Moisture-proof decorative paper, moisture-proof decorative boards and fittings

Abstract

To provide moisture-proof decorative paper for preventing warpage even when used in a place having a large difference between temperature and humidity environments on both sides.SOLUTION: Moisture-proof decorative paper 10 has decorative paper a1 in which a printed pattern layer 2 and a protective resin layer 1 are laminated on one surface of a paper base material 3, and a moisture-proof layer a2 in which an anchor coat layer 4, a vapor-deposited layer 5, and an overcoat layer 6 are laminated, wherein the anchor coat layer 4 contains first polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group and carboxylate, and the overcoat layer 6 contains second polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group and carboxylate.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to moisture-proof decorative paper used in fittings such as interior doors, kitchen doors, storage doors, and sliding doors, as well as moisture-proof decorative panels and fittings such as doors that use the same, and more specifically to moisture-proof decorative paper that has the function of preventing warping caused by humidity changes, temperature changes, etc., and moisture-proof decorative panels and fittings such as doors that use the same. [Background technology]

[0002] Traditionally, interior doors, kitchen doors, storage doors, and other fixtures have been known to gradually warp during use due to humidity and temperature fluctuations. This phenomenon occurs primarily due to uneven moisture content distribution within the fixture itself, caused by humidity and temperature differences between indoors and outdoors. Humidity differences create differences in moisture absorption and release on the front and back surfaces of the fixture, resulting in expansion on the higher humidity side and contraction on the lower humidity side, resulting in warping. Temperature differences also cause moisture to migrate to the colder side of the fixture's base material, creating a moisture content gradient across the thickness and resulting in warping. Typically, the lower temperature side experiences high humidity and moisture content, and these two effects act in the same direction, resulting in the most pronounced warping.

[0003] Methods for preventing warping of wooden fixtures include using sheets of the same material on the front and back of doors and other fixtures to prevent warping in one direction, and using metal supports for the frame of the fixture. Another widely used method is to use moisture-proof sheets with low moisture permeability as fixture components to reduce the moisture absorption and release amount of the components. Patent Document 1 proposes attaching a moisture-proof decorative sheet having a five-layer structure (protective resin layer / printed pattern layer / interleaving paper / synthetic resin layer / interleaving paper) to the front side of a board substrate such as plywood via an adhesive, and attaching a moisture-proof back sheet having a three-layer structure (interleaving paper / synthetic resin / interleaving paper) to the back side of the board substrate via an adhesive to form a moisture-proof decorative board, which is then attached to the front and back of a flush door via an adhesive. The moisture permeability of the moisture-proof sheet in this case is 5 (g / m 2 ·24h) or more 30(g / m) 2 According to this structure, in the moisture-proof decorative board used as the front and back decorative surface material of a flush door, the moisture-proof sheet and moisture-proof back sheet attached to the front and back of the board base material have a high moisture-proof function, so changes in the moisture content of the board base material of the moisture-proof decorative board due to temperature and humidity differences between the front and back sides of the flush door are suppressed, and as a result, it is said to have an anti-warping effect. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 3206408 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, from the viewpoint of door design, doors that are over 2m in height are increasingly being adopted. As doors have become taller, even a slight amount of warping can cause the entire door to warp significantly, so higher moisture resistance is required. As a sheet with high moisture resistance, a moisture-proof sheet with a synthetic resin base material, a metal vapor deposition film and a coating layer has been proposed. The moisture permeability is 5 (g / m 2 24 hours or less, and is said to be highly effective in preventing warping.

[0006] However, since these moisture-proof sheets all use plastic materials, reducing the amount of plastic used is desirable from an environmental perspective. Furthermore, when recycling decorative panels, doors, and other fixtures to which these moisture-proof sheets are attached, the wood base material and the plastic portion (synthetic resin layer and synthetic resin base material) must be separated, making them unsuitable for recycling.

[0007] The present invention has been made to solve the above-mentioned unresolved problems, and aims to provide a moisture-proof decorative paper that can reduce the amount of plastic used and prevent warping even when used in a place where there is a large difference in temperature and humidity environment on both sides, a moisture-proof decorative board using the same, and fittings such as doors. [Means for solving the problem]

[0008] In order to achieve the above-mentioned object, according to one aspect of the present invention, there is provided a moisture-proof decorative paper comprising a decorative paper and a moisture-proof layer, wherein the decorative paper comprises a printed pattern layer and a protective resin layer, in that order, on one side of a paper base material, and the moisture-proof layer comprises an anchor coat layer comprising a first polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group, and a carboxylic acid ester, a vapor deposition layer, and an overcoat layer comprising a second polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic acid anhydride group, and a carboxylic acid ester, in that order.

