Decorative sheets and decorative materials

Abstract

To provide a decorative sheet having excellent cleaning properties as a decorative material, and a decorative material using the decorative sheet.SOLUTION: A decorative sheet 10 includes a surface protective layer 7 formed on a base material sheet 1. In layers composing the surface protective layer 7, at least a second surface protective layer 6 located on an outermost surface contains paraffin of 1 to 10 wt.%.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a resin decorative sheet and decorative material, and in particular to a technology relating to a decorative sheet and decorative material thereof that have excellent cleanability and can be attached to a substrate such as a wood-based substrate and used for flooring or its surroundings. [Background technology]

[0002] Decorative sheets have been developed and expanded as the residential construction industry has developed. In particular, prefabricated buildings have played a leading role in the development of residential buildings such as apartments and condominiums, as well as individual homes.

[0003] Traditionally, people built houses using materials that were characteristic of the region, such as wood and stone, and in styles rooted in unique cultures, but as the housing industry developed and industrialization progressed, natural materials were replaced by artificial materials. In recent years, the heavy use of high-quality wood and stone has led to concerns that it could lead to deforestation and environmental problems, which has also become a factor in the expansion of demand for decorative sheets.

[0004] For example, in recent years, decorative materials in which a decorative sheet is bonded to the surface of a substrate, such as a wood substrate such as plywood, MDF (medium density fiberboard), or particle board, as well as a resin substrate, an inorganic non-flammable substrate, or a metal substrate, have become widely used (for example, Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 5045180 [Patent Document 2] JP 2017-24201 A Summary of the Invention [Problem to be solved by the invention]

[0006] Here, the fundamental need for building materials as a whole is the simplification of cleaning. For example, there is an increasing demand for easy cleaning of food, dust, sweat, and other stains that occur during the life of residents. In addition, after the completion of interior construction work in apartments, condominiums, and private homes, the interior is cleaned by management companies and beautifying companies, and the floor is cleaned by wiping off the plasterboard, putty, and other adhesive debris, dust, etc. that have accumulated on the floor using water and detergent. When wiping and cleaning sheet flooring materials, if the dry wiping ability after wiping with water is difficult or if the wiping is prone to unevenness, problems such as time-consuming cleaning may occur.

[0007] The present invention has been made in consideration of the above-mentioned points, and aims to provide a decorative sheet that is easy to wipe off when cleaning and has excellent cleaning properties as a decorative material, and a decorative material using said decorative sheet. [Means for solving the problem]

[0008] In order to solve the above problems, a decorative sheet according to one embodiment of the present invention comprises a surface protective layer provided on a substrate sheet, and at least the outermost layer among the layers constituting the surface protective layer contains 1% by weight to 10% by weight of paraffin, and the surface protective layer has a 60 degree specular gloss in the range of 5 to 35 according to JIS Z 8741. The paraffin is liquid paraffin. It is characterized by the above.

[0009] In order to solve the above problems, a decorative material according to another aspect of the present invention is characterized by using the above decorative sheet. Effect of the Invention

[0010] According to one aspect of the present invention, it is possible to provide a decorative sheet that has light wiping properties when cleaning and has excellent cleanability as a decorative material, and a decorative material using said decorative sheet. [Brief description of the drawings]

[0011] [Figure 1]1 is a schematic cross-sectional view illustrating a decorative sheet according to one embodiment of the present invention and a decorative material using the decorative sheet. FIG. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. In this embodiment, a decorative sheet and a decorative material for floors and fittings will be described as an example, but the decorative sheet and the decorative material may be used for other parts. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc. differ from the actual ones. Furthermore, the embodiments shown below are 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, structures, 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.

[0013] 1, the decorative sheet 10 of this embodiment is formed by laminating, in this order, a picture pattern layer 2, a transparent adhesive layer 3, a transparent thermoplastic resin layer 4, and a surface protective layer 7 on a base sheet 1. This embodiment is an example in which the surface protective layer 7 is made up of two layers, a first surface protective layer 5 and a second surface protective layer 6. In addition, on the surface (rear surface) of the base sheet 1 opposite to the picture pattern layer 2, a rear resin coat layer 8 made of a resin layer is provided. The decorative sheet 10 may have a configuration comprising at least a base sheet 1 and a surface protective layer 7 provided on the base sheet 1 .

[0014] [Cosmetic materials] 1, a decorative sheet 10 is used for the decorative material 20. Specifically, the decorative material 20 is constructed by bonding the decorative sheet 10 to a base material 11.

[0015] [Base material 11] As the substrate 11, tropical plywood, particle board, medium density fiberboard (hereinafter referred to as MDF), ordinary plywood as specified by the Japanese Agricultural Standards, etc. can be used. Substrates made of olefin resin with added wood powder can also be used. The thickness of the substrate 11 is preferably about 3 mm or more and 25 mm or less. The substrate 11 may be made of metal such as aluminum, resin such as plastic, or a composite material thereof.

