Formation of decorative paper for resin-impregnated decorative panels) The decorative paper for resin-impregnated decorative panels was formed as follows. As a base paper, it has good absorbency and a basis weight of 80 g / m². 2 I prepared titanium paper. Next, a sealing layer was formed on one side of the base paper. The sealing layer was formed by applying a mixed resin containing nitrated cotton resin and titanium dioxide, with the titanium dioxide content being 40% by mass, to the base paper and allowing it to cure. The amount of the sealing layer after drying was 7 g / m².2 It was formed so as to be

[0050] Subsequently, a pattern layer was formed on the stopper layer. The pattern layer was formed by printing a wood grain pattern by the direct gravure printing method using an aqueous ink with casein as the main component. Finally, a liquid repellent layer was formed on the pattern layer. The liquid repellent layer was formed by printing a conduit pattern in synchronization with the wood grain pattern of the pattern layer using a thermosetting urethane resin ink containing 5% by mass of silicone oil by the direct gravure printing method, and then heating and curing it. The liquid repellent layer had an applied amount after drying of 18 g / m 2 It was formed so as to be Thus, the decorative paper for a resin-impregnated decorative board of Example 1 was formed.

[0051] (Formation of transfer sheet) A transfer sheet was formed as follows. Note that the manufacturing order of the transfer sheet and the decorative paper for the resin-impregnated decorative board does not matter. As a base material layer, a raw stock in which a polypropylene resin was laminated on one surface of thin paper was prepared. The basis weight of the thin paper was 40 g / m 2 and the thickness of the polypropylene was 16 μm. Subsequently, a one-component curable ultraviolet-curable resin having tack-free property only by heat drying was applied on the surface of the base material layer on which the polypropylene resin was laminated to form a transfer layer. The applied amount of the ultraviolet-curable resin after drying was 6 g / m 2 and it was set as such.

[0052] Subsequently, a urethane resin containing no component that exhibits liquid repellency such as silicone oil was applied on one surface of the transfer layer to form an adhesion layer 33. The applied amount of the urethane resin after drying was 2 g / m 2 and it was set as such. Thus, the transfer sheet of Example 1 was formed.

[0053] (Formation of melamine decorative board) Next, the decorative paper for resin-impregnated decorative panels was immersed in an aqueous melamine resin solution that repelled water due to its liquid-repellent layer. After the aqueous melamine resin solution was sufficiently repelled from the liquid-repellent layer, it was thoroughly dried. At this time, the basis weight of the decorative paper for resin-impregnated decorative panels after impregnation and drying was 200 g / m². 2 The amount of resin impregnation was adjusted to achieve this result. Next, decorative paper for resin-impregnated decorative panels, which had been impregnated and dried with water-based melamine resin solution, and a transfer sheet were placed on top of each other so that the liquid-repellent layer-forming surface of the decorative paper and the adhesion layer-forming surface of the transfer sheet faced each other, and a laminate was formed.

[0054] Next, the formed laminate was sandwiched between two mirror plates 101 and 102, and the laminate was subjected to pressure and heat (thermal transfer). The thermal transfer was performed using a hot press at a pressure of 100 kg / cm². 2 The process was carried out under conditions of a molding temperature of 160°C and a heating and pressurizing time of 10 minutes. Subsequently, the transfer sheet was peeled off the decorative paper for resin-impregnated decorative panels, and then ultraviolet light was irradiated onto the peeled decorative paper to cure the ultraviolet-curable resin of the transfer layer transferred from the transfer sheet to the surface of the decorative paper. Based on the above, the melamine decorative laminate of Example 1 was formed.

[0055] <Example 2> A melamine decorative laminate of Example 2 was formed in the same manner as in Example 1, except that the resin material for the sealing layer was an acrylic resin.

[0056] <Example 3> A melamine decorative laminate of Example 3 was formed in the same manner as in Example 1, except that the resin material for the sealing layer was a urethane-based resin.

[0057] <Example 4> The amount of coating after drying of the liquid-repellent layer is 8 g / m². 2 The melamine decorative laminate of Example 4 was formed in the same manner as in Example 1, except that a thermosetting urethane resin-based ink was applied to achieve the desired result.

[0058] <Example 5> The resin material for the sealing layer is a urethane-based resin, and the coating amount after drying of the liquid-repellent layer is 8 g / m². 2 The melamine decorative laminate of Example 4 was formed in the same manner as in Example 1, except that a thermosetting urethane resin-based ink was applied to achieve the desired result.

[0059] <Example 6> The resin material for the sealing layer is a urethane-based resin that does not contain titanium dioxide, and the coating amount after drying of the liquid-repellent layer is 8 g / m². 2 The melamine decorative laminate of Example 6 was formed in the same manner as in Example 1, except that a thermosetting urethane resin-based ink was applied to achieve the desired result.

[0060] <Example 7> The resin material for the sealing layer is a thermosetting resin that does not contain titanium dioxide, and the coating amount after drying of the liquid-repellent layer is 6 g / m². 2 The melamine decorative laminate of Example 7 was formed in the same manner as in Example 1, except that a thermosetting urethane resin-based ink was applied to achieve the desired result.

[0061] <Example 8> The resin material for the sealing layer is a UV-curing resin that does not contain titanium dioxide, and the coating amount after drying of the liquid-repellent layer is 6 g / m². 2 The melamine decorative laminate of Example 8 was formed in the same manner as in Example 1, except that a thermosetting urethane resin-based ink was applied to achieve the desired result.

[0062] <Example 9> The resin material for the sealing layer is a nitrate-based resin that does not contain titanium dioxide, and the coating amount after drying of the liquid-repellent layer is 4 g / m². 2 The melamine decorative laminate of Example 9 was formed in the same manner as in Example 1, except that a thermosetting urethane resin-based ink was applied to achieve the desired result.