[0009] According to another aspect of the present invention, the moisture-proof decorative paper of the above aspect is stuck to a board substrate such as plywood with the overcoat layer side facing the surface of the board substrate, and the moisture permeability is 5 (g / m 2 A moisture-proof decorative board is provided in which a back moisture-proof sheet having a durability of 24 hours or less is attached to the back surface of a board substrate.

[0010] Furthermore, according to another aspect of the present invention, there is provided a door or other fixture with anti-warping properties, which includes a moisture-proof decorative panel of the above-mentioned aspect and a wood-based core member to which the back moisture-proof sheet side of the moisture-proof decorative panel is pressed so that it contacts the front and back surfaces. [Effects of the Invention]

[0011] According to one aspect of the present invention, it is possible to further prevent warping while reducing the amount of plastic used. [Brief explanation of the drawings]

[0012] [Figure 1] 1 is a cross-sectional view showing an example of the configuration of moisture-proof decorative paper according to one embodiment of the present invention. [Figure 2] FIG. 2 is a cross-sectional view showing another example of the configuration of moisture-proof decorative paper according to one embodiment of the present invention. [Figure 3] 1 is a cross-sectional view showing an example of the configuration of a moisture-proof decorative board according to one embodiment of the present invention. [Figure 4] FIG. 4 is a cross-sectional view showing another example of the configuration of a moisture-proof decorative board according to one embodiment of the present invention. [Figure 5] FIG. 2 is a cross-sectional view showing an example of the configuration of a door according to an embodiment of the present invention. [Figure 6] FIG. 10 is a cross-sectional view showing another example of the configuration of the door according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

[0014] The drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of each thickness, etc., differ from the actual ones. Furthermore, the embodiments shown below are merely examples of configurations for embodying the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited to the materials, shapes, etc. of the components described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims. <Configuration>

[0015] As shown in Figure 1, the moisture-proof decorative paper 10 of the present invention is formed by laminating, in this order, a protective resin layer 1, a printed pattern layer 2, a paper substrate 3, an anchor coat layer 4, a vapor deposition layer 5, and an overcoat layer 6. The protective resin layer 1 and the printed pattern layer 2 constitute the decorative paper a1, and the anchor coat layer 4, the vapor deposition layer 5, and the overcoat layer 6 constitute the moisture-proof layer a2.

[0016] As shown in FIG. 2, it is also possible to provide an adhesive primer layer 7 on the exposed surface of the overcoat layer 6 of the moisture-proof decorative paper 10, that is, on the surface opposite to the vapor deposition layer 5.

[0017] The anchor coat layer 4 contains a first polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester, and the overcoat layer 6 contains a second polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester.

[0018] 3 is a cross-sectional view showing an example of a moisture-proof decorative board 21. The moisture-proof decorative board 21 comprises a board substrate S, a moisture-proof decorative paper 10 provided on one side of the board substrate S, and a back moisture-proof sheet 11 provided on the other side of the board substrate S. The moisture-proof decorative paper 10 is provided so that the overcoat layer 6 is in contact with one side of the board substrate S. A back moisture-proof sheet 11 having the same moisture permeability as the moisture-proof decorative paper 10 is suitable, with a moisture permeability of 5 g / m 2 24 hours or less, preferably 3g / m 2· A moisture-proof sheet on the backside for 24 hours or less is preferable. For example, a moisture-proof sheet having a metal vapor-deposited film and a coating layer on a synthetic resin substrate can be used as the back moisture-proof sheet. However, from the environmental perspective of reducing the amount of plastic used, a moisture-proof sheet having a moisture-proof layer on a paper substrate is preferred.

[0019] As shown in the moisture-proof decorative board 22 of Figure 4, the back moisture-proof sheet 11 may be a back moisture-proof sheet 12 having a moisture-proof layer with properties equivalent to the moisture-proof layer a2 of the moisture-proof decorative paper 10. Specifically, the back moisture-proof sheet 12 is formed by laminating, in this order, an anchor coat layer 4 containing a first polyolefin having at least one selected from a carboxyl group, a carboxyl group salt, a carboxylic acid anhydride group, and a carboxylic acid ester on a paper substrate 3, a vapor-deposited layer 5, and an overcoat layer 6 containing a second polyolefin having at least one selected from a carboxyl group, a carboxyl group salt, a carboxylic acid anhydride group, and a carboxylic acid ester, with the overcoat layer 6 being in contact with the board substrate S. The back moisture-proof sheet 12 may also have an adhesive primer layer (not shown) on the exposed surface of the overcoat layer 6, i.e., the surface opposite to the vapor-deposited layer 5.

[0020] 3 and 4, moisture-proof decorative boards 21, 22 with anti-warping properties can be obtained by adhering moisture-proof decorative paper 10 to the surface of board substrate S and back moisture-proof sheet 11 or back moisture-proof sheet 12 to the back side of board substrate S via an adhesive. Note that the board substrate S used in this embodiment can be an organic board substrate such as medium-density fiberboard (MDF), plywood, or particle board.

