Noncombustible decorative plate and method for manufacturing the same

Abstract

To provide a decorative plate in which a thermosetting resin-impregnated paper is crimped on a ceramic-based base material that has excellent adhesion between a decorative paper and a base material, and causes less color change and has excellent incombustibility.SOLUTION: A noncombustible decorative plate is one in which a surface or the surface and a rear surface of a ceramic-based base material includes a sealer layer, and a thermosetting resin-impregnated paper is crimped on an upper layer of the sealer layer. The sealer layer contains a phenol resin and isocyanate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a non-combustible decorative board and a method for manufacturing the decorative board. [Background technology]

[0002] In decorative boards in which a paper impregnated with a thermosetting resin, typically melamine resin, is pressed onto a ceramic substrate such as a calcium silicate board, the alkaline nature of the substrate inhibits the curing of the melamine resin, resulting in poor adhesion between the decorative paper and the substrate. Patent Document 1 therefore proposes improving adhesion by providing an acid-containing phenolic resin layer between the decorative paper and the substrate. However, because phenolic resins significantly discolor from yellow to reddish-brown, the discoloration is easily visible through the surface of the decorative board after molding, adversely affecting the appearance of the decorative board. In response to this, methods have been reported that use melamine resin-impregnated paper, which has excellent hiding power, such as decorative paper made by blending acrylic emulsion with melamine resin (Patent Document 2), and that place urea resin-impregnated paper between phenol resin-impregnated paper and melamine resin-impregnated paper (Patent Document 3). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-158951 [Patent Document 2] Japanese Patent Application Publication No. 59-84947 [Patent Document 3] Japanese Patent Application Laid-Open No. 2007-261145 Summary of the Invention [Problem to be solved by the invention]

[0004] However, when using the above-mentioned method of using melamine resin-impregnated paper, which has excellent hiding power, the decorative paper contains a large amount of organic matter, and therefore the non-combustibility of the decorative board cannot be obtained. Therefore, the object of the present invention is to provide a decorative board in which thermosetting resin-impregnated paper is pressed onto a ceramic substrate that has excellent adhesion between the decorative paper and the substrate, little discoloration, and excellent non-flammability, and a method for manufacturing the same. [Means for solving the problem]

[0005] Therefore, after extensive investigations, the inventors discovered that in a non-combustible decorative board in which thermosetting resin-impregnated paper is pressed onto the front or both surfaces of a ceramic substrate, a non-combustible decorative board that solves the above-mentioned problems can be obtained by providing a sealer layer containing a phenolic resin and an isocyanate between the substrate and the thermosetting resin-impregnated paper, and thus completed the present invention. That is, the present invention provides the following [1] to

[12] . [1] A non-combustible decorative board having a sealer layer on the surface or both surfaces of a ceramic substrate, with a thermosetting resin-impregnated paper pressed onto the top layer of the sealer layer, wherein the sealer layer is a sealer layer containing a phenolic resin and an isocyanate. [2] The non-combustible decorative board according to [1], wherein the content ratio of the phenolic resin to the isocyanate is 60 to 75 parts by weight of the phenolic resin and 25 to 40 parts by weight of the isocyanate. [3] The non-combustible decorative board according to [1] or [2], wherein the thermosetting resin-impregnated paper is a thermosetting resin-impregnated paper selected from melamine resin-impregnated paper, diallyl phthalate resin-impregnated paper, and polyester resin-impregnated paper. [4] The non-combustible decorative board according to any one of [1] to [3], wherein the pressure bonding means is a hot press. [5] The non-flammable decorative board according to any one of [1] to [4], wherein the isocyanate is a non-yellowing isocyanate. [6] The non-combustible decorative board according to any one of [1] to [5], wherein the ceramic substrate is a substrate selected from the group consisting of fiber-reinforced cement boards, fiber-reinforced cement calcium silicate boards, calcium silicate boards, wood-based cement boards, wood wool cement laminate boards, volcanic glass multi-layer boards, extruded cement boards, slag gypsum boards, lightweight aerated concrete boards, glass boards, ceramic boards, geopolymer hardened boards, and magnesia cement boards. [7] A step of providing a sealer layer on the surface or both surfaces of the ceramic substrate; and A step of pressing a thermosetting resin-impregnated paper onto the upper layer of the sealer layer. A method for manufacturing a non-combustible decorative board, The method for producing a non-flammable decorative board, wherein the sealer layer is a sealer layer containing a phenolic resin and an isocyanate. [8] The method for producing a non-combustible decorative board according to [7], wherein the content ratio of the phenolic resin to the isocyanate is 60 to 75 parts by weight of the phenolic resin and 25 to 40 parts by weight of the isocyanate. [9] The method for producing a non-combustible decorative board according to [7] or [8], wherein the thermosetting resin-impregnated paper is selected from the group consisting of melamine resin-impregnated paper, diallyl phthalate resin-impregnated paper, and polyester resin-impregnated paper.

