Decorative panels

Abstract

To provide a metal decorative board which is excellent in adhesion between a resin-impregnated layer and a metal base material, and is easily taken out after hot-press molding.SOLUTION: Decorative sheets 1,1' have such a structure that a metal base material 3 and resin-impregnated layers 2,2' obtained by impregnating an impregnation base material with a thermosetting type resin composition are laminated, in which the metal base material 3 has an aluminum-zinc alloy plated layer 3b on a surface on the sides of the resin-impregnated layers 2,2'. The metal base material 3 is preferably an aluminum-zinc alloy plated steel plate. The thermosetting resin composition preferably contains a diallyl phthalate-based resin or a melamine-based resin.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a decorative board. [Background technology]

[0002] Conventionally, for the surfaces of tables, counters, walls, floors, etc., decorative panels have been used which are obtained by laminating a resin-impregnated layer, such as impregnated paper obtained by impregnating a paper base material such as titanium paper with a thermosetting resin such as diallyl phthalate resin, on a base material, and then superimposing a mirror plate on the resin-impregnated layer and thermo-pressing the layer to harden the thermosetting resin.

[0003] As the decorative board, a so-called metal decorative board is known, which uses a metal layer as a substrate for the purpose of providing non-combustibility and metallic luster. The metal decorative board generally uses aluminum or iron as the metal substrate, but such metal substrates have low adhesion to the resin-impregnated layer and tend to peel off between the layers. Therefore, a method of interposing an adhesive layer between the resin-impregnated layer and the metal substrate has been adopted (see, for example, Patent Documents 1 to 4). However, the method of improving the adhesion between the resin-impregnated layer and the metal substrate using an adhesive layer requires the preparation and formation of the adhesive layer, which is costly.

[0004] As a method for improving the adhesion between the resin-impregnated layer and the metal substrate without using an adhesive layer, a method for improving the composition of the resin composition in the resin-impregnated layer has been investigated (see, for example, Patent Documents 5 and 6). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2002-248708 A [Patent Document 2] Japanese Patent Publication No. 4-238026 [Patent Document 3] JP 2014-208453 A [Patent Document 4] JP 2018-1430 A [Patent Document 5] Special Publication No. 47-27359 [Patent Document 6] Special Publication No. 47-32825 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in conventional metal decorative panels in which a resin-impregnated layer and a metal substrate are laminated without an adhesive layer, the adhesion between the layers is still insufficient in some cases. In addition, in order to improve the adhesion between the layers, many of the resin-impregnated layers are made without a release agent, and as a result, a release layer is sometimes required to remove the decorative panel after thermo-compression molding. Furthermore, there are cases in which the surface hardness of the decorative panel is required to be high when it is in use.

[0007] Accordingly, an object of the present invention is to provide a metal decorative sheet which has excellent adhesion between a resin-impregnated layer and a metal substrate and which can be easily removed after thermocompression molding. [Means for solving the problem]

[0008] As a result of intensive research to achieve the above object, the present inventors have found that by using a metal substrate having an aluminum-zinc alloy plating layer on the side of the resin-impregnated layer as the metal substrate, a metal decorative sheet can be obtained that has excellent interlayer adhesion even when the resin-impregnated layer and the metal substrate are laminated so as to be in contact with each other, and that can be easily removed after thermocompression molding even when a separate release layer is not provided. The present invention was completed based on these findings.

[0009] That is, the present invention provides a decorative sheet having a laminated structure of a metal substrate and a resin-impregnated layer in which a thermosetting resin composition has been impregnated into the impregnated substrate, the metal substrate having an aluminum-zinc alloy plating layer on the surface of the resin-impregnated layer.

[0010] The metal substrate is preferably an aluminum-zinc alloy plated steel sheet.

[0011] The thermosetting resin composition preferably contains a diallyl phthalate-based resin or a melamine-based resin.

[0012] The thermosetting resin composition preferably contains an unsaturated polyester resin.

[0013] The decorative sheet preferably has a region where the aluminum-zinc alloy plating layer of the metal base material and the resin-impregnated layer are in contact with each other.

[0014] The decorative sheet may have the resin-impregnated layers provided on both sides of the metal base material.

[0015] The decorative sheet may include a core layer provided on one surface of the metal substrate with the resin-impregnated layer interposed therebetween. Effect of the Invention

[0016] The decorative board of the present invention has excellent interlayer adhesion even when a metal substrate is used as the substrate and an adhesive is interposed between the layers, and even when the resin-impregnated layer is laminated so as to be in contact with the metal substrate. Furthermore, it is easy to remove the laminate after thermocompression molding, not only when a separate release layer is provided on the resin-impregnated layer, but also when no release layer is provided. Therefore, it is possible to reduce the thickness of the adhesive layer or release layer or to not provide it, and the cost for forming the adhesive layer or release layer can be reduced, resulting in excellent economic efficiency. In addition to these effects, a decorative board with high surface hardness can be provided. [Brief description of the drawings]

[0017] [Figure 1] 1 is a cross-sectional view showing one embodiment of a decorative board of the present invention. [Diagram 2] FIG. 4 is a cross-sectional view showing another embodiment of the decorative board of the present invention. [Diagram 3]FIG. 4 is a cross-sectional view showing still another embodiment of the decorative board of the present invention. [Figure 4] 1A to 1C are diagrams showing an embodiment of a method for producing a decorative board of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] [Decorative board] The decorative board of the present invention has a structure in which a metal substrate and a resin-impregnated layer in which a thermosetting resin composition is impregnated into the impregnated substrate are laminated. The metal substrate has an aluminum-zinc alloy plating layer on the side of the resin-impregnated layer. In the decorative board of the present invention, the resin-impregnated layer is provided on at least one side of the metal substrate, and may be provided on only one side or on both sides.