[0021] Figures 5 and 6 show a portion of a flush door or other fitting 30 that has been flush processed using moisture-proof decorative boards 21, 22 shown in Figures 3 and 4 on both sides. The fitting 30 shown in Figures 5 and 6 is made by pressing moisture-proof decorative board 21 (Figure 5) or moisture-proof decorative board 22 (Figure 6) with the back moisture-proof sheet 11 or back moisture-proof sheet 12 facing inward using an adhesive to form a warp-resistant fitting 30 such as a flush door.

[0022] The core member SS used in this embodiment can be made of wood-based board substrates such as medium-density fiberboard (MDF), plywood, particle board, etc., and in the case of flush doors, core materials such as honeycomb panels can also be used as the core member SS.

[0023] The adhesive used in this embodiment is not limited to, and any type can be applied, such as, for example, an aqueous adhesive, a solvent adhesive, a chemical reaction adhesive, a hot melt adhesive, etc. As the adhesive, a known adhesive or a commercially available product can be appropriately selected and used.

[0024] Next, the structure of each layer will be described. <Surface protective layer>

[0025] The surface protective layer 1 is a layer for protecting the surface of the moisture-proof decorative paper 10, and is provided to impart surface properties such as scratch resistance, abrasion resistance, stain resistance, water resistance, and weather resistance required for moisture-proof decorative paper, moisture-proof decorative boards, and fittings such as doors. The formation of the surface protective layer 1 is not particularly limited, and it can be formed by a known coating method such as gravure coating.

[0026] The material for the surface protective layer 1 is not particularly limited, and materials similar to those used as surface protective layers in conventional decorative papers can be used. For example, acrylic urethane resins and ionizing radiation curable resins can be used for the surface protective layer 1. For example, the acrylic urethane resin can be a reaction product containing an acrylic polyol compound as the main component and an isocyanate compound as the curing agent. For example, the ionizing radiation curable resin can be a composition containing, as the main component, at least one of a prepolymer, oligomer, and monomer having a polymerizable unsaturated bond such as a (meth)acryloyl group, which undergoes a crosslinking reaction upon irradiation with ionizing radiation such as electron beams or ultraviolet rays.

[0027] The surface protection layer 1 may be a single layer or a multi-layer structure consisting of two or three layers. In the case of a multi-layer structure, a glossy matte finish can be achieved by applying a matte resin and a glossy resin separately. It is also possible to create a textured finish by partially raising the resin. Furthermore, antibacterial agents, antiviral agents, etc. can also be added. <Printed pattern layer>

[0028] The printed pattern layer 2 is intended to impart design, and any pattern can be used as the pattern, such as a wood grain pattern, a stone pattern, a fabric pattern, a cork pattern, an abstract pattern, or a combination of two or more of these. A solid ink layer can be provided between the printed pattern layer 2 and the paper substrate 3 to ensure hiding power. There are no particular limitations on the printing method, and known printing methods such as gravure printing, offset printing, silk screen printing, and inkjet printing can be used.

[0029] There are no particular limitations on the printing ink, etc., and either oil-based or water-based inks are acceptable. The same printing inks as those used for the print pattern layer of conventional decorative paper can be used, such as acrylic ink. For example, a two-component curing urethane resin ink made by blending an isocyanate curing agent with an acrylic polyol vehicle can be used as the acrylic ink. <Paper base material>

[0030] The paper substrate 3 is not particularly limited and may be appropriately selected depending on the intended use of the moisture-proof decorative paper. Specific examples of the paper substrate 3 include tissue paper, fine paper, art paper, cast-coated paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, fine paper, coated paper, parchment paper, glassine paper, parchment paper, wax paper, and Japanese paper.

[0031] As the paper base material 3, it is preferable to use thin paper (so-called inter-paper reinforced paper) in which synthetic resin is mixed to strengthen the inter-paper strength, or paper impregnated with latex or synthetic resin. There is no particular limitation on the basis weight of the paper base material 3, but it is preferably 20 g / m 2 In the case of less than 200g / m, the material is too flexible and wrinkles easily occur during processing. 2 In the above cases, problems such as peeling from the paper base material 3 are likely to occur, such as the base material layer of the paper base material 3 itself being torn in two. 2 More than 200g / m 2 Less than 20 g / m is preferred 2 More than 100g / m 2 Less than 20 g / m is more preferable. 2 More than 50g / m 2 The following is even more preferred:

[0032] Furthermore, the paper substrate 3 may be subjected to surface treatment such as corona treatment, plasma treatment, or flame treatment, if necessary.