[10] The method for producing a non-combustible decorative board according to any one of [7] to [9], wherein the pressure bonding means is a hot press.

[11] The method for producing a non-flammable decorative board according to any one of [7] to

[10] , wherein the isocyanate is a non-yellowing isocyanate.

[12] The method for producing a non-combustible decorative board according to any one of [7] to

[11] , wherein the ceramic substrate is a substrate selected from the group consisting of fiber reinforced cement boards, fiber reinforced cement calcium silicate boards, calcium silicate boards, wood cement boards, wood wool cement laminated boards, volcanic glass multi-layer boards, extruded cement boards, slag gypsum boards, lightweight aerated concrete boards, glass boards, ceramic boards, geopolymer hardened boards and magnesia cement boards. [Effects of the Invention]

[0006] The decorative board of the present invention has excellent adhesion between the ceramic substrate and the thermosetting resin-impregnated paper, is less susceptible to discoloration, and is highly non-flammable, and is particularly useful as a non-flammable decorative board for use on interior walls, ceilings, etc. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 2 is a schematic diagram of a crimping means in the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0008] Terms used in this specification are used in the sense commonly used in the art unless otherwise specified.

[0009] In this specification, "decorative laminate" refers to a general term for a decorative finish applied to the surface of a plate-shaped product (plate-shaped substrate). Examples of substrates that can be used include plywood, fiber-reinforced cement board, fiber-reinforced cement calcium silicate board, calcium silicate board, wood-based cement board, wood wool cement laminate board, volcanic glass composite board, extruded cement board, slag gypsum board, lightweight aerated concrete board, glass board, ceramic board, geopolymer hardened board, and magnesia cement board. Decorative finishes are extremely diverse, including applying a textured pattern to the substrate surface, painting, applying decorative paper, cloth, veneer (thin wooden boards approximately 1 mm thick), resin film, or metal plate, and printing. In addition to improving the appearance of plate-shaped products, decorative finishes often contribute to improving various performance characteristics, such as water resistance, stain resistance, abrasion resistance, and chemical resistance. The non-combustible decorative board in this specification is a decorative board having a total calorific value of 8 MJ / m according to a cone calorimeter heat generation test. 2 By satisfying this requirement, the heat generation rate will be Class 1 (heating time 20 minutes) as specified in JIS A 5430:2018, Appendix JA, and the material will exhibit high non-flammability. A more preferable total heat generation rate is 7.2 MJ / m 2 The following is the result.

[0010] One aspect of the present invention is a non-combustible decorative board having a sealer layer on the surface or both surfaces of a ceramic substrate, with a thermosetting resin-impregnated paper laminated to the top layer of the sealer layer, wherein the sealer layer is a sealer layer containing a phenolic resin and an isocyanate. Another aspect of the present invention is a method for manufacturing a ceramic substrate, comprising the steps of: providing a sealer layer on a surface or both surfaces of the ceramic substrate; A step of pressing a thermosetting resin-impregnated paper onto the upper layer of the sealer layer. A method for manufacturing a non-combustible decorative board, In the method for producing a non-flammable decorative board, the sealer layer contains a phenolic resin and an isocyanate.