[0019] In this specification, the thermosetting resin composition includes both a composition containing a resin having thermosetting properties (thermosetting resin) and a composition containing a resin obtained by curing the thermosetting resin (thermosetting resin). That is, the resin-impregnated layer includes a layer in which an impregnated base material is impregnated with a composition containing the thermosetting resin (a layer before thermosetting, a prepreg) and a layer in which the thermosetting resin in the composition is cured (a layer after thermosetting).

[0020] 1 and 2 show an embodiment of the decorative board of the present invention. The decorative board 1 shown in FIG. 1 includes a metal substrate 3 and a resin-impregnated layer 2. The resin-impregnated layer 2 is a layer (prepreg) in which a thermosetting resin composition is impregnated into an impregnated substrate before heat curing, and is formed so as to contact one surface of the metal substrate 3. The metal substrate 3 has a metal layer 3a and an aluminum-zinc alloy plating layer 3b formed on both sides of the metal layer 3a. That is, the metal substrate 3 has an aluminum-zinc alloy plating layer 3b on both sides including the side on the resin-impregnated layer 2 side.

[0021] The decorative board 1' shown in Fig. 2 includes a metal substrate 3 and a resin-impregnated layer 2'. The resin-impregnated layer 2' is a layer in which an impregnated substrate is impregnated with a thermosetting resin composition that has already been heat-cured, and is obtained by heat-curing the resin-impregnated layer 2.

[0022] (metal base material) The metal substrate has an aluminum-zinc alloy plating layer at least on the surface on the resin-impregnated layer side. By having the aluminum-zinc alloy plating layer, the plating layer has excellent adhesion to the thermosetting adhesive composition in the resin-impregnated layer. The metal substrate may be a single layer or a multi-layer. When it is a multi-layer, the aluminum-zinc alloy plating layer may be provided only on the metal substrate located on the surface on the resin-impregnated layer side.

[0023] The metal substrate may be one in which the surface of the metal layer is subjected to an aluminum-zinc alloy plating treatment. The metal layer may be a substrate made of a known or common metal used in decorative sheets, such as a metal foil, a metal plate, or a metal deposition layer. The metal may be aluminum, copper, or iron. Specific examples of the metal layer include an aluminum plate, a copper plate, a stainless steel plate, a cast iron plate, or a steel plate. Of these, a steel plate is preferable as the metal layer. Examples of metal substrates in which the metal layer is a steel plate include an aluminum-zinc alloy plated steel plate (for example, Galvalume Steel Plate (registered trademark), Galvastar (registered trademark), etc.).

[0024] The aluminum-zinc alloy plating layer may be provided on at least the surface of the metal layer on the side of the resin-impregnated layer, and may be provided on both surfaces. When the resin-impregnated layer is provided on both surfaces of the metal base material, the aluminum-zinc alloy plating layer may be provided on at least one of the two surfaces of the metal base material, but is preferably provided on both surfaces. The aluminum-zinc alloy plating layer may be provided partially on the surface of the metal layer, or may be provided on the entire surface.

[0025] The total content of aluminum and zinc in the aluminum-zinc alloy plating layer is preferably 90 mass% or more, more preferably 95 mass% or more, and even more preferably 97 mass% or more, relative to the total amount (100 mass%) of the aluminum-zinc alloy plating layer.

[0026] The aluminum-zinc alloy plating layer may contain other metal elements in addition to aluminum and zinc. Examples of the other metal elements include magnesium. When magnesium is contained, the corrosion resistance is excellent when used outdoors. The content ratio of the other metal elements is preferably 0.1 to 5 mass %, more preferably 0.5 to 3 mass %, based on the total amount (100 mass %) of the aluminum-zinc alloy plating layer.

[0027] The mass ratio of aluminum to zinc (former:latter) in the aluminum-zinc alloy plating layer is preferably 20:80 to 90:10, more preferably 40:60 to 70:30, and even more preferably 51:49 to 60:40. The volume ratio of aluminum to zinc (former:latter) in the aluminum-zinc alloy plating layer is preferably 60:40 to 95:5, more preferably 70:30 to 90:10, and even more preferably 75:25 to 85:15.

[0028] The thickness of the aluminum-zinc alloy plating layer (thickness of one side when both sides are provided) is not particularly limited, but is, for example, 1 to 70 μm, and preferably 5 to 50 μm. When the thickness is 1 μm or more, the adhesion with the resin-impregnated layer is improved. When the thickness is 70 μm or less, it is economically advantageous.

[0029] The thickness of the metal substrate is not particularly limited, but is, for example, 10 to 2500 μm, and preferably 200 to 1200 μm. If the thickness is 10 μm or more (particularly, 200 μm or more), it is easy to handle. If the thickness is 2500 μm or less (particularly, 1200 μm or less), it is economical.