[0033] The paper substrate 3 may have a coating layer at least on the side that comes into contact with the anchor coat layer 4, which will be described later. The coating layer prevents the anchor coat layer from penetrating into the paper substrate 3 and also serves as a sealant that fills in any irregularities in the paper substrate 3, allowing the anchor coat layer to be formed uniformly and without defects. The coating layer may contain, for example, various copolymers such as styrene-butadiene, styrene-acrylic, and ethylene-vinyl acetate copolymers, polyvinyl alcohol resins, cellulose resins, paraffin (wax), etc. as binder resins, and may also contain clay, kaolin, calcium carbonate, talc, mica, etc. as fillers.

[0034] The thickness of the coating layer is not particularly limited, but may be, for example, 1 μm or more and 10 μm or less, or 3 μm or more and 8 μm or less.

[0035] The weight of the paper substrate 3 is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the moisture-proof layer a2. When the weight of the paper substrate 3 is 50% by mass or more based on the moisture-proof layer a2, the amount of plastic used is less than that of conventional moisture-proof materials such as synthetic resin sheets (90% by mass or more of plastic material) made of vinyl chloride, polyethylene, polypropylene, etc., or moisture-proof sheets made of paper / polyethylene / paper (depending on the thickness of the polyethylene, 50% by mass or more of polyethylene is required to maintain moisture-proof performance), and the proportion of plastic material in the moisture-proof decorative paper can be significantly reduced. Furthermore, since 50% or more is paper material, the moisture-proof decorative paper of the present invention can be said to be made of paper. <Anchor coat layer>

[0036] The anchor coat layer 4 is provided on the surface of the paper substrate 3 to improve adhesion between the paper substrate 3 and the vapor-deposited layer 5 described below, and to improve the gas barrier properties of the gas barrier laminate. The anchor coat layer 4 contains a first polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester. Such an anchor coat layer 4 has excellent flexibility, can suppress cracking of the vapor-deposited layer 5, and can improve adhesion between the anchor coat layer 4 and the vapor-deposited layer 5. Furthermore, the inclusion of the above-mentioned polyolefin enables the formation of a dense film due to the crystallinity of the polyolefin. Furthermore, polyolefins have excellent water vapor barrier properties due to their low polar group content.

[0037] The anchor coat layer 4 may contain other components in addition to the first polyolefin, such as polyolefins other than the first polyolefin, silane coupling agents, organic titanates, polyacrylics, polyesters, polyurethanes, polycarbonates, polyureas, polyamides, polyimides, melamine, and phenols.

[0038] The content of the first polyolefin in the anchor coat layer 4 may be, for example, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass.

[0039] The thickness of the anchor coat layer 4 may be, for example, 1 μm or more, 2 μm or more, 20 μm or less, 10 μm or less, or 5 μm or less. If the thickness of the anchor coat layer 4 is 1 μm or more, the irregularities of the paper base material 3 described above can be efficiently filled, and the vapor deposition layer 5 described below can be evenly laminated. Furthermore, if the thickness of the anchor coat layer 4 is 20 μm or less, the vapor deposition layer 5 can be evenly laminated while keeping costs down.

[0040] Examples of solvents contained in the coating liquid for the anchor coat layer 4 include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, and butyl acetate. These solvents may be used alone or in combination. Among these, from the viewpoint of properties, methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred. Furthermore, from the viewpoint of the environment, methyl alcohol, ethyl alcohol, isopropyl alcohol, and water are preferred.

[0041] The anchor coat layer 4 can be formed by applying a coating liquid containing at least the first polyolefin and a solvent to the paper substrate 3 and drying it. The smaller the average particle size of the first polyolefin in the coating liquid, the better, from the viewpoints of smoothing the coating surface after drying, uniformly depositing the vapor deposition layer 5, and improving barrier properties. Specifically, it may be 1 μm or less, preferably 0.7 μm or less, and more preferably 0.5 μm or less. The lower limit of the average particle size of the first polyolefin is not particularly limited, but may be, for example, 1 nm or more. <Vapour-deposited layer>

[0042] The vapor-deposited layer 5 is a layer obtained by vapor-depositing a metal or an inorganic compound. The vapor-deposited layer 5 may be obtained by vapor-depositing aluminum, or may contain aluminum oxide (AlOx), silicon oxide (SiOx), or the like.

[0043] The thickness of the vapor-deposited layer 5 may be appropriately set depending on the intended use, but is preferably 10 nm to 300 nm, more preferably 30 nm to 100 nm. A thickness of 10 nm or more of the vapor-deposited layer 5 makes it easy to ensure sufficient continuity of the vapor-deposited layer 5, while a thickness of 300 nm or less makes it easy to sufficiently suppress the occurrence of curling and cracking, and to easily achieve sufficient gas barrier performance and flexibility.