[0011] The ceramic substrate that is the raw material for the non-combustible decorative board of the present invention is preferably a substrate selected from a fiber reinforced cement board, a fiber reinforced cement calcium silicate board, a calcium silicate board, a wood cement board, a wood wool cement laminate board, a volcanic glass multilayer board, an extruded cement board, a slag gypsum board, a lightweight aerated concrete board, a glass board, a ceramic board, a geopolymer hardened board, and a magnesia cement board, more preferably a substrate selected from a fiber reinforced cement board, a fiber reinforced cement calcium silicate board, a calcium silicate board, a gypsum slag board, and a magnesia cement board, and even more preferably a substrate selected from a fiber reinforced cement board, a fiber reinforced cement calcium silicate board, and a calcium silicate board.

[0012] The substrate selected from fiber reinforced cement boards, fiber reinforced cement calcium silicate boards, and calcium silicate boards is, for example, a substrate that uses hydraulic cement such as Portland cement as the main raw material for forming the matrix, uses fibers other than asbestos as the fiber raw material, and optionally uses admixtures such as wollastonite and calcium carbonate powder as raw materials, specifically a substrate such as a fiber reinforced cement board specified in JIS A 5430. In particular, 0.8 calcium silicate boards and 1.0 calcium silicate boards, which are types of fiber reinforced cement boards that use calcareous raw materials and siliceous raw materials as raw materials for forming the matrix and are autoclave cured in the curing step, are substrates that have excellent flexibility, high strength, and a small rate of length change due to water absorption, and are therefore suitable as ceramic substrates for use in the present invention.

[0013] Examples of the fiber raw materials include organic fibers such as pulp, synthetic pulp, polypropylene fiber, rayon fiber, acrylic fiber, vinylon fiber, nylon fiber, and polyester fiber; metal fibers such as steel fiber (steel wire fiber) and amorphous metal fiber; and inorganic fibers such as glass fiber, carbon fiber, rock wool fiber, and whiskers. In the present invention, even when the autoclave curing is adopted, pulp is preferably used from the viewpoint of improving the reinforcement and toughness of the decorative sheet. The pulp referred to here is so-called cellulose pulp, which is obtained by mechanically or chemically processing plant materials such as wood to extract cellulose. The content of fibers in fiber-reinforced cement boards, particularly organic fibers such as pulp, varies depending on the matrix, but is preferably 5 to 9 mass%, more preferably 6 to 8 mass%, from the viewpoint of ensuring strength and non-combustibility. If the content of organic fibers such as pulp is low, the mechanical strength of the decorative board decreases and it becomes more susceptible to cracking due to heat load, drying, carbonation, and impact. Conversely, if the content of organic fibers such as pulp is high, it becomes difficult to maintain non-combustibility.

[0014] The hydraulic cement may be any of those commonly used in the industry, such as Portland cement. Various additives used as needed include those commonly used in the industry, and are not particularly limited, but examples thereof include powders of wollastonite, mica, calcium carbonate, etc., and powders of waste fiber-reinforced cement boards and gypsum boards, etc. When autoclave curing is performed, in order to further increase strength by hydrothermal reaction hardening with the lime in the cement, it is preferable to add a siliceous raw material, for example, crystalline silica such as powdered silica stone, amorphous silica such as fly ash, etc., and, if necessary, add a calcareous raw material, for example, quicklime, slaked lime, etc., to adjust the molar ratio of CaO / SiO2 in the matrix component to 0.7 to 1.2.

[0015] In the present invention, the thickness of the substrate is preferably 2 to 12 mm, more preferably 2 to 8 mm, and even more preferably 2.5 to 6 mm, from the viewpoints of impact resistance, lightness, and workability. In the present invention, the bulk density of the substrate is 0.6 to 1.8 g / cm from the viewpoints of lightness, mechanical strength, and workability. 3 is preferred, and 0.6 to 1.2 g / cm 3 It is more preferable that: In the present invention, the total calorific value of the substrate is 5MJ / m from the viewpoint of non-combustibility. 2 Preferably, it is 4.7MJ / m or less. 2 More preferably, it is: In the present invention, the thickness of the substrate is a value measured in accordance with JIS A 5430:2018, section 8.2.2 b), and the bulk density is a value measured in accordance with JIS A 5430:2018, section 8.5. The total heat generation value of the substrate is the value measured in accordance with JIS A 5430:2018, Appendix JA.