[0030] (Resin impregnated layer) The resin-impregnated layer is a layer in which a thermosetting resin composition is impregnated into an impregnated substrate. The thermosetting resin composition includes at least a thermosetting resin. The thermosetting resin includes both a resin having thermosetting properties (thermosetting resin) and a resin obtained by curing the thermosetting resin (thermosetting resin). The resin-impregnated layer may be a single layer or a multilayer (laminate). The resin-impregnated layer may have a single layer of a thermosetting resin composition, or may have a plurality of different layers of a thermosetting resin composition (multi-laminate).

[0031] The thermosetting resin may be any known or commonly used resin used in the manufacture of decorative panels, such as melamine resins, diallyl phthalate resins, phenol resins, epoxy resins, benzoguanamine resins, urethane resins, alkyd resins, unsaturated polyester resins, urea resins, etc. Only one type of thermosetting resin may be used, or two or more types may be used.

[0032] As the thermosetting resin, among others, melamine-based resin, diallyl phthalate-based resin, and unsaturated polyester-based resin are preferable. In particular, diallyl phthalate-based resin is preferable, and diallyl phthalate-based resin and unsaturated polyester-based resin are more preferable.

[0033] When the thermosetting resin is a thermosetting resin, each of the resins is a prepolymer having a thermosetting functional group. When the thermosetting resin is a diallyl phthalate resin or an unsaturated polyester resin, the thermosetting functional group is an unsaturated carbon-carbon double bond.

[0034] The melamine-based resin contains at least a structural unit derived from a melamine derivative. Examples of the melamine derivative include melamine and compounds in which functional groups such as imino groups, methylol groups, and alkoxymethyl groups such as methoxymethyl groups and butoxymethyl groups have been introduced into melamine. In addition, a compound obtained by reacting a melamine derivative having a methylol group with a lower alcohol to partially or completely etherify the melamine derivative can also be used as a monomer. The melamine derivative may be used alone or in combination of two or more kinds. The melamine resin may be either a melamine resin for high-pressure molding or a melamine resin for low-pressure molding. The melamine resin may be used alone or in combination of two or more kinds.

[0035] The diallyl phthalate resin contains at least a constituent unit derived from a diallyl phthalate monomer. Examples of the diallyl phthalate monomer include diallyl orthophthalate, diallyl isophthalate, and diallyl terephthalate. The diallyl phthalate monomer may be used alone or in combination of two or more. The diallyl phthalate resin may be used alone or in combination of two or more. The weight average molecular weight of the diallyl phthalate resin measured by GPC is preferably 10,000 to 50,000.

[0036] The unsaturated polyester resin may be in a liquid state or a solid state at room temperature. Only one type of unsaturated polyester resin may be used, or two or more types of unsaturated polyester resins may be used.

[0037] The unsaturated polyester resin may be a compound containing a structural unit derived from a polybasic unsaturated acid and a structural unit derived from a polyhydric alcohol.The unsaturated polyester resin may further contain a structural unit derived from a polybasic saturated acid.The unsaturated acid, the saturated acid, and the polyhydric alcohol may each be used in one kind or in two or more kinds.

[0038] Examples of the polybasic unsaturated acid include maleic acid, fumaric acid, itaconic acid, phthalic acid monomers (orthophthalic acid, isophthalic acid, terephthalic acid), etc. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, neopentyl glycol, diethylene glycol, hydrogenated bisphenol A, etc.

[0039] In addition, the unsaturated polyester resin may be an air-curable unsaturated polyester resin, for example, a polyester resin containing a structural unit derived from an aliphatic cyclic unsaturated acid such as tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, or methyl-3,6-endomethylenetetrahydrophthalic acid as the unsaturated acid, and a structural unit derived from allyl glycidyl ether as the polyhydric alcohol.

[0040] The content of the thermosetting resin in the thermosetting resin composition is preferably 20 to 100% by mass, more preferably 40 to 90% by mass, and further preferably 50 to 80% by mass, based on the total amount (100% by mass) of the thermosetting resin composition. When the content is 20% by mass or more, a resin-impregnated layer having sufficient strength can be obtained by hot and pressure molding.

[0041] When the thermosetting resin contains a diallyl phthalate-based resin and / or an unsaturated polyester-based resin, the content of the diallyl phthalate-based resin and / or the unsaturated polyester-based resin in the thermosetting resin is preferably 50 mass% or more, more preferably 70 mass% or more, and even more preferably 80 mass% or more, relative to the total amount (100 mass%) of the thermosetting resin.

[0042] When the thermosetting resin contains a diallyl phthalate resin and / or an unsaturated polyester resin, the mass ratio of the diallyl phthalate resin to the unsaturated polyester resin (the former:the latter) is preferably 10:90 to 100:0, more preferably 10:90 to 90:10, even more preferably 20:80 to 80:20, still more preferably 30:70 to 70:30, and particularly preferably 40:60 to 60:40. When the mass ratio is within the above range, the adhesion between the resin-impregnated layer and the metal substrate is improved.

[0043] The thermosetting resin composition may contain a monomer constituting the thermosetting resin or an oligomer of the monomer (e.g., a polymer of two or three monomers). For example, when the thermosetting resin contains a diallyl phthalate resin, the thermosetting resin composition may contain the diallyl phthalate monomer, which is a structural unit of the diallyl phthalate resin.