[0044] The deposition layer 5 is preferably formed by a vacuum deposition method from the viewpoint of oxygen gas barrier performance and film uniformity. There are known deposition methods such as vacuum deposition, sputtering, and chemical vapor deposition (CVD), but vacuum deposition is preferred due to its fast deposition rate and high productivity. Among vacuum deposition methods, electron beam heating is particularly effective because it allows for easy control of the deposition rate by adjusting the irradiation area and electron beam current, and allows for rapid heating and cooling of the deposition material. <Overcoat layer>

[0045] The overcoat layer 6 is provided on the surface of the vapor-deposited layer 5 so as to be in contact with the vapor-deposited layer 5, and contains a second polyolefin having at least one selected from a carboxyl group, a salt of a carboxyl group, a carboxylic anhydride group, and a carboxylic acid ester.

[0046] Such an overcoat layer 6 has excellent flexibility and excellent adhesion to the vapor-deposited layer 5. Furthermore, by including the second polyolefin described above, it is possible to form a dense film due to the crystallinity of the polyolefin. Furthermore, polyolefin has excellent water vapor barrier properties due to its small number of polar groups.

[0047] The overcoat layer 6 may contain other components in addition to the second polyolefin, such as a silane coupling agent, organic titanate, polyacrylic, polyester, polyurethane, polycarbonate, polyurea, polyamide, polyolefin emulsion, polyimide, melamine, and phenol.

[0048] The content of the second polyolefin in the overcoat layer 6 may be, for example, 50% by mass or more, preferably 70% by mass or more, more preferably 90% by mass or more, or even 100% by mass. The thickness of the overcoat layer 6 may be, for example, 0.05 μm to 20 μm, preferably 0.5 μm to 10 μm, and more preferably 1 μm to 5 μm.

[0049] Furthermore, if the thickness of the overcoat layer 6 is 20 μm or less, it is possible to suppress costs while still exhibiting sufficient adhesion to the vapor deposition layer 5 and sufficient barrier properties.

[0050] Examples of solvents contained in the coating liquid for the overcoat layer 6 include water, methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, n-pentyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, toluene, hexane, heptane, cyclohexane, acetone, methyl ethyl ketone, diethyl ether, dioxane, tetrahydrofuran, ethyl acetate, and butyl acetate. These solvents may be used alone or in combination. Among these, from the viewpoint of properties, methyl alcohol, ethyl alcohol, isopropyl alcohol, toluene, ethyl acetate, methyl ethyl ketone, and water are preferred. Furthermore, from the viewpoint of the environment, methyl alcohol, ethyl alcohol, isopropyl alcohol, and water are preferred.

[0051] The overcoat layer 6 can be provided by applying a coating liquid containing the second polyolefin and a solvent onto the vapor-deposited layer 5 and drying the coating liquid. The average particle size of the second polyolefin in the coating liquid is not particularly limited, but specifically may be 1 μm or less, preferably 0.7 μm or less, and more preferably 0.5 μm or less.

[0052] The first polyolefin and the second polyolefin contained in the anchor coat layer 4 and the overcoat layer 6, respectively, may be the same or different, but considering ease of production, it is preferable that they are the same. <Adhesion primer>

[0053] The adhesive primer layer 7 is provided to ensure sufficient adhesion with various laminating adhesives, such as isocyanate-curing urethane resins and modified vinyl acetate resin emulsions, used when laminating onto the surface of various substrates. Known primer materials include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, and nitrocellulose resins. A primer from these is selected to match the type of laminating adhesive. For example, when using a modified vinyl acetate resin emulsion adhesive, a urethane adhesive primer will provide good adhesion.

[0054] If an inorganic fine powder such as silica is added to the adhesive primer layer 7, the surface of the adhesive primer layer will be roughened, which will prevent blocking when the moisture-proof sheet is rolled up and stored, and will also have an anchoring effect, improving adhesion to the laminating adhesive. These adhesive primers can be used alone or in combination to form an adhesive composition, which can be applied using an appropriate application method such as roll coating or gravure printing. <Effects>

[0055] The moisture-proof decorative paper of the present invention can have a lower moisture permeability (JIS Z 0208) than moisture-proof sheets made of synthetic resins such as vinyl chloride, polyethylene, or polypropylene, or paper / polyethylene / paper. Therefore, a moisture-proof decorative paper with excellent moisture-proof performance can be obtained. Furthermore, by forming fittings such as doors using a moisture-proof decorative board made from this moisture-proof decorative paper, it is possible to prevent the doors and other fittings from warping, and a moisture permeability of 5 (g / m) or less, which is considered to have a high warp prevention effect, can be obtained. 2 ·24h) or less of building materials can be obtained.