[0016] [Base sheet 1] The base sheet 1 may be made of paper or plastic film, and examples of the material include coated paper, thermoplastic resin, thermosetting resin, ionizing radiation curable resin, and other curable resins. These resins may be used as a single composition or as a mixture of several types. Examples of the thermoplastic resin include polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, and the like. Among them, polyolefin-based resins can be preferably used in terms of environmental compatibility, processability, and price. Examples of the thermosetting resin include one-liquid or two-liquid reactive curable polyurethane-based resins and epoxy-based resins. Examples of the ionizing radiation curable resin include a composition mainly composed of at least one of a prepolymer, oligomer, and monomer having a polymerizable unsaturated bond such as a (meth)acryloyl group, which has a property of undergoing a crosslinking reaction when irradiated with ionizing radiation. Examples of the ionizing radiation that can be used include electron beams and ultraviolet rays. The grade and composition of the resin can be selected in consideration of the ease of sheeting, printability, and suitability for bending.

[0017] When the base sheet 1 is colored, the base material to which the decorative sheet 10 is attached is concealed, and a suitable hue can be selected as the base color of the picture pattern layer 2. For example, coloring can be achieved by mixing or kneading a coloring agent such as a pigment when sheeting the thermoplastic resin. Alternatively, a colored layer can be provided under the picture pattern layer 2 as a solid ink layer using a coating or printing technique before providing the picture pattern layer 2.

[0018] [Pattern layer 2] The picture pattern layer 2 can be provided using a known printing method. When the base sheet 1 can be prepared in a rolled state, printing for forming the picture pattern layer 2 can be performed using a roll-to-roll printing device. The printing method is not particularly limited, but if productivity and quality of the pattern are taken into consideration, for example, gravure printing can be used.

[0019] The design pattern can be any pattern that takes into consideration the design of the flooring material, and for wood-based patterns, various wood grains are often preferred, and cork can also be used as a pattern other than wood grain. For example, if the design is based on a stone floor such as marble, marble grain may be used as the pattern. In addition to patterns made from natural materials, artificial patterns based on natural materials or geometric patterns can also be used.

[0020] The printing ink is not particularly limited, but can be selected appropriately according to the printing method. It is preferable to select the ink taking into consideration the adhesion to the base sheet 1, printability, and weather resistance as a flooring material.

[0021] [Transparent adhesive layer 3] The transparent adhesive layer 3 is provided for the purpose of strengthening the adhesion between the base sheet 1 and the picture pattern layer 2 and the transparent thermoplastic resin layer 4. This strong adhesion can impart bending processability to the decorative sheet 10 so that it can conform to curved surfaces and right-angled surfaces.

[0022] If necessary, an adhesive layer (not shown) may be provided on the picture pattern layer 2 or on the transparent adhesive layer 3 in order to improve adhesion between the picture pattern layer 2 and the transparent adhesive layer 3, and between the transparent adhesive layer 3 and the transparent thermoplastic resin layer 4. The resin used for this adhesive layer (not shown) is not particularly limited, but for example, a two-component curing urethane resin can be used. The adhesive layer can be provided using, for example, a coating device or a gravure printing device.

[0023] [Transparent thermoplastic resin layer 4] For example, vinyl chloride resin, acrylic resin, polyolefin-based polypropylene resin, polyethylene resin, etc. can be used for the transparent thermoplastic resin layer 4. Among them, polyolefin-based resins can be preferably used in terms of environmental compatibility, processability, and cost.

[0024] The grade and composition of the resin can also be selected taking into consideration the ease of sheeting, printability, and suitability for bending. In particular, it is important to select a resin that will not whiten or crack at the bent part.

[0025] The transparent adhesive layer 3 and the transparent thermoplastic resin layer 4 can be formed, for example, by simultaneously extruding them by coextrusion.

[0026] The transparent thermoplastic resin layer 4 not only gives the decorative sheet 10 a design effect of thickness and depth, but also improves the weather resistance and abrasion resistance of the decorative sheet 10.

[0027] [Surface protection layer 7] A surface protective layer 7 is provided on the transparent thermoplastic resin layer 4. The surface protective layer 7 may be a single layer, or multiple layers may be laminated to form the surface protective layer 7. As shown in FIG. 1, in the decorative sheet 10 of this embodiment, two layers, a first surface protective layer 5 and a second surface protective layer 6, are provided as the surface protective layer 7. When the surface protective layer 7 has a structure consisting of one layer (single layer structure), the second surface protective layer 6 becomes the surface protective layer 7.

[0028] To provide the surface protective layer 7 consisting of the first surface protective layer 5 and the second surface protective layer 6, each layer can be applied and the coating cured using a known coating device, heat drying device, and ultraviolet irradiation device depending on the type of curable resin.

[0029] The surface protective layer 7 plays an important role in determining the superiority or inferiority of bending workability, scratch resistance, and cleanability. The surface protective layer 7 is mainly composed of a curable resin. In other words, it is preferable that the resin component is substantially composed of a curable resin. "Substantially" refers to, for example, 80 parts by mass or more when the entire resin is taken as 100 parts by mass. The surface protective layer 7 may contain weathering agents, plasticizers, stabilizers, fillers, dispersants, colorants such as dyes and pigments, solvents, etc., as necessary.