[0044] The thermosetting resin composition may contain a crosslinking agent for crosslinking the thermosetting resin. By using the crosslinking agent, the crosslink density in the cured resin-impregnated layer is increased, and the surface hardness of the resin-impregnated layer can be increased. The crosslinking agent is appropriately selected according to the type of the thermosetting resin. When the thermosetting resin is a diallyl phthalate resin or an unsaturated polyester resin, examples of the crosslinking agent include a polyfunctional monomer having at least two polymerizable functional groups having an unsaturated carbon-carbon double bond such as a (meth)acryloyl group or a vinyl group, and a polyfunctional compound such as a polymer of the polyfunctional monomer. The crosslinking agent may be used alone or in combination of two or more types.

[0045] Examples of the polyfunctional monomer include polyfunctional (meth)acrylates such as hexanediol di(meth)acrylate, dodecanediol di(meth)acrylate, butanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di(meth)acrylate, and hexyl di(meth)acrylate. Of the polyfunctional compounds, poly(meth)acrylates of dipentaerythritol having three or more (meth)acryloyl groups in the molecule are preferred.

[0046] The content of the crosslinking agent (the structural part derived from the crosslinking agent when the thermosetting resin is a thermoset resin) is preferably 0.5 to 50 parts by mass relative to 100 parts by mass of the total amount of the thermosetting resin. When the content is within the above range, the hardness of the resin-impregnated layer after heat curing becomes more appropriate. The content of the curing agent may be 10 to 47 parts by mass, or may be 30 to 45 parts by mass, relative to 100 parts by mass of the total amount of the thermosetting resin. In particular, when the content ratio of the diallyl phthalate resin in the thermosetting resin is high (for example, 60% by mass or more, preferably 80% by mass or more), the content of the crosslinking agent is preferably within the above range. In addition, the content of the crosslinking agent may be 0.6 to 20 parts by mass, or may be 1 to 16 parts by mass, relative to 100 parts by mass of the total amount of the thermosetting resin. In particular, when the diallyl phthalate resin and the unsaturated polyester resin are included as the thermosetting resin, the content of the crosslinking agent is preferably within the above range. In addition, the content of the crosslinking agent relative to 100 parts by mass of the diallyl phthalate resin and the unsaturated polyester resin is preferably within the above range. When the content of the crosslinking agent is equal to or greater than the lower limit, the crosslink density of the cured resin-impregnated layer can be increased, and the surface hardness of the resin-impregnated layer can be further increased.

[0047] The thermosetting resin composition preferably contains a polymerization initiator (curing agent). By using the polymerization initiator, the curing speed is faster than that of the thermosetting resin alone, and a thermosetting layer having a sufficient degree of curing can be obtained in a short time. When the thermosetting resin is a diallyl phthalate resin or an unsaturated polyester resin, examples of the polymerization initiator include organic peroxide curing agents such as benzoyl peroxide, tertiary butyl perbenzoate, methyl ethyl ketone peroxide, and dicumyl peroxide.

[0048] The content of the polymerization initiator (the structural part derived from the polymerization initiator when the thermosetting resin is a thermoset resin) is preferably 0.1 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass, relative to 100 parts by mass of the total amount of the thermosetting resin.

[0049] The thermosetting resin composition preferably contains a release agent (internal release agent). Even if the thermosetting resin composition contains a release agent, the decorative board of the present invention has excellent adhesion to the metal substrate, so that the decorative board obtained by thermocompression molding can be easily removed without providing a separate release layer.

[0050] Examples of the release agent include fluorine-based release agents, silicone-based release agents, wax-based release agents, acidic phosphate-based release agents, etc. The release agents may be used alone or in combination of two or more.

[0051] The content of the release agent is preferably 0.1 to 8 parts by mass, more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total amount of the thermosetting resin. When the content is 0.1 part by mass or more, the decorative sheet can be more easily removed after thermocompression molding. When the content is 8 parts by mass or less, the adhesion between the resin-impregnated layer and the metal substrate is better.

[0052] The thermosetting resin composition may contain other components other than the thermosetting resin. Examples of the other components include a curing catalyst, a curing accelerator, a polymerization inhibitor, a filler, a plasticizer, a dispersant, a thickener, a viscosity modifier, a flame retardant, a colorant (pigment, dye, etc.), a defoamer, a preservative, an ultraviolet absorber, a depleting agent, an antibacterial agent, a leveling agent, and a silane coupling agent. Only one of the other components may be used, or two or more of them may be used.

[0053] The impregnated substrate is not particularly limited as long as it can be impregnated with the thermosetting resin composition, and examples thereof include impregnated paper and cloth such as titanium paper, tissue paper, reinforced paper, kraft paper, and cellulose paper; and woven or nonwoven fabrics such as polyester, rayon, acrylic, and vinylon. The impregnated paper and cloth may be printed. The impregnated substrate may be a single layer or a multilayer.

[0054] The amount of the thermosetting resin composition impregnated into the impregnated substrate is 10 to 500 g / m per area of ​​the impregnated substrate. 2 is preferable, and more preferably 50 to 300 g / m 2 The above impregnation amount is 10g / m 2 When the impregnation amount is 500 g / m or more, the impregnation amount is sufficient and the adhesion to the metal substrate is improved. 2 If it is less than this, the cost can be reduced.