[0056] In addition, in the moisture-proof decorative paper, the weight of the paper base material 3 is 50% or more by mass based on the moisture-proof layer a2, so the weight of the plastic used is less than that of conventional moisture-proof materials such as synthetic resin sheets such as polyvinyl chloride, polyethylene, polypropylene, etc. (90% or more by mass of plastic material) or moisture-proof sheets made of paper / polyethylene / paper (50% or more by mass of plastic material), and therefore the amount of plastic material used in the moisture-proof decorative paper can be significantly reduced. Therefore, by using this moisture-proof decorative paper to form a moisture-proof decorative board, and then using this moisture-proof decorative board to form doors and other fixtures, it is possible to reduce the amount of plastic material used. Furthermore, moisture-proof decorative boards and doors using moisture-proof decorative paper have high moisture-proof performance and, because they are made from wood materials and paper components, are also highly recyclable. [Example]

[0057] The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to the following examples in any way. Example 1

[0058] Paper base material 3: 30 g / m 2A coating solution containing a carboxyl group salt (product name: Chemipearl S100, ionomer-based, Chemipearl particle size: <0.1 μm, solvent: water, IPA (isopropyl alcohol), manufactured by Mitsui Chemicals, Inc.) was applied to one side of the paper using a bar coater and dried in an oven to form an anchor coat layer 4. Note that "Chemipearl particle size: <0.1 μm" means that the particle size of the Chemipearl is smaller than 0.1 μm. The same applies hereinafter.

[0059] The thickness of the anchor coat layer 4 was 3.0 μm. Subsequently, AL (aluminum) was vapor-deposited onto the anchor coat layer 4.

[0060] The thickness of the aluminum vapor-deposited layer 5 was 50 nm. A solution containing a carboxyl salt (product name: Chemipearl S100, ionomer-based, Chemipearl particle size: <0.1 μm, solvent: water, IPA, manufactured by Mitsui Chemicals, Inc.) was then applied onto the vapor-deposited layer 5 using a bar coater and dried in an oven to form an overcoat layer 6, yielding a moisture-proof layer a2. The thickness of the overcoat layer 6 was 3.0 μm.

[0061] Next, a solid ink layer was formed by gravure printing using an ink containing soluble nitrocellulose and acrylic resin as a binder on the surface opposite to the surface on which the moisture-proof layer a2 was formed of the paper substrate 3. On top of that, a pattern ink layer (printed pattern layer 2) was formed by gravure printing using an ink also containing soluble nitrocellulose and acrylic resin as a binder.

[0062] Subsequently, a surface protective layer (protective resin layer 1) was formed by gravure printing using a urethane-based acrylic polyol and isocyanate, and a moisture-proof decorative paper 10 was obtained. <Example 2>

[0063] A moisture-proof decorative paper 10 was obtained in the same manner as in Example 1, except that the vapor-deposited layer 5 was formed from alumina (Al2O3). Example 3

[0064] The moisture-proof decorative paper 10 was obtained in the same manner as in Example 1, except that the anchor coat layer 4 was formed from a solution containing a salt of a carboxyl group (product name: Chemipearl S500, ionomer-based, Chemipearl particle size: 0.7 μm, solvent: water, IPA, manufactured by Mitsui Chemicals, Inc.). Example 4

[0065] A moisture-proof decorative paper 10 was obtained in the same manner as in Example 1, except that the thickness of the anchor coat layer 4 was set to 1.0 μm. <Example 5>

[0066] A moisture-proof decorative paper 10 was obtained in the same manner as in Example 1, except that the thickness of the anchor coat layer 4 was set to 0.9 μm. Example 6

[0067] As the paper base material 3, 30 g / m 2 A coating solution containing a carboxyl group salt (product name: Chemipearl S500, ionomer-based, Chemipearl particle size: 0.7 μm, solvent: water, IPA, manufactured by Mitsui Chemicals, Inc.) was applied to one side of the paper using a bar coater and dried in an oven to form an anchor coat layer 4 (thickness: 3.0 μm). Subsequently, aluminum was vapor-deposited on the anchor coat layer 4. The thickness of the aluminum vapor-deposited layer 5 was 50 nm. A solution containing a carboxyl group salt (product name: Chemipearl S100, ionomer-based, Chemipearl particle size: <0.1 μm, solvent: water, IPA, manufactured by Mitsui Chemicals, Inc.) was then applied to the vapor-deposited layer 5 using a bar coater and dried in an oven to form an overcoat layer 6 (thickness: 3.0 μm), resulting in a back moisture-proof sheet 12 serving as a moisture-proof layer a2.

[0068] The moisture-proof decorative paper 10 obtained in Example 3 was laminated, with the moisture-proof layer a2 side facing the adhesive side, to the surface of an MDF board substrate (manufactured by Hokushin Co., Ltd.: thickness: 3 mm), and the back moisture-proof sheet 12 obtained in Example 4 was laminated, with the moisture-proof layer side facing the adhesive side, to the back surface of the board substrate using a vinyl acetate resin-based adhesive (manufactured by Konishi Co., Ltd.) (5 g applied per square meter in wet state), to obtain a moisture-proof decorative board 22 with anti-warping properties.