[0030] The surface of the surface protection layer 7 may be unevenly formed to impart a given design. Usually, the uneven pattern is formed by embossing. The embossing method is not particularly limited. A known sheet-fed or rotary embossing machine is used for embossing. Examples of the uneven shape include the duct grooves of a wood grain board, the uneven surface of a stone slab (such as the cleavage surface of granite), the texture of a cloth surface, matte finish, sand grain, hairline, and linear grooves.

[0031] [Second surface protective layer 6] The second surface protective layer 6 is the layer (outermost layer) located on the outermost surface (outermost surface) of the layers (first surface protective layer 5, second surface protective layer 6) constituting the surface protective layer 7. Examples of materials for forming the second surface protective layer 6 include thermosetting resins and ionizing radiation curing resins. The second surface protective layer 6 can be generally formed by a method in which a coating film is formed by coating a reactive resin, and then the coating film is cured by heating or irradiating with ionizing radiation. The second surface protective layer 6 also has differences in characteristics due to differences in the curing method. For example, the second surface protective layer 6 generally formed of an ionizing radiation curing resin has a high degree of crosslinking after the curing reaction, so it has a high hardness and tends to be excellent in scratch resistance. On the other hand, the second surface protective layer 6 formed of a thermosetting resin has a relatively low degree of crosslinking, so it has a low hardness and tends to be excellent in flexibility, such as bending and conforming to the substrate.

[0032] The second surface protective layer 6 may be mainly composed of either an ionizing radiation curable resin or a thermosetting resin, or a mixture (mixed material) of an ionizing radiation curable resin and a thermosetting resin. In other words, the main component of the second surface protective layer 6 may be an ionizing radiation curable resin alone, a thermosetting resin alone, or a mixture of these (ionizing radiation curable resin and thermosetting resin). When the main component is the mixture, the ratio of the thermosetting resin and the ionizing radiation curable resin in the second surface protective layer 6 can be controlled depending on the intended use, so that the decorative sheet 10 can be used according to the requirements of various applications. For example, when the decorative sheet 10 is used as a flooring material, scratch resistance is often required. For this reason, for example, in the decorative sheet 10 used as a flooring material, it is preferable that the mixture of the thermosetting resin and the ionizing radiation curable resin, which is the main component of the second surface protective layer 6, contains more ionizing radiation curable resin than thermosetting resin. Specifically, the ionizing radiation curable resin needs to exceed 50% by weight in the mixture, preferably 70% by weight or more, more preferably 75% by weight or more, and even more preferably 80% by weight or more.

[0033] Furthermore, when the decorative sheet 10 is used as a component in fittings that often have complex shapes, flexibility is often required. For this reason, for example, in the decorative sheet 10 used in fittings, the mixture of thermosetting resin and ionizing radiation curable resin that is the main component of the second surface protective layer 6 preferably contains more thermosetting resin than ionizing radiation curable resin. Specifically, it is sufficient that the thermosetting resin in the mixture exceeds 50% by weight, and it is preferable that it accounts for 70% by weight or more, more preferably 75% by weight or more, and even more preferably 80% by weight or more.

[0034] In this way, by using a mixture of ionizing radiation curable resin and thermosetting resin as the main component of the second surface protective layer 6, which is the outermost layer of the surface protective layer 7, scratch resistance is satisfied when used on a floor, and at the same time, whitening and cracking of the surface protective layer is less likely to occur during bending. In applications where scratch resistance is not a major concern, only thermosetting resin can be used as the main component of the second surface protective layer 6, and in applications where bending workability is not required, only ionizing radiation curable resin can be used as the main component. However, the performance of the decorative sheet 10, such as the scratch resistance and flexibility, described above, is not determined solely by the difference in the curing method of the resin used in the second surface protective layer 6. The performance of the decorative sheet 10 (here, scratch resistance and flexibility) is also greatly influenced by the material design of the resin itself and the addition of additives such as fillers. For this reason, the design of the second surface protective layer 6 as a whole becomes important.

[0035] The thickness of the second surface protective layer 6 in the decorative sheet 10 may be within the range of 2 μm to 30 μm. If the thickness of the second surface protective layer 6 is less than 2 μm, the coating method becomes limited and stable production becomes difficult, which may result in reduced productivity. Furthermore, weather resistance and scratch resistance may decrease, resulting in greater variation. On the other hand, if the thickness of the second surface protective layer 6 exceeds 30 μm, the balance between performance and cost may be lost, resulting in higher costs. Furthermore, flexibility may decrease. In view of this, it is more preferable that the thickness of the second surface protective layer 6 is 10 μm or less.

[0036] [Ionizing radiation curable resin] The ionizing radiation curable resin used in the second surface protective layer 6 is not particularly limited, and a transparent resin mainly composed of a prepolymer (including oligomer) and / or monomer containing a radically polymerizable double bond in the molecule that can undergo a polymerization / crosslinking reaction when irradiated with ionizing radiation such as ultraviolet light or an electron beam can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction in the ionizing radiation curable resin is usually a crosslinking curing reaction.