[0055] The thickness of the resin-impregnated layer is not particularly limited, but is, for example, 10 to 200 μm, and preferably 20 to 100 μm. If the thickness is 10 μm or more, the occurrence of defects such as poor flow during thermocompression molding can be suppressed. If the thickness is 200 μm or less, warping of the molded product due to resin shrinkage can be suppressed.

[0056] The resin-impregnated layer can be produced by a known or conventional method, and can be produced, for example, as follows. First, a thermosetting resin composition, which is a composition before heat curing, is prepared. The thermosetting resin composition is obtained by mixing the thermosetting resin and the various components described above as necessary. When the thermosetting resin composition has a low viscosity, the impregnated substrate can be immersed in the thermosetting resin composition bath to be impregnated. When the thermosetting resin composition is a high-viscosity liquid or solid, the thermosetting resin composition is diluted or dissolved in an appropriate solvent, for example, an organic solvent such as acetone, toluene, or methyl ethyl ketone, to obtain a resin liquid of appropriate viscosity, and the impregnated substrate is immersed therein, and then dried to volatilize the solvent. The impregnation temperature is, for example, 10 to 35°C, and preferably 20 to 30°C. Although the method of immersing the impregnated substrate in the thermosetting resin composition bath has been described, the impregnation may be performed by applying the thermosetting resin composition to the surface of the impregnated substrate and leaving it to soak in.

[0057] The metal substrate preferably has an area where the aluminum-zinc alloy plating layer and the resin-impregnated layer contact on the surface of the resin-impregnated layer. It is more preferable that the metal substrate and the resin-impregnated layer do not have any other layers such as an adhesive layer between them. The decorative plate of the present invention has excellent adhesion between the metal substrate and the resin-impregnated layer, so that the amount of adhesive layer used can be reduced or there is no need to use an adhesive layer, which is economical.

[0058] The decorative board may have other layers in addition to the above-mentioned layers. Examples of the other layers include a core layer and a protective film for protecting the surface of the resin-impregnated layer. By providing the core layer, it is possible to obtain effects such as imparting shape stability to the decorative board, imparting non-combustibility to the decorative board using the core layer, and improving the flexibility of the decorative board.

[0059] The core layer may be a known or conventional substrate used in decorative boards. The core layer may be an organic substrate or an inorganic substrate. The organic substrate may be, for example, a wood substrate such as a single board, a plywood, a laminated lumber, a particle board, a medium density fiberboard (MDF), a high moisture fiberboard, or a kenaf board; a fibrous substrate such as a paperboard, a woven fabric, a nonwoven fabric, a resin-impregnated paper, or a resin-impregnated cloth; or a synthetic resin substrate such as an acrylic resin board, a styrene resin board, an ABS resin board, a polycarbonate resin board, a nylon resin board, a polystyrene resin board, a polypropylene resin board, a polyester resin board, or a glass fiber reinforced plastic board. Examples of the inorganic substrate include metal substrates such as aluminum plates, stainless steel plates, duralumin plates, steel plates, and brass plates; inorganic substrates such as magnesium oxide plates, aluminum hydroxide plates, aluminum oxide plates, silicon oxide plates, titanium oxide plates, magnesium chloride plates, calcium silicate plates, volcanic glassy material plates, gypsum (calcium sulfate) plates, slag gypsum plates, limestone (calcium carbonate) plates, wood wool cement plates, slag cement plates, lightweight aerated concrete plates, and glass fiber reinforced concrete plates. The core layer may be a single layer or a laminate of the same or different layers. The core layer may be subjected to an easy-adhesion treatment such as a sealer treatment or a primer treatment to improve adhesion with the resin-impregnated layer.

[0060] The core layer is preferably a non-combustible material, but since non-combustibility can be obtained by using a metal substrate, the above-mentioned wood-based substrate or a heat insulating material such as urethane, glass wool, or phenol can also be used. Examples of the non-combustible material include the above-mentioned inorganic substrate. The core layer is preferably porous.

[0061] The thickness of the core layer is not particularly limited, but is, for example, 2 to 50 mm, and preferably 3 to 30 mm. If the thickness is 2 mm or more, the strength is sufficient and the core layer is less likely to break. If the thickness is 50 mm or less, the core layer is light and easy to handle.

[0062] The core layer is preferably provided on the metal substrate via the resin-impregnated layer. In this case, the resin-impregnated layer also functions as an adhesive layer that improves the adhesion between the core layer and the metal substrate. In addition, when the core layer is provided, the resin-impregnated layer is provided on both sides of the metal substrate, and the core layer is provided via one of the resin-impregnated layers, and the other resin-impregnated layer is preferably a layer that forms the surface of the decorative plate. Both resin-impregnated layers are preferably provided on the aluminum-zinc alloy plating layer surface of the metal substrate.

[0063] Fig. 3 shows an embodiment of the decorative board of the present invention having the above-mentioned core material layer. The decorative board 10 shown in Fig. 3 includes a metal substrate 3, a resin-impregnated layer 2' formed on one side of the metal substrate 3, and a core material layer 4 formed on the metal substrate 3 via the resin-impregnated layer 2'. The resin-impregnated layer 2' is formed on the surface of the aluminum-zinc alloy plating layer 3b of the metal substrate 3. The resin-impregnated layer 2' may be formed on both sides of the metal substrate 3. In this case, the resin-impregnated layers 2' on both sides are both formed on the surface of the aluminum-zinc alloy plating layer 3b of the metal substrate 3.