[0069] Next, a flush door (810mm x 2030mm) was fabricated using a vinyl acetate resin adhesive (manufactured by Konishi Co., Ltd.) on the front and back of a four-sided frame made of LVL (27mm x 26mm, manufactured by First Wood Co., Ltd.) with the back moisture-proof sheet side of the moisture-proof decorative panel 22 facing inward. <Comparative Example 1>

[0070] The moisture-proof decorative paper 10 was obtained in the same manner as in Example 1, except that the anchor coat layer 4 was made of a urethane-cured acrylic resin, which is a cured product of acrylic polyol (acrylic polyol is a polymer of an acrylic acid derivative monomer or a polymer of an acrylic acid derivative monomer and other monomers, and has hydroxyl groups at the terminals) and polyisocyanate. <Comparative Example 2>

[0071] A moisture-proof decorative paper 10 was obtained in the same manner as in Example 1, except that the overcoat layer 6 was formed from a mixture of PVA (polyvinyl alcohol) and TEOS (tetra ethoxy silane) hydrolysate. <Comparative Example 3>

[0072] As a conventional moisture-proof sheet, a 30g / m2 sheet with corona treatment on one side was used. 2 The corona-treated surfaces of two sheets of reinforced inter-paper paper (manufactured by Tenma Special Paper Co., Ltd.) were sandwich-laminated with 50 μm of molten polyethylene resin extruded from a T-die extruder to produce a moisture-proof sheet (reinforced inter-paper paper / polyethylene / reinforced inter-paper paper).

[0073] Next, a solid ink layer was formed on the exposed surface of the moisture-proof sheet by gravure printing using an ink containing soluble nitrocellulose and acrylic resin as a binder, in the same manner as in Example 1. A pattern ink layer was then formed on top of this by gravure printing, also using an ink containing soluble nitrocellulose and acrylic resin as a binder.

[0074] Subsequently, a surface protective layer was formed by gravure printing using a urethane-based acrylic polyol and isocyanate, to obtain a moisture-proof decorative sheet.

[0075] The moisture-proof decorative sheet obtained above was laminated to the surface of an MDF (medium density fiberboard) board substrate (3 mm, manufactured by Hokushin Co., Ltd.), and the moisture-proof sheet was laminated to the back of the board substrate using a vinyl acetate resin adhesive (manufactured by Konishi Co., Ltd.) (5 g applied per square meter in wet state), to obtain a moisture-proof decorative board with anti-warping properties.

[0076] Next, a flush door (810mm x 2030mm) was created using a vinyl acetate resin adhesive (manufactured by Konishi Co., Ltd.) on the front and back of a four-sided frame made of a core of LVL (Laminated Veneer Lumber) (manufactured by First Wood Co., Ltd.: 27mm x 26mm) with the moisture-proof sheet side of the moisture-proof decorative panel facing inward. <Comparative Example 4>

[0077] 30g / m 2 A solid ink layer was formed on one side of a reinforced paper (manufactured by Tenma Tokushu Paper Co., Ltd.) by gravure printing using an ink containing soluble nitrocellulose and acrylic resin as a binder, in the same manner as in Example 1. A pattern ink layer was formed thereon by gravure printing using an ink containing soluble nitrocellulose and acrylic resin as a binder, in the same manner as in Example 1.

[0078] Subsequently, a surface protective layer was formed by gravure printing using a urethane-based acrylic polyol and an isocyanate, to obtain decorative paper.

[0079] The decorative paper obtained above was applied to the surface of an MDF board substrate (Hokushin Co., Ltd.: 3 mm) at a rate of 30 g / m 2 The backside of the laminate was laminated with a reinforced inter-paper paper (manufactured by Tenma Tokushu Paper Co., Ltd.) using a vinyl acetate resin adhesive (manufactured by Konishi Co., Ltd.) (5 g / square square applied in wet state) to obtain a decorative board.

[0080] Next, a flush door (810mm x 2030mm) was created using vinyl acetate resin adhesive (Konishi Co., Ltd.) on the front and back of a four-sided frame made of LVL (27mm x 26mm, manufactured by First Wood Co., Ltd.) with the reinforced paper side facing inward on the back side. <Evaluation> <Rating 1>

[0081] The moisture permeability was calculated in accordance with JIS Z 0208 for the moisture-proof decorative papers of Examples 1 to 5 and Comparative Examples 1 and 2, and the moisture-proof sheet of Comparative Example 3, and a comparison was made between them. The results are shown in Table 1.