[0037] Specifically, the above-mentioned prepolymer or monomer may be a compound having, in the molecule, a radically polymerizable unsaturated group such as a (meth)acryloyl group or a (meth)acryloyloxy group, or a cationic polymerizable functional group such as an epoxy group, etc. Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

[0038] Examples of prepolymers having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, silicone (meth)acrylate, etc. The molecular weight of these is usually preferably about 250 to 100,000.

[0039] Examples of the monomer having a radically polymerizable unsaturated group include monofunctional monomers such as methyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and phenoxyethyl(meth)acrylate. Examples of the polyfunctional monomers include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0040] Examples of prepolymers having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers.

[0041] In addition, the above-mentioned prepolymer is preferably a polyene / thiol-based prepolymer obtained by combining a polyene and a polythiol. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include polyurethanes obtained by adding allyl alcohol to both ends of the polyurethanes made of diols and diisocyanates.

[0042] The ionizing radiation used to cure the ionizing radiation curable resin is electromagnetic waves or charged particles having energy capable of causing a curing reaction of the molecules in the ionizing radiation curable resin (composition). Usually, ultraviolet rays or electron beams are used, but visible light, X-rays, ion beams, etc. may also be used.

[0043] Examples of the ultraviolet light source that can be used include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black lights, metal halide lamps, etc. The wavelength of the ultraviolet light is preferably in the range of 190 nm to 380 nm.

[0044] As the electron beam source, various electron beam accelerators can be used, such as Cockcroft-Walton type, Van de Graff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. Among them, those capable of irradiating electrons having an energy in the range of 100 keV to 1000 keV are particularly preferred, and those capable of irradiating electrons having an energy in the range of 100 keV to 300 keV are more preferred.

[0045] [Thermosetting resin] Here, the thermosetting resin used in the second surface protective layer 6 is not particularly limited, but may be, for example, a two-component curing urethane-based resin. The two-component curing urethane-based resin is not particularly limited, but may be one containing a polyol component having an OH group (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) as a main component and an isocyanate component (tolylene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, etc.) as a curing agent component. The thermosetting resin is not limited to these, and may be a one-component reactive curing polyurethane-based resin, a one-component or two-component reactive curing epoxy-based resin, etc.

[0046] In the decorative sheet 10 according to the present embodiment, at least the second surface protective layer 6 of the surface protective layer 7 contains 1% by weight or more and 10% by weight or less of paraffin. It is widely known that when paraffin is mixed with a resin, it bleeds to the surface. The decorative sheet 10 utilizes this characteristic, and by containing paraffin in the second surface protective layer 6, it has the effect of removing dirt attached to the surface together with the paraffin. When the paraffin content in the second surface protective layer 6 is 1% by weight or more, the paraffin bleeds to the surface, and when wiping off dirt attached to the surface of the decorative sheet 10, the dry wiping property after wiping with water becomes light, and there is an effect that unevenness is less likely to occur when wiping off. In other words, the decorative sheet 10 has light wiping property and exhibits excellent cleaning property. In contrast, when the paraffin content in the second surface protective layer 6 is less than 1% by weight, the amount of paraffin that bleeds to the surface is small, and sufficient cleaning property cannot be expected. For the above reasons, the paraffin content in the second surface protective layer 6 is preferably 1 wt % or more, more preferably 2 wt % or more, and even more preferably 3 wt % or more.

[0047] On the other hand, if the content of paraffin contained in the second surface protective layer 6 exceeds 10% by weight, paraffin may become a factor inhibiting hardening during the process of hardening the resin when forming the second surface protective layer 6. Since paraffin itself has low hardness, if the hardening of the resin is inhibited, the surface hardness of the second surface protective layer 6 decreases, which causes the layer to be easily scratched. In addition, when the decorative sheet 10 is used as a flooring material, flooring wax may be applied when cleaning the surface. In this case, if the weight ratio of paraffin in the second surface protective layer 6 exceeds 10%, the flooring wax is repelled by the surface of the decorative sheet 10. This may cause practical problems such as the flooring wax not being applied evenly or peeling off later. For the above reasons, the paraffin contained in the second surface protective layer 6 is preferably 10% by weight or less, more preferably 9% by weight or less, and even more preferably 8% by weight or less. Furthermore, when considering scratch resistance and wax adhesion in addition to cleaning ease, the paraffin content in the second surface protective layer 6 is more preferably in the range of 3% by weight to 8% by weight.

[0048] Thus, the decorative sheet 10 contains 1% by weight to 10% by weight of paraffin in at least the second surface protective layer 6 of the surface protective layer 7. This makes it easier for the decorative sheet 10 to wipe away dirt such as food, dust, and sweat that accumulates during the life of the resident, as well as debris and dust from gypsum boards, adhesives, putty, and the like that accumulates during indoor construction. As a result, the decorative sheet 10 is easy to wipe off when cleaning, and has excellent cleanability.

[0049] [paraffin] Examples of paraffin contained in the second surface protective layer 6 include normal paraffin, isoparaffin, and cycloparaffin. In the second surface protective layer 6, normal paraffin and isoparaffin may be used alone, or normal paraffin and isoparaffin may be mixed and used. Paraffin may be solid paraffin (paraffin wax) or liquid paraffin. The paraffin used in the second surface protective layer 6 may have a carbon number in the range of 15 to 40. Since the volatility increases as the carbon number decreases, if the carbon number is 14 or less, the paraffin may volatilize after the sheet is produced, and the effect may be lost. On the other hand, the viscosity increases and the movement becomes difficult as the carbon number increases, so if the carbon number is greater than 41, the paraffin is less likely to fall off together with the surface dirt as described above.