[0016] The non-combustible decorative board of the present invention has a sealer layer on the front surface or both surfaces of the ceramic substrate, and the sealer layer is a sealer layer containing a phenolic resin and an isocyanate. Here, the sealer layer is provided on the surface or on both the front and back surfaces of the ceramic substrate.

[0017] The sealer layer cannot satisfy both the discoloration prevention and adhesion requirements of the decorative board when made solely of phenolic resin or isocyanate. Only by using them in combination can a non-flammable decorative board be obtained that satisfies both the discoloration prevention and adhesion requirements. The phenolic resin is not particularly limited, and examples thereof include novolac-type phenolic resins and resol-type phenolic resins. Novolac type phenolic resins include, for example, those obtained by reacting a phenol with an aldehyde in a ratio of 0.1 to 3 moles of the aldehyde per 1 mole of the phenol in the presence of an acid catalyst. Examples of the acidic catalyst include organic sulfonic acids such as oxalic acid, sulfuric acid, hydrochloric acid, boric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, trifluoroacetic acid, methanesulfonic acid, aminotrismethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid, and 2-phosphonobutane-1,2,4-tricarboxylic acid. Furthermore, examples of resol-type phenolic resins include those obtained by reacting phenols with aldehydes in the presence of a basic catalyst in a ratio of 1 to 3 moles of the aldehydes per mole of phenolic hydroxyl group of the phenols. Examples of the phenols include phenol, cresol, xylenol, octylphenol, para-tertiary butylphenol, phenylphenol, bisphenol A, bisphenol S, bisphenol F, naphthol, ethylphenol, isopropylphenol, nonylphenol, cumylphenol, aminophenol, nitrophenol, naphthol, hydroquinone, and dihydroxynaphthalene. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, acrolein, propionaldehyde, chloral, furfural, glyoxal, trioxal, caproaldehyde, allylaldehyde, benzaldehyde, crotonaldehyde, phenylacetaldehyde, tolualdehyde, and salicylaldehyde. Examples of the basic catalyst include oxides and hydroxides of alkali metals such as sodium and potassium, and alkaline earth metals such as magnesium and calcium, and amines such as triethylamine, triethanolamine, and ammonia. If necessary, a formaldehyde scavenger may be added to the phenolic resin.

[0018] Examples of isocyanates include yellowing isocyanates and non-yellowing isocyanates, but non-yellowing isocyanates are more preferred from the viewpoint of preventing discoloration.Specifically, aliphatic diisocyanates such as xylene diisocyanate, isophorone diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanates are more preferred.

[0019] In order to obtain a non-flammable decorative board that satisfies both discoloration prevention and adhesion, the sealer layer used in the present invention preferably contains the phenolic resin and isocyanate in a ratio of 60 to 75 parts by weight of phenolic resin and 25 to 40 parts by weight of isocyanate.

[0020] The sealer layer may be formed, for example, by applying a mixture of phenolic resin and isocyanate to the front or back surface of the ceramic substrate and then curing the mixture.

[0021] The non-combustible decorative board of the present invention is a non-combustible decorative board in which a thermosetting resin-impregnated paper is pressure-bonded to the upper layer of the above-mentioned sealer layer. Examples of the thermosetting resin that constitutes the thermosetting resin-impregnated paper include melamine resin, diallyl phthalate resin, and polyester resin, with melamine resin being more preferred. Melamine resin-impregnated paper is prepared by impregnating pattern paper with melamine resin at a predetermined impregnation rate, followed by heating and drying. Titanium paper is used as the pattern paper. The basis weight of the pattern paper is 30 to 150 g / m², taking into account the thickness and weight of the pattern paper. 2 It is preferable that the density is 60 to 150 g / m 2 It is more preferable that the impregnation rate of the melamine resin is 50 to 160 mass % in order to fully exert the functions of the impregnated melamine resin. The impregnation rate is calculated by dividing the weight of the melamine resin before drying by the weight of the melamine-impregnated paper before drying. The heating and drying temperature is preferably set to 100 to 140°C in order to firmly fix the melamine resin to the pattern paper.