[0064] As the protective film, any known or conventional film used for decorative panels can be used, such as a plastic film such as a polyethylene terephthalate film (PET film), a polypropylene film, or a polybutylene terephthalate film that has been subjected to a release treatment, or a low-adhesion film.

[0065] [Manufacturing method of decorative panels] An embodiment of the manufacturing method of the decorative board of the present invention will be described with reference to FIG. 4. First, as described above, the thermosetting resin composition prepared by diluting or dissolving with a solvent as necessary is impregnated into the impregnated substrate, and then, as necessary, the solvent is evaporated by drying to prepare a resin-impregnated layer 2 in which the thermosetting resin composition is impregnated into the impregnated substrate. Next, as necessary, a plastic film for surface protection such as a polyethylene film is laid on the resin-impregnated layer 2 to obtain a decorative sheet. When a plastic film is used, a small amount of a volatile solvent may be used at the end to temporarily adhere the plastic film to the decorative sheet.

[0066] Next, the decorative sheet is placed on the metal substrate 3 so that the resin-impregnated layer 2 contacts the aluminum-zinc alloy plating layer 3b surface of the metal substrate 3, and if a plastic film for surface protection is provided, the plastic film is peeled off, and the mirror plate 5 is superimposed on the resin-impregnated layer 2 to obtain a laminate in which the decorative plate 1 and the mirror plate 5 are laminated. The surface of the mirror plate 5 facing the resin-impregnated layer 2 has a shape for transferring a design to the resin-impregnated layer as necessary.

[0067] Next, a press is used to apply heat and pressure from above and below the laminate including the decorative plate 1 to perform thermocompression molding, hardening the resin-impregnated layer 2 to form a thermoset resin-impregnated layer 2', and obtaining a laminate in which the decorative plate 1' and the mirror plate 5 are laminated. As described above, the thermocompression molding method is preferably a laminate thermocompression molding method, in which the resin-impregnated layer 2 and the metal substrate 3 are overlapped and placed in a mold, and then heated and pressurized for hardening. The thermocompression molding is preferably performed at a pressure of, for example, 10 to 25 kgf / cm. 2 The heating can be preferably performed under conditions of a temperature of 120 to 190° C. and a time of 30 seconds to 15 minutes.

[0068] The laminate obtained after the thermocompression molding includes a decorative plate 1' in which a metal substrate 3 and a thermoset resin-impregnated layer 2' provided on the aluminum-zinc alloy plating layer 3b of the metal substrate 3 are laminated. The mirror plate 5 is then removed to obtain the decorative plate 1'. In the decorative plate of the present invention, the resin-impregnated layer has excellent adhesion to the metal substrate even when it contains a release agent, so the resin-impregnated layer can contain a release agent. As a result, the mirror plate 5 can be easily removed even without providing a release layer on the resin-impregnated layer.

[0069] A protective film such as a PET film may then be attached to the surface of the resin-impregnated layer 2' of the decorative board 1'.

[0070] In addition, when manufacturing the decorative board 10 shown in FIG. 3, first, a laminate having a configuration of [metal substrate 3 / resin-impregnated layer 2 before thermosetting / core layer 4] is obtained, and then, using a press, heat and pressure are applied from above and below the laminate to perform thermocompression molding, and the resin-impregnated layer before thermosetting is cured to form a thermoset resin-impregnated layer 2', and each layer of the metal substrate 3, the resin-impregnated layer, and the core layer 4 may be bonded together. In addition, before laminating the core layer 4, thermocompression molding may be performed, and the core layer 4 may be attached to the formed thermoset resin-impregnated layer 2' via an adhesive layer to bond each layer in stages. In addition, when manufacturing the decorative board 10 shown in FIG. 3, the decorative sheet may be placed on either the metal substrate 3 or the core layer 4 first. When the decorative sheet is placed on the core layer 4, the target to be laminated on the resin-impregnated layer is the metal substrate 3, and when the decorative sheet is placed on the metal substrate 3, the target to be laminated on the resin-impregnated layer is the core layer 4. In either case, the layers may be bonded together at once by thermocompression molding, or the layers may be bonded stepwise by thermocompression molding and the use of adhesive layers.

[0071] In addition, in the case of manufacturing a decorative board in which the resin-impregnated layer 2' is formed on both sides of the metal substrate 3 in the decorative board 10 shown in FIG. 3, a laminate having a configuration of [resin-impregnated layer 2 before thermosetting / metal substrate 3 / resin-impregnated layer 2 before thermosetting / core layer 4] is first obtained, and then thermo-compression molding is performed to cure the resin-impregnated layer before thermosetting to form the thermo-cured resin-impregnated layer 2', and the resin-impregnated layer, metal substrate 3, resin-impregnated layer, and core layer 4 may be bonded together. In addition, the resin-impregnated layer 2 may be first formed on one side of the metal substrate 3 and thermo-compression molding is performed, and then the resin-impregnated layer 2 and the core layer 4 may be superimposed on the other side, and the metal substrate 3, resin-impregnated layer, and core layer 4 may be bonded together by thermo-compression molding. In addition, as described above, the metal substrate 3 or the core layer 4 may be bonded to the resin-impregnated layer 2' after thermosetting via an adhesive layer. In this manner, the decorative board of the present invention can be manufactured.