[0050] Manufacturers of these paraffins include, for example, Nippon Seiro Co., Ltd., Kaneda Co., Ltd., MORESCO Co., Ltd., Hayashi Pure Chemical Industries Co., Ltd., and the like.

[0051] In addition, the second surface protective layer 6 may contain a matting agent as a filler to adjust the surface gloss to a desired gloss level. Examples of the matting agent include organic matting agents such as acrylic resins and granular rubber, and inorganic matting agents such as silica powder, mica powder, talc, alumina, silicon carbide, and calcium carbonate. The matting agent may be a single substance selected from the group consisting of organic and inorganic matting agents, or may be a combination of two or more substances selected from the group. Among the matting agents, it is preferable to use a porous filler made of a porous material as the matting agent. Examples of the material of the porous filler include silica, alumina, silicon nitride, boron nitride, magnesia, boehmite, calcium carbonate, and aluminum hydroxide. Among these porous fillers, porous silica is more preferable as the matting agent because it has a higher matting effect.

[0052] The decorative sheet 10 may contain 1 wt % or less of a matting agent in the second surface protective layer 6, or may not contain any matting agent at all in the second surface protective layer 6. By containing 1 wt % or less of a matting agent in the second surface protective layer 6, the decorative sheet 10 can adjust the surface gloss to a desired gloss level while exhibiting sufficient cleanability. On the other hand, if the matting agent contained in the second surface protective layer 6 exceeds 1 wt %, the matting agent becomes easily soiled, and sufficient cleanability may not be achieved. For example, the decorative sheet 10 may contain 1 wt % or less of a porous filler in the second surface protective layer 6, or may not contain any porous filler at all.

[0053] The average particle size of the matting agent is preferably in the range of 0.1 μm or more and 20 μm or less, and more preferably in the range of 1 μm or more and 10 μm or less, particularly from the viewpoint of imparting a matte appearance. In addition, by adjusting the blending amount of the matting agent and its amount, the 60-degree specular gloss value of the second surface protective layer 6 according to JIS Z 8741 is adjusted to a desired gloss value according to the purpose of the decorative sheet 10. In this embodiment, the desired 60-degree specular gloss value is set to a range of 5 to less than 20, or 20 to 35. In this way, by setting the 60-degree specular gloss value of the second surface protective layer 6 according to JIS Z 8741 to 5 to 35, unevenness after wiping during cleaning becomes less noticeable. Here, the higher the gloss value, the better the wiping property, but the worse the design property. The 60-degree specular gloss value is set to 5 to 35 in consideration of the balance between improving wiping property and imparting design property above the required level. At this time, when design property is relatively emphasized, it is preferable to adjust it to 5 to 20, and when wiping property is relatively emphasized, it is preferable to adjust it to 20 to 35.

[0054] [First surface protective layer 5] The first surface protective layer 5 may be made of a resin having the same composition as the second surface protective layer 6, which is the outermost layer, or may be made of a resin having a different type, composition, or ratio. For example, the first surface protective layer 5 may contain paraffin. It is expected that paraffin will migrate from the first surface protective layer 5 to the second surface protective layer 6, and as a result, the same effect as when paraffin is contained in the second surface protective layer 6 can be obtained. In this case, the time it takes for paraffin to bleed to the surface is controlled based on the compatibility between the first surface protective layer 5 and paraffin, etc. The thickness of the first surface protective layer 5 may be within a range of 2 μm to 50 μm. If the thickness of the first surface protective layer 5 is less than 2 μm, the coating method becomes limited and stable production becomes difficult, which may result in reduced productivity. Furthermore, weather resistance and scratch resistance may decrease and variation may increase. On the other hand, if the thickness of the first surface protective layer 5 exceeds 50 μm, the balance between performance and cost may be lost, resulting in increased costs and reduced flexibility. In view of this, it is more preferable that the thickness of the first surface protective layer 5 is 20 μm or less.

[0055] [Backside resin coating layer 8] The side of the picture pattern layer 2 of the base sheet 1 in the decorative sheet 10 is as described above. Here, when the decorative sheet 10 is to be used as the decorative material 20 by bonding it to, for example, a wooden base material 11, or when the decorative sheet 10 is to be further processed as a component, a back resin coating layer 8 may be provided on one side of the resin base sheet 1. Specifically, a resin layer containing silica powder may be provided as the back resin coating layer 8 on the side opposite the picture pattern layer 2 of the front and back sides of the base sheet 1. This can improve the adhesive strength between the base material 11 and the decorative sheet 10. As the adhesive used to bond the back resin coating layer 8, for example, an emulsion type adhesive of ethylene vinyl acetate copolymer can be used.

[0056] The decorative sheet 10 according to the present embodiment, which is made of the above-mentioned materials, is easy to wipe off and has excellent cleaning properties, making it suitable as a decorative sheet. The decorative sheet 10 according to the present embodiment can be used as a decorative sheet for various building materials such as flooring, stair treads, fittings, and furniture.