[0022] The melamine resin-impregnated paper is placed on the sealer layer to form a laminate, and the melamine resin-impregnated paper is pressed against the sealer layer. The bonding method may be heat and pressure, i.e., hot pressing. For example, the laminate composed of the sealer layer and the surface decorative layer obtained above may be sandwiched between metal plates such as stainless steel plates, placed in a pressure device, and heated and pressure molded to produce a non-combustible decorative board. The conditions for the heat and pressure molding are a hot plate temperature of about 130 to 200°C and a pressure of 10 to 120 kgf / cm. 2 After heating and pressurizing for 1 minute to 2 hours, the plate can be removed. After the heating and pressurizing step, water can be passed through the hot plate and the plate can be cooled for 1 to 2 hours.

[0023] Thus, the non-combustible decorative board of the present invention is obtained. The non-combustible decorative board of the present invention has a total calorific value of 8 MJ / m according to a cone calorimeter heat generation test. 2 By satisfying this requirement, the heat generation rate will be Class 1 (heating time 20 minutes) as specified in JIS A 5430:2018, Appendix JA, and the material will exhibit high non-flammability. A more preferable total heat generation rate is 7.2 MJ / m 2 The following is the result. The non-combustible decorative board of the present invention not only satisfies the above-mentioned requirements for non-combustibility, but also has little color difference from the original color and good adhesion. [Example]

[0024] The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples in any way.

[0025] Examples 1 to 4 and Comparative Example 1 (1) Fiber-reinforced cement board (base material) The substrate used was Hilac M manufactured by A&A Material Co., Ltd. Hilac M is a fiber-reinforced cement board that corresponds to "Calcium silicate board Type 2 1.0 calcium silicate board" in Table 1 of JIS A 5430:2018. The Hilac M used in the examples and comparative examples had been polished with 150 grit sandpaper using a platen polisher to smooth the surface on which the decorative layer was to be formed (hereinafter referred to as the "surface").

[0026] (2) Formation of a sealer layer A sealer stock solution was prepared by mixing Ubimild PF Sealer, a novolac-type phenolic resin manufactured by Natoco Corporation, with hexamethylene diisocyanate in a mass ratio of 75:25. This sealer stock solution was then mixed with butyl acetate in a mass ratio of 10:7 to prepare a sealer solution. The viscosity of the sealer solution after the addition of butyl acetate was 50 mPa·s at 20°C. The sealer solution was applied to the substrate using a roll coater at a coating amount of 40 g / m on the surface side. 2 After coating with 40g / m2 on the back side 2 and then dried with hot air at 80°C for 30 minutes to form a sealer layer on the front and back surfaces of the substrate.

[0027] (3) Melamine resin-impregnated paper The impregnation solution is made of water-based melamine resin for low-pressure melamine decorative panels, and the basis weight is 80 g / m. 2 The titanium paper for resin impregnation was impregnated by dipping, and then dried in a ventilation heating dryer to obtain impregnated paper for low-pressure melamine decorative laminates. The resin coating amount of the impregnated paper for decorative laminates was 128 g / m. 2 The volatile content is 5.7% and the density is 0.9 g / cm 2 The volatile content was measured by drying the impregnated paper at 150°C for 10 minutes and dividing the weight loss by the weight before drying.

[0028] (4) Pressing of melamine resin-impregnated paper As shown in Figure 1, a calcium silicate board was laminated on top of a base material with a sealer layer on both sides, and melamine resin-impregnated paper was laminated on top of it. Metal plates were sandwiched between the top and bottom of the base material and heated and pressurized using a heat source at a heating temperature of 150°C and a pressure of 15 kgf / cm. 2 The holding time was 5 minutes. The total calorific value of the obtained decorative panels in the heat generation test using a cone calorimeter was 8MJ / m 2 It was confirmed that the following is true.