[0082] Furthermore, the moisture-proof decorative papers of Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated for film uniformity of the vapor-deposited layer 5. This evaluation was made indirectly based on the moisture permeability. 2 If the moisture permeability is less than 24 hours, it is marked as "○" and if the moisture permeability is 4g / m 2 The results are shown in Table 1. [Table 1]

[0083] As is clear from the results in Table 1, the moisture-proof decorative papers of Examples 1 to 5, which contain a first polyolefin as the anchor coat layer and a second polyolefin as the overcoat layer, were confirmed to have lower moisture permeability than the moisture-proof decorative papers of Comparative Examples 1 and 2, which do not contain the first polyolefin as the anchor coat layer or the second polyolefin as the overcoat layer, and the conventional moisture-proof sheet of Comparative Example 3. In particular, it was confirmed that the moisture-proof decorative papers of Examples 1 to 5 have significantly lower moisture permeability than the conventional moisture-proof sheet of Comparative Example 3.

[0084] Furthermore, it was confirmed that the moisture-proof decorative papers of Examples 1 to 4, which contain a first polyolefin as the anchor coat layer and a second polyolefin as the overcoat layer, and further have an anchor coat layer thickness of 1.0 μm or more, have excellent film uniformity of the vapor-deposited layer 5, while the moisture-proof decorative paper of Example 5, in which the anchor coat layer 4 is thinner than 1.0 μm, has poor film uniformity of the vapor-deposited layer 5. <Rating 2>

[0085] The flush doors fabricated in Example 6 and Comparative Examples 3 and 4 were subjected to warpage testing in a two-chamber, one-piece environmental test chamber. The test consisted of placing a flush door at the boundary between two chambers, with one side exposed to a high-humidity environment and the other to a low-humidity environment, and measuring the amount of warpage. The test consisted of leaving the door stationary for 8 hours at a humidity of 90% ± 5% and a temperature of 20°C on the high-humidity side and a humidity of 50% ± 5% and a temperature of 20°C on the low-humidity side. After that, both chambers were left stationary for 16 hours at a humidity of 50% ± 5% and a temperature of 20°C. This 24-hour cycle consisted of five cycles of humidity and repetition. The maximum displacement of the flush door in the vertical, horizontal, and diagonal directions was measured. The results are shown in Table 2. [Table 2]

[0086] From the results in Table 2, it was confirmed that the flush door of Example 6 had a smaller maximum displacement amount than the flush doors of Comparative Examples 3 and 4 in all directions, height, width and diagonal.

[0087] From Tables 1 and 2, it was possible to verify that it is possible to provide moisture-proof decorative panels and doors and other fittings that can prevent warping even when used in places where there is a large difference in temperature and humidity environments on both sides, which is the objective of the present invention. [Explanation of symbols]

[0088] 1. Protective resin layer 2 Printed pattern layer 3 Paper base material 4 Anchor coat layer 5 Deposited layer 6 Overcoat layer 7 Adhesive primer layer 10 Moisture-proof decorative paper 11 Moisture-proof sheet on the back 12 Moisture-proof sheet on the back 21 Moisture-proof decorative board 22 Moisture-proof decorative board a1 decorative paper a2 Moisture-proof layer S plate base material SS core material

Claims

1. A moisture-proof decorative paper comprising a decorative paper and a moisture-proof layer, The decorative paper has a print pattern layer and a protective resin layer provided in this order on one surface of a paper base material, The moisture-proof layer is provided on the other surface of the paper substrate and includes an anchor coat layer containing a first polyolefin copolymer having a monomer unit having a salt of a carboxyl group; a deposition layer; an overcoat layer comprising a second polyolefin copolymer having a monomer unit having a salt of a carboxyl group, and Further, an adhesive primer layer is provided on the surface of the overcoat layer opposite to the vapor deposition layer, The moisture-proof decorative paper is characterized in that the thickness of the anchor coat layer is 1 μm or more.

2. 2. The moisture-proof decorative paper according to claim 1, wherein the paper substrate is a reinforced inter-paper paper.

3. The moisture-proof decorative paper according to claim 1 or 2 is stuck to a board substrate with the overcoat layer side facing the surface of the board substrate, and the moisture permeability is 5 (g / m ２ A moisture-proof decorative board characterized in that a back moisture-proof sheet having a shelf life of 24 h or less is attached to the back surface of the board substrate.

4. The back moisture-proof sheet is provided on a paper substrate, and includes an anchor coat layer including a first polyolefin copolymer having a monomer unit having a salt of a carboxyl group; a deposition layer; an overcoat layer including a second polyolefin copolymer having a monomer unit having a salt of a carboxyl group, and 4. The moisture-proof decorative board according to claim 3, wherein the overcoat layer side is attached to the back surface of the board substrate.

5. A moisture-proof decorative panel according to claim 3 or claim 4, characterized in that it includes a wood-based core member pressed against the front and back surfaces of the moisture-proof decorative panel so that the back moisture-proof sheet side of the moisture-proof decorative panel is in contact with the front and back surfaces.

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