[0057] (Modification) The configuration of the surface protective layer 7 in the decorative sheet 10 is not limited to the above embodiment. For example, silicone resin or fluorine resin may be applied to the outermost surface (second surface protective layer 6) of the decorative sheet 10 to improve stain resistance. [Fluororesin] In particular, fluororesins are widely known to have the lowest level of surface tension and are suitable as anti-staining materials. Examples of fluororesins contained in the second surface protective layer 6 include tetrafluoroethylene resin, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and many other derivatives can also be used.

[0058] Manufacturers of these fluororesins include Daikin Industries, Ltd. and Mitsui DuPont Fluorochemicals Co., Ltd. The amount of fluororesin contained in the second surface protective layer 6 is preferably 10 parts by mass or more and 100 parts by mass or less. More preferably, it is 20 parts by mass or more. Here, the fluororesin itself may be a curable resin. That is, a part of the fluororesin may also serve as a part of the curable resin that is the main component of the surface protective layer 7 (first surface protective layer 5, second surface protective layer 6). In this way, the entire resin component of the second surface protective layer 6 may be a fluororesin. Furthermore, the above-mentioned paraffin may be contained in the second surface protective layer 6, which is mainly composed of a fluororesin. This provides the decorative sheet 10 with excellent cleanability and improved stain resistance.

[0059] The decorative sheet 10 according to the present embodiment comprises a surface protective layer 7 provided on a base sheet 1, and of the layers constituting the surface protective layer 7, at least the second surface protective layer 6 located on the outermost surface contains paraffin in an amount of 1% by weight to 10% by weight. This allows the decorative sheet 10 to be easily wiped off during cleaning, and provides excellent cleanability as a decorative material. Furthermore, the decorative sheet 10 may contain 3% by weight or more and 8% by weight or less of paraffin in the second surface protective layer 6. This allows the decorative sheet 10 to achieve both scratch resistance and cleanability.

[0060] Furthermore, in the decorative sheet 10 according to this embodiment, the paraffin contained in the second surface protective layer 6 may be at least one of normal paraffin and isoparaffin. Furthermore, the paraffin contained in the second surface protective layer 6 in the decorative sheet 10 according to this embodiment may have a carbon number in the range of 15 or more and 40 or less.

[0061] Furthermore, the decorative sheet 10 according to this embodiment may contain 1% by weight or less of a porous filler in the surface protective layer 7, or may not contain any.

[0062] Furthermore, at least the second surface protective layer among the layers constituting the surface protective layer 7 may be mainly composed of either an ionizing radiation curable resin or a thermosetting resin, or a mixture of an ionizing radiation curable resin and a thermosetting resin. The mixture may also contain more ionizing radiation curable resin than thermosetting resin. The mixture may also contain more thermosetting resin than ionizing radiation curable resin.

[0063] Moreover, the decorative material 20 according to this embodiment may use the above-mentioned decorative sheet 10. This allows the decorative material 20 to be easily wiped off during cleaning, and provides excellent cleanability as a decorative material. EXAMPLES

[0064] The present invention will now be described more specifically and in detail with reference to examples, but the present invention is not limited to these examples.

[0065] <Example 1> A decorative sheet 10 having the layer structure shown in FIG. 1 was produced using the following materials and procedures. (1) As the base sheet 1, a colored polyethylene film (FZ manufactured by RIKEN TECHNOS CORPORATION) was used. (2) On the surface of the base sheet 1, a picture pattern layer 2 was formed by printing a wood grain pattern using gravure ink (Lamistar (registered trademark) manufactured by Toyo Ink Mfg. Co., Ltd.) with a gravure printing machine. (3) On the back surface of the base sheet 1, a back surface resin coating layer 8 was formed by gravure printing using a two-component urethane resin containing silica powder so that the thickness after drying would be 1 μm. (4) As an adhesive layer (not shown in FIG. 1), a two-component urethane resin adhesive is applied on the picture pattern layer 2 in an amount of 2 g / m2 after drying. 2 The coating was applied so that the

[0066] (5) A maleic acid-modified polypropylene resin was used as the transparent adhesive layer 3 (thickness 10 μm). A polypropylene (manufactured by Prime Polymer Co., Ltd.) with a main component isotactic pentad fraction of 95% was used as the transparent thermoplastic resin layer 4 (thickness 80 μm). At this time, the transparent adhesive layer 3 and the transparent thermoplastic resin layer 4 were co-extruded using an extruder, and the two were laminated so that the transparent adhesive layer 3 was on the picture pattern layer 2 side.