[0063] <Comparative Example 1> A melamine decorative laminate of Comparative Example 1 was formed in the same manner as in Example 1, except that a sealing layer was not provided.

[0064] <Rating> The following aesthetic evaluations were performed on the melamine decorative laminates of each of the above-described examples and comparative examples. (Design) In evaluating the aesthetic appeal, the design of the melamine decorative laminate was visually assessed. Particular attention was paid to the whitening of the pore patterns. Ten judges each evaluated whether the design of the melamine decorative laminate in each example and comparative example was good or not, based on the following criteria. Here, "good design of melamine decorative laminate" means: ◎: When 10 judges determined that the design of the melamine decorative laminate was good. ○: When the number of judges who determined that the design of the melamine decorative laminate was good is between 7 and 9. △: When the number of judges who determined that the design of the melamine decorative laminate was good is between 1 and 6. ×: When the number of judges who determined that the design of the melamine decorative laminate was good is 0.

[0065] <Evaluation Results> The evaluation results are shown in Table 1.

[0066] [Table 1]

[0067] As shown in Table 1, the melamine decorative laminates of each embodiment with a sealing layer showed improved design compared to the melamine decorative laminate of Comparative Example 1 without a sealing layer. Furthermore, as shown in Examples 1, 4, and 9, for example, the design quality improves as the amount of liquid-repellent layer applied after drying increases, with a total application amount of 8 g / m² after drying being sufficient. 2 In the cases described above, particularly high design quality was achieved. Furthermore, as shown in Examples 5 and 6, when the amount of resin material in the sealing layer and the amount of the liquid-repellent layer applied after drying were the same, adding titanium dioxide to the sealing layer improved the aesthetic appearance.

[0068] While embodiments of this disclosure have been described above, the technical scope of this disclosure is not limited to the embodiments described above. It is possible to make various changes or improvements to the embodiments described above, and it is clear from the claims that such modified or improved forms may also be included in the technical scope of this disclosure. [Explanation of Symbols]

[0069] 1. Decorative paper for resin-impregnated decorative panels 11 Base paper 12. Sealing layer 13 Pattern Layers 14 Liquid repellent layer 2 Melamine decorative laminate 25 Transfer layer 26. Close contact layer 3 Transfer Sheet 31 Base material layer 32 Transfer layer 33. Adhesion layer 40-layer structure 101,102 Mirror plate

Claims

1. The original paper and A pattern layer provided on the aforementioned base paper, A liquid-repellent layer provided on the pattern layer, A sealing layer provided between the base paper and the pattern layer, or between the pattern layer and the liquid-repellent layer, Equipped with, The sealing layer comprises a resin material and an inorganic additive added to the resin material. The inorganic additive comprises only titanium dioxide, The titanium oxide content is 40% by mass or more and 50% by mass or less relative to the resin material. Decorative paper for resin-impregnated decorative panels.

2. The sealing layer includes titanium dioxide and additives other than titanium dioxide as additives added to the resin material. The content of additives other than titanium dioxide is 80% by mass or less relative to the titanium dioxide. The decorative paper for resin-impregnated decorative boards according to claim 1.

3. The sealing layer is formed of one or more of the resin materials selected from inks containing nitrose cotton resin, urethane resin, and acrylic resin, or coating resins containing thermosetting resin and ionizing radiation-curable resin. Decorative paper for resin-impregnated decorative boards according to claim 1 or 2.

4. The liquid-repellent layer is formed of a thermosetting resin or an ionizing radiation-curable resin having urethane bonds. The amount of the thermosetting resin or the ionizing radiation-curable resin applied after drying is 4 g / m². ２ 18g / m or more ２ The following is Decorative paper for resin-impregnated decorative panels according to any one of claims 1 to 3.

5. The sealing layer does not contain acrylic resin as the resin material. Decorative paper for resin-impregnated decorative boards according to claim 1 or 2.

6. The sealing layer comprises only the resin material and the inorganic additive. The aforementioned resin material may consist solely of nitrated cotton resin, or The aforementioned resin material may consist solely of acrylic resins, or The aforementioned resin material includes only urethane-based resins. The decorative paper for resin-impregnated decorative boards according to claim 1.

7. A decorative paper for resin-impregnated decorative boards according to any one of claims 1 to 6, A transfer layer is provided via an adhesion layer in the area on the pattern layer of the resin-impregnated decorative paper for decorative boards where the liquid-repellent layer is not formed, Melamine decorative laminate with the following features.

8. A transfer sheet is formed by forming a transfer layer and an adhesion layer in this order on one surface of a substrate layer. A decorative paper for resin-impregnated decorative boards according to any one of claims 1 to 6 is immersed in an aqueous melamine resin solution, and the transfer sheet is laminated onto the liquid-repellent layer side of the immersed decorative paper for resin-impregnated decorative boards to form a laminate. The laminate is subjected to pressure and heat to cure the uncured aqueous melamine resin liquid contained in the base paper. The base material layer of the transfer sheet is peeled off from the decorative paper for resin-impregnated decorative boards, and the portion of the transfer layer of the transfer sheet that is in contact with the layers of the decorative paper for resin-impregnated decorative boards other than the liquid-repellent layer is transferred to the decorative paper for resin-impregnated decorative boards. The decorative paper for the resin-impregnated decorative panel is irradiated with ionizing radiation to cure the ionizing radiation-curable resin of the transfer layer transferred to the decorative paper for the resin-impregnated decorative panel. A method for manufacturing melamine decorative laminates.

9. The method for manufacturing a melamine decorative laminate according to claim 8, wherein the transfer layer of the transfer sheet is formed of the uncured ionizing radiation-curable resin.

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