[0029] (5) Measurement of discoloration prevention effect The decorative panels were immersed in water at 40°C for three days and the presence or absence of discoloration was measured. The presence or absence of discoloration was measured using a Konica Minolta CR-410 colorimeter, based on the CIELab color space and the color difference ΔE measurement method, with the color difference ΔE set to Illuminant C. It has been confirmed that immersing decorative panels in 40°C water for three days results in discoloration equivalent to that achieved by curing the panels for three months indoors at a room temperature of 23°C and a humidity of 60%RH.

[0030] (6) Evaluation of crimping properties When the decorative board was burned by applying radiant heat from a heat source at 700°C, the height (h) to which the impregnated paper at the edge of the decorative board was turned up was measured.

[0031] Table 1 shows the composition of the sealer layer in the resulting decorative board, the color difference ΔE, and the peeling height (h). As a result, it was confirmed that a non-flammable decorative board, which has a sealer layer containing phenolic resin and isocyanate on the surface or both sides of a ceramic substrate and has thermosetting resin-impregnated paper pressed onto the top layer of the sealer layer, has excellent adhesion between the ceramic substrate and the thermosetting resin-impregnated paper, is less susceptible to discoloration, and has excellent non-flammability.

[0032] [Table 1]

Claims

1. A non-combustible decorative board having a sealer layer on the surface or both surfaces of a ceramic substrate, with a thermosetting resin-impregnated paper pressed onto the top layer of the sealer layer, wherein the sealer layer is a sealer layer containing a phenolic resin and an isocyanate.

2. 2. The non-combustible decorative board according to claim 1, wherein the content ratio of the phenolic resin to the isocyanate is 60 to 75 parts by weight of the phenolic resin and 25 to 40 parts by weight of the isocyanate.

3. 2. The non-combustible decorative board according to claim 1, wherein the thermosetting resin-impregnated paper is selected from the group consisting of melamine resin-impregnated paper, diallyl phthalate resin-impregnated paper, and polyester resin-impregnated paper.

4. 2. The non-combustible decorative board according to claim 1, wherein the pressure-bonding means is a hot press.

5. 2. The non-flammable decorative board according to claim 1, wherein the isocyanate is a non-yellowing isocyanate.

6. The non-combustible decorative board according to claim 1, wherein the ceramic substrate is a substrate selected from the group consisting of fiber reinforced cement boards, fiber reinforced cement calcium silicate boards, calcium silicate boards, wood cement boards, wood wool cement laminated boards, volcanic glass multi-layer boards, extruded cement boards, slag gypsum boards, lightweight aerated concrete boards, glass boards, ceramic boards, geopolymer hardened boards, and magnesia cement boards.

7. A step of providing a sealer layer on the surface or both surfaces of the ceramic substrate; A step of pressing a thermosetting resin-impregnated paper onto the upper layer of the sealer layer. A method for manufacturing a non-combustible decorative board, The method for producing a non-flammable decorative board, wherein the sealer layer is a sealer layer containing a phenolic resin and an isocyanate.

8. The method for producing a non-combustible decorative board according to claim 7, wherein the content ratio of the phenolic resin to the isocyanate is 60 to 75 parts by weight of the phenolic resin and 25 to 40 parts by weight of the isocyanate.

9. 8. The method for producing a non-combustible decorative board according to claim 7, wherein the thermosetting resin-impregnated paper is selected from the group consisting of melamine resin-impregnated paper, diallyl phthalate resin-impregnated paper, and polyester resin-impregnated paper.

10. 8. The method for producing a non-combustible decorative board according to claim 7, wherein the pressure bonding means is a hot press.

11. 8. The method for producing a non-flammable decorative board according to claim 7, wherein the isocyanate is a non-yellowing isocyanate.

12. The method for producing a non-combustible decorative board according to claim 7, wherein the ceramic substrate is selected from the group consisting of fiber reinforced cement boards, fiber reinforced cement calcium silicate boards, calcium silicate boards, wood cement boards, wood wool cement laminated boards, volcanic glass multilayer boards, extrusion molding cement boards, slag gypsum boards, lightweight aerated concrete boards, glass boards, ceramic boards, geopolymer hardened boards and magnesia cement boards.

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