[0067] (6) As a first surface protective layer 5, a coating liquid containing a thermosetting acrylic polyol resin (manufactured by Toyo Ink Co., Ltd.) with silica added thereto and an isocyanate-based curing agent (manufactured by Toyo Ink Co., Ltd.) was applied onto the transparent thermoplastic resin layer 4 to a thickness of 9 μm after drying. Furthermore, as the second surface protective layer 6, a coating liquid containing a mixture of ultraviolet-curable urethane acrylate resin (A: manufactured by Toyo Ink Co., Ltd.), thermosetting acrylic polyol resin (B: manufactured by Toyo Ink Co., Ltd.), isocyanate-based curing agent (C: manufactured by Toyo Ink Co., Ltd.), paraffin (D: MORESCO White (registered trademark), manufactured by MORESCO Corporation) and porous silica (E: CARPLEX (registered trademark), manufactured by EVONIK Corporation) was applied to a thickness of 6 μm after drying. Here, the mixing ratio of the above-mentioned materials (A) to (E) forming the second surface protective layer 6 was set as shown in Table 1 below. That is, in the second surface protective layer 6, 64 weight % of ultraviolet-curable urethane acrylate resin (A), 25 weight % of thermosetting acrylic polyol resin (B), 5 weight % of isocyanate-based curing agent (C), 5 weight % of paraffin (D), and 1 weight % of porous silica (E) were mixed.

[0068] (7) The thermosetting acrylic polyol resin (B) and the isocyanate-based curing agent (C) are then cured by heating at 60°C for 30 seconds, and then exposed to an ultraviolet light source (high pressure mercury lamp, 200 mJ / cm 2 ) to cure the ultraviolet-curable urethane acrylate resin (A), thereby obtaining the decorative sheet of Example 1.

[0069] <Example 2> For the second surface protective layer 6, the mixing ratio of each material was the same as in Example 1, except that the ultraviolet-curable urethane acrylate resin (A) was 66 weight %, the thermosetting acrylic polyol resin (B) was 27 weight %, and the paraffin (D) was 1 weight %, and the decorative sheet of Example 2 was obtained in the same manner as in Example 1. <Example 3> For the second surface protective layer 6, the mixing ratio of each material was the same as in Example 1, except that the ultraviolet-curable urethane acrylate resin (A) was 62 weight %, the thermosetting acrylic polyol resin (B) was 22 weight %, and the paraffin (D) was 10 weight %, and the decorative sheet of Example 2 was obtained in the same manner as in Example 1. <Example 4> For the second surface protective layer 6, the mixing ratio of each material was the same as in Example 1, except that the ultraviolet-curable urethane acrylate resin (A) was 65% by weight and no porous silica (E) was added, and the decorative sheet of Example 2 was obtained in the same manner as in Example 1. <Example 5> The mixing ratio of each material forming the second surface protective layer 6 was the same as that of Example 1, except that the thermosetting acrylic polyol resin (B) was 24% by weight and the porous silica (E) was 2% by weight, and the decorative sheet of Example 2 was obtained in the same manner as Example 1.

[0070] <Comparative Example 1> For the second surface protective layer 6, the ultraviolet-curable urethane acrylate resin (A) was 67% by weight, the thermosetting acrylic polyol resin (B) was 27% by weight, and paraffin (D) was not added. Except for this, the mixing ratio of each material was the same as in Example 1, and the decorative sheet of Comparative Example 1 was obtained using the same procedure as in Example 1. <Comparative Example 2> For the second surface protective layer 6, the mixing ratio of each material was the same as in Example 1, except that the ultraviolet-curable urethane acrylate resin (A) was 61 weight %, the thermosetting acrylic polyol resin (B) was 21 weight %, and the paraffin (D) was 12 weight %. The decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1.

[0071] <Preparation of decorative materials for evaluation> Each of the decorative sheets of Examples 1 to 5 and Comparative Examples 1 and 2 was attached to the surface of a 3 mm-thick MDF (hardwood) to prepare a decorative material for evaluation. The adhesive used for bonding was a two-part water-based emulsion adhesive (Rikabond (registered trademark) BA-10L / BA-11B = 100:2.5 manufactured by Chuo Rika Kogyo Co., Ltd.) at a wet rate of 100 g / m 2 The coated sheets were then left to cure for 24 hours to prepare the decorative material for evaluation.

[0072] <Evaluation items and evaluation methods> The decorative materials for evaluation using the decorative sheets produced according to the material configurations and procedures of Examples 1 to 5 and Comparative Examples 1 and 2 were tested and evaluated according to the following evaluation items and evaluation methods.

[0073] [Putty Wipeability Test (F)] "Tiger Putty 120 (Yoshino Gypsum Co., Ltd.)" was hand-painted onto each decorative material, and after curing for 1 hour, the surface was wiped clean with a mop that had been wrung out thoroughly, and then wiped dry. A sensory test was conducted on 10 panelists to evaluate the appearance of wiping unevenness.

[0074] The evaluation criteria are as follows: ◎: 7 to 10 people who liked it ○: 1 to 6 people who thought it was good ×: 0 people thought it was good

[0075] [Bond removal test (G)] "Nedabond (Konishi Co., Ltd.)" was applied to each cosmetic material, and after 24 hours, the material was peeled off with a metal spatula. A sensory test was conducted on 10 testers to determine the amount of force required to peel the film off.

[0076] The evaluation criteria are as follows: ◎: 7 to 10 people who said it peeled off with slight force ○: 1 to 6 people who said it peeled off with a slight force ×: 0 people who said it peeled off with slight force

[0077] [Wax adhesion test (H)] We evaluated the repelling properties of the flooring wax "All (Rinrei Co., Ltd.)" applied to the decorative material. We performed the evaluation with and without wiping the surface dry with a cloth before application.