[0072] The decorative board of the present invention has excellent interlayer adhesion even when a metal substrate is used as the substrate and the resin-impregnated layer and the metal layer are laminated so as to be in direct contact with each other, as well as when an adhesive is interposed between the layers. Furthermore, it is easy to remove the laminate after thermocompression molding, not only when a separate release layer is provided on the resin-impregnated layer, but also when no release layer is provided. Therefore, it is possible to reduce the thickness of the adhesive layer or release layer, or to not provide it at all, and the cost of forming the adhesive layer or release layer can be reduced, resulting in excellent economic efficiency. Furthermore, since the decorative board of the present invention can be made to have a high surface hardness on the decorative sheet side, it can also be used for applications requiring high surface hardness, such as whiteboards. EXAMPLES

[0073] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0074] Example 1 A resin composition solution was prepared by dissolving 60 parts by mass of diallyl orthophthalate prepolymer (viscosity (30°C) of 96.5 mPa·s in a 50% by mass solution in methyl ethyl ketone, manufactured by Osaka Soda Co., Ltd.), 50 parts by mass of unsaturated polyester (product name "DH-2000B", manufactured by DIC Material Co., Ltd.), 5 parts by mass of dipentaerythritol hexaacrylate, 17.5 parts by mass of aluminum hydroxide (product name "BF013STM", manufactured by Nippon Light Metal Co., Ltd.), 3 parts by mass of benzoyl peroxide, 1 part by mass of an internal mold release agent (product name "Zelec UN", manufactured by DuPont), 0.05 parts by mass of hydroquinone (polymerization inhibitor), and 3 parts by mass of finely powdered silica (product name "Carplex", manufactured by Shionogi & Co., Ltd.) in acetone. 60 g / m was added to the above resin composition solution at 25°C. 2 After impregnating a printed pattern paper of 160 g / m with the resin composition, the paper was heated in a hot air circulating oven at 105° C. for 90 seconds to volatilize the solvent, and the resin composition was dried to a density of 160 g / m 2 A decorative sheet made of impregnated paper (amount of impregnation per 100 parts by mass of printed pattern paper: 167 parts by mass) was obtained.

[0075] A steel plate (trade name: "Galvastar", manufactured by Nippon Steel Corporation, thickness 270 μm) with aluminum-zinc alloy plating on both sides was placed on the rotating plate as a metal substrate, and the decorative sheet was placed on the metal substrate so that the impregnated paper was in contact with the metal substrate. Then, using a press machine, pressure was applied so that the hot plate on which the mirror plate was set was on the impregnated paper side and the other hot plate was on the rotating plate side, and heat was applied to perform thermo-compression molding. The thermo-compression molding was performed at a temperature of 125°C and a pressure of 16 kgf / cm. 2 The pressure was then released, and the laminate of the guide plate, the metal substrate, and the resin-impregnated layer was removed from the press and cooled to room temperature to obtain a decorative plate. The aluminum-zinc alloy plating layer of the steel plate used had a density of 3.69 g / cm 3 , standard coverage 200g / m 2 (AZ150), the total proportion of aluminum and zinc is 98.4 mass%, 99 volume%, the mass ratio of aluminum and zinc is 55.9:44.1, and the volume ratio is 80.8:19.2.

[0077] Example 3 A decorative sheet was produced in the same manner as in Example 1, except that a steel plate having an aluminum-zinc alloy plating on both sides (product name: "SGL", manufactured by Nippon Steel Corporation, thickness 350 μm, Mg ratio in the plating layer: 2%) was used as the metal substrate.

[0078] Example 4 A resin composition solution was prepared by dissolving 70 parts by mass of diallyl orthophthalate prepolymer (viscosity (30°C) of 96.5 mPa·s in a 50% by mass solution in methyl ethyl ketone, manufactured by Osaka Soda Co., Ltd.), 30 parts by mass of dipentaerythritol hexaacrylate, 3 parts by mass of benzoyl peroxide, 1.5 parts by mass of an internal release agent (trade name "Zelec UN", manufactured by DuPont), 0.1 parts by mass of hydroquinone (polymerization inhibitor), 50 parts by mass of aluminum hydroxide (trade name "BF013STM", manufactured by Nippon Light Metal Co., Ltd.), 5 parts by mass of magnesium hydroxide (trade name "Magseeds N-6", manufactured by Konoshima Chemical Co., Ltd.), and 0.1 parts by mass of an antifoaming agent in acetone. 60 g / m was added to the above resin composition solution at 25°C. 2 After impregnating a printed pattern paper of 160 g / m with the resin composition, the paper was heated in a hot air circulating oven at 105° C. for 90 seconds to volatilize the solvent, and the resin composition was dried to a density of 160 g / m 2 A decorative sheet made of impregnated paper (amount of impregnation per 100 parts by mass of printed pattern paper: 167 parts by mass) was obtained.

[0079] A decorative board was produced in the same manner as in Example 1, except that the above decorative sheet was used.

[0080] Comparative Example 1 A decorative sheet was produced in the same manner as in Example 1, except that a zinc-plated steel sheet (thickness: 300 μm) was used as the metal substrate.