[0078] The evaluation criteria are as follows: ◎: No bounce even if dry wiped ○: If you do not wipe dry, there is bounce, if you wipe dry, there is no bounce ×: Plays well whether or not you wipe it dry

[0079] <Evaluation Results> The evaluation results of the above tests (F), (G), and (H) are shown in Table 1.

[0080] [Table 1]

[0081] In Example 1, all of the evaluation results in the above tests (F), (G), and (H) were rated as excellent, indicating good results.

[0082] On the other hand, for the above tests (F) and (G), the decorative sheet of Example 2 (paraffin (D) content of 1% by weight) was evaluated as "○", while the decorative sheet of Comparative Example 1 (containing no paraffin (D)) was evaluated as "×". In other words, compared to Example 1 (containing paraffin (D) content of 5% by weight), the decorative sheets of Example 2 and Comparative Example 1 were evaluated as having lower results in the above tests (F) and (G). This indicates that paraffin (D) makes it easier to remove deposits such as putty and glue. In particular, since the decorative sheet of Comparative Example 1 was evaluated as having "×" in tests (F) and (G), it can be seen that when paraffin (D) is not contained in the second surface protective layer 6, there is no effect on the cleaning ability against such deposits.

[0083] In addition, in the above test (H), the decorative sheet of Example 3 (paraffin (D) content of 10% by weight) was evaluated as "○", while the decorative sheet of Comparative Example 2 (paraffin (D) content of 12% by weight) was evaluated as "×". In other words, compared to the decorative sheet of Example 1 (paraffin (D) content of 5% by weight), the decorative sheets of Example 3 and Comparative Example 2, which have paraffin (D) contents above the upper limit of the appropriate range (10% by weight in this example), were evaluated as low in the above test (H). This shows that paraffin (D) makes it easier to repel flooring wax. In particular, it can be seen that in the decorative sheet of Comparative Example 2, which contains more than 10% by weight of paraffin (D), the wax is repelled by the surface of the decorative sheet, making it impossible to apply wax.

[0084] Moreover, the decorative sheet of Example 4, which does not contain porous silica (E) in the second surface protective layer 6, was evaluated as "◎" in all of the above tests (F), (G), and (H), which was a good evaluation result similar to that of the decorative sheet of Example 1. On the other hand, the decorative sheet of Example 5, which contains more than 1 wt% of porous silica (E) (porous silica (E) content is 2 wt%), was evaluated as "○" in the above tests (F) and (G), which was a lower evaluation result compared to Examples 1 and 4. This is thought to be because the unevenness of the surface formed by the porous silica (E) caused some putty to remain unwiped and some glue to remain unpeeled.

[0085] From the above results, it has been verified that according to the present invention, it is possible to provide a decorative sheet that is easy to wipe off when cleaning and has good cleaning properties, and a decorative material using said decorative sheet. [Explanation of symbols]

[0086] 1 Base sheet 2. Pattern layer 3 Transparent adhesive layer 4 Transparent thermoplastic resin layer 5 1st surface protection layer 6 Second surface protection layer 7 Surface protective layer 8 Backside resin coating layer 10 Decorative Sheet 11 Base material 20 Cosmetic materials

Claims

1. A surface protective layer is provided on a base sheet, At least the outermost layer among the layers constituting the surface protective layer contains paraffin in an amount of 1% by weight to 10% by weight, the surface protective layer has a 60-degree specular gloss in accordance with JIS Z 8741 in the range of 5 to 35; The paraffin is liquid paraffin. A decorative sheet characterized by:

2. The 60-degree specular gloss of the surface protective layer is within a range of 5 or more and less than 20.

2. The decorative sheet according to claim 1,

3. The 60-degree specular gloss of the surface protective layer is within a range of 20 to 35.

2. The decorative sheet according to claim 1,

4. The paraffin content is 3% by weight or more and 8% by weight or less.

4. The decorative sheet according to claim 1, wherein the decorative sheet is a sheet having a thickness of 100 nm or less.

5. The paraffin has a carbon number of 15 or more and 40 or less.

5. The decorative sheet according to claim 1, wherein the decorative sheet is a laminate.

6. The surface protective layer contains a porous filler in an amount of 1% by weight or less.

6. The decorative sheet according to claim 1, wherein the decorative sheet is a sheet having a thickness of 100 nm or less.

7. The layer located on the outermost surface is mainly composed of either an ionizing radiation curable resin or a thermosetting resin, or a mixture of the ionizing radiation curable resin and the thermosetting resin.

7. The decorative sheet according to claim 1, wherein the decorative sheet is a sheet having a thickness of 100 nm or less.

8. the surface protective layer is composed of a first layer located on the base sheet side and a second layer which is the layer located on the outermost surface, The paraffin is contained in the first layer and the second layer of the surface protective layer.

8. The decorative sheet according to claim 1, wherein the decorative sheet is

9. The decorative sheet according to any one of claims 1 to 8 is used. A cosmetic material characterized by:

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