[0081] Comparative Example 2 A decorative board was produced in the same manner as in Example 1, except that iron foil (thickness: 20 μm) was used as the metal substrate.

[0082] Comparative Example 3 A decorative board was produced in the same manner as in Example 2, except that iron foil (thickness: 20 μm) was used as the metal substrate.

[0083] Comparative Example 4 A decorative board was produced in the same manner as in Example 1, except that an aluminum plate (thickness: 300 μm) was used as the metal substrate.

[0084] Comparative Example 5 A decorative board was produced in the same manner as in Example 2, except that an aluminum plate (thickness: 300 μm) was used as the metal substrate.

[0085] (evaluation) The decorative boards obtained in the Examples and Comparative Examples were evaluated as follows. The evaluation results are shown in the table. In the table, "-" indicates that no evaluation was performed.

[0086] (1) Cross-cut test (JIS K5600 compliant) On the surface of each of the decorative panels obtained in the examples and comparative examples, 6 vertical and 6 horizontal lattice-shaped cuts were made at 2 mm intervals using a cutter knife to create 25 lattices (5 vertical × 5 horizontal). Then, adhesive tape was attached to the lattices by hand and peeled off vigorously to check whether the impregnated paper had peeled off in each lattice. Then, the following criteria were used to judge. [Judgment criteria] ○ (Good): The number of peeled lattices is 5 or less. × (bad): The number of peeled lattices is 6 or more.

[0087] (2) Water resistance test (based on JAS2 type immersion peel test) Test pieces measuring 75 mm x 75 mm were cut out from each of the decorative boards obtained in the examples, and the test pieces were immersed in warm water at 70°C for 2 hours, and then dried in an oven at 60°C for 3 hours to check whether the impregnated paper had peeled off. Note that the decorative boards obtained in the comparative examples were not subjected to a water resistance test because they were rated x (poor) in the cross-cut test. [Judgment criteria] ○(Good): No peeling. × (bad): peeling is observed.

[0088] (3) Boiling resistance test (JIS K6902 compliant) A test piece of 50 mm x 50 mm size was cut out from each of the decorative boards obtained in the examples, and the test piece was dried at 50 ° C for 24 hours, and then immersed in boiling water and left for 2 hours. The test piece was then immersed in water at 23 ° C for 15 minutes and removed to check whether the impregnated paper had peeled off. Note that the decorative boards obtained in the comparative examples were not subjected to a boiling resistance test because they were × (bad) in the cross-cut test. [Judgment criteria] ○(Good): No peeling. × (bad): peeling is observed.

[0089] (4) Pencil hardness test (JIS K5600-5-4 compliant) The pencil hardness of the surface of each decorative panel (the surface on the decorative sheet side) obtained in Examples 1 and 4 was evaluated according to JIS K5600-5-4, General Test Method for Paints - Scratch Hardness (Pencil Method), and was performed by hand scratching on the molded decorative panel surface.

[0090] [Table 1]

[0091] As shown in the table, the decorative boards (Examples) of the present invention, which were prepared using a steel plate having an aluminum-zinc alloy plating layer on both sides as the metal substrate, showed good results in the cross-cut test, water resistance test, and boiling resistance test, and were evaluated as having excellent adhesion between the metal substrate and the impregnated paper. Furthermore, the decorative boards of Examples 1 and 4 also showed good results in the pencil hardness test, and were evaluated as having excellent surface hardness. Note that the decorative board of Example 2 had blisters on the surface of the decorative sheet after the boiling resistance test. On the other hand, when a metal substrate having another plating layer was used (Comparative Example 1) or when an iron foil or aluminum plate that was not plated was used (Comparative Examples 2 to 5), the amount of peeling was large even in the cross-cut test, and it was evaluated that the adhesion between the metal substrate and the impregnated paper was insufficient. Note that the water resistance test and the boiling resistance test are more severe adhesion tests than the cross-cut test. [Explanation of symbols]

[0092] 1,1' Veneer 2 Resin-impregnated layer (before heat curing, prepreg) 2' Resin impregnated layer (heat cured) 3 Metal base material 3a metal layer 3b Aluminum-zinc alloy plating layer 4 Core layer 5 Mirror plate 10 Decorative panels 21, 22 Resin impregnated layer

Claims

1. The laminate has a structure in which a metal substrate and a resin-impregnated layer in which a thermosetting resin composition is impregnated into the impregnated substrate are laminated, the metal base material has an aluminum-zinc alloy plating layer on a surface on the resin-impregnated layer side, A decorative sheet having an area where the aluminum-zinc alloy plating layer and the resin-impregnated layer of the metal substrate are in contact with each other.

2. 2. The decorative sheet according to claim 1, wherein the metal substrate is an aluminum-zinc alloy plated steel sheet.

3. The decorative board according to claim 1 or 2, wherein the thermosetting resin composition contains a diallyl phthalate-based resin or a melamine-based resin.

4. The decorative board according to any one of claims 1 to 3, wherein the thermosetting resin composition contains an unsaturated polyester resin.

5. The present invention relates to a method for manufacturing a metal substrate, the method comprising: forming a resin-impregnated layer on both sides of the metal substrate; The decorative panel described.

6. A core layer is provided on one surface of the metal base material via the resin-impregnated layer.

6. The decorative board according to any one of 1 to 5.

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