JP7600586B2 - Decorative sheets and panels - Google Patents

Description

The present invention relates to decorative sheets and decorative panels.

Traditionally, decorative sheets have been applied to the surfaces of various items, such as the walls of buildings, building materials, furniture, and electrical appliances, to add a decorative touch.

Various items such as building walls, building materials, furniture, and electrical appliances are subject to contact and rubbing by people and objects in daily life, and the decorative sheets attached to these surfaces are required to be scratch-resistant.

In addition, a surface protective layer containing a filler such as alumina is formed on the decorative sheet to impart scratch resistance, etc. A decorative material using such a decorative sheet with a surface protective layer has been proposed in which a design layer and a protective layer are formed on the surface of a substrate, and the protective layer is an abrasion-resistant decorative material made of an ionizing radiation curable resin layer containing spherical alumina and inorganic or organic spherical filler (see Patent Document 1).

However, the above-mentioned decorative materials have not been examined for their whitening resistance. When the hardness of the surface protective layer of a decorative sheet is increased to impart scratch resistance to the surface protective layer, there is a problem that when the decorative sheet is applied to a non-flat substrate such as the corners of a wall, cracks occur at the folded portion, and whitening occurs due to peeling between the resin and the spherical filler. In particular, when the decorative sheet is applied to a non-flat wall surface, the decorative sheet may be applied (tack-attached) to the wall surface using an adhesive layer provided on the back side of the decorative sheet, and the sheet may be heated with a dryer or the like to conform to the shape of the surface to be applied, and may be applied by an application method that allows the sheet to conform to the shape of the wall surface. The above-mentioned whitening due to cracks in the surface protective layer occurs in a normal temperature environment or a low temperature environment when the sheet is applied to a non-flat wall surface, and there is a problem that the whitening remains even in the decorative sheet after it is applied by conforming it to the wall surface by heating.

Therefore, there is a need to develop a decorative sheet that has excellent scratch resistance and in which the whitening that occurs on the surface can be reduced by heating the decorative sheet after application.

Japanese Patent Application Publication No. 10-286932

The present invention aims to provide a decorative sheet that has excellent scratch resistance and in which whitening on the surface can be reduced by heating the decorative sheet after application.

As a result of extensive research, the inventors have discovered that the above object can be achieved by configuring a decorative sheet having at least an adhesive layer, a base sheet, and a surface protective layer in this order, in which the surface protective layer contains a curable resin and a specific inorganic filler, and 90% or more of the inorganic filler has a particle size of 1 μm or more and less than 10 μm, thereby completing the present invention.

That is, the present invention relates to the following decorative sheet and decorative board.
1. A decorative sheet having at least a pressure-sensitive adhesive layer, a base sheet, and a surface protective layer in this order,
(1) The surface protective layer contains a curable resin and an inorganic filler,
(2) The inorganic filler is spherical alumina and another spherical inorganic filler other than alumina,
(3) The particle diameter of 90% or more of the inorganic filler particles out of any 100 particles of the inorganic filler particles, which is measured by observing a cross section of the decorative sheet cut in a direction parallel to the normal line of the surface of the decorative sheet, is 1 μm or more and less than 10 μm.
A decorative sheet characterized by:
2. The decorative sheet according to item 1, wherein the inorganic filler has a volume-based cumulative 50% particle size (D50) in a particle size distribution of 3 to 7 μm.
3. The decorative sheet according to item 1 or 2, wherein the inorganic filler has a volume-based cumulative 10% particle size (D10) in a particle size distribution of 1 to 2 μm.
4. The decorative sheet according to any one of Items 1 to 3, wherein the inorganic filler has a volume-based cumulative 90% particle size (D90) in a particle size distribution of 8 to 9 μm.
5. The decorative sheet according to any one of items 1 to 4, wherein the surface protective layer contains a deodorant.
Item 6. The decorative sheet according to item 5, wherein the deodorant is an amorphous filler, and the amorphous filler is at least one selected from the group consisting of silica, a simple metal salt, a complex of a metal salt, and a zeolite.
7. The decorative sheet according to item 5 or 6, wherein the average particle size of the deodorant is less than 1 μm.
8. The decorative sheet according to any one of items 1 to 7, wherein the curable resin contains a copolymer of vinyl chloride resin and vinyl acetate resin, and an acrylic polyol.
9. The decorative sheet according to item 8, wherein the curable resin contains 30% by mass or more of vinyl chloride resin units.
10. The decorative sheet according to any one of items 1 to 9, wherein the surface protective layer has a thickness of 3 to 10 μm.
11. The decorative sheet according to any one of items 1 to 10, wherein the base sheet contains 70% by mass or more of a polyvinyl chloride resin.
12. The decorative sheet according to any one of items 1 to 11, wherein the surface protective layer contains an antiviral agent.
13. The decorative sheet according to any one of items 1 to 12, wherein the pressure-sensitive adhesive layer contains an acrylic resin.
14. The decorative sheet according to any one of items 1 to 13, which is a decorative sheet for wall materials.
15. A decorative board having the decorative sheet according to any one of items 1 to 14 on a substrate.

The decorative sheet of the present invention has excellent scratch resistance, and the whitening that occurs on the surface is reduced by heating the decorative sheet after application.

FIG. 1 is a schematic diagram showing an example of the layer structure of a decorative sheet of the present invention. FIG. 1 is a schematic diagram showing an example of the layer structure of a decorative sheet of the present invention. FIG. 2 is a schematic diagram showing an example of a layer structure of the decorative board of the present invention.

The decorative sheet and decorative board of the present invention will be described in detail below. In the decorative sheet of the present invention, the side of the decorative sheet opposite to the side laminated with the substrate is the so-called "front side", which is the side that is visible when applied to a wall surface, the surface of an object, etc. Therefore, in this specification, the direction of the side of the decorative sheet opposite to the side laminated with the substrate is referred to as "top", and the direction of the opposite side, i.e., the side laminated with the substrate, is referred to as "back" or "bottom". Similarly, in this specification, the direction of the side of the decorative board facing the decorative sheet is referred to as "top", and the direction of the opposite side, i.e., the side facing the substrate, is referred to as "back" or "bottom".

In addition, in this specification, normal temperature means 23°C, and low temperature means 5°C or lower.

The decorative sheet of the present invention is a decorative sheet having at least a pressure-sensitive adhesive layer, a base sheet, and a surface protective layer in this order, characterized in that (1) the surface protective layer contains a curable resin and an inorganic filler, (2) the inorganic filler is spherical alumina and other spherical inorganic fillers other than alumina, and (3) the particle diameter of 90% or more of the inorganic fillers out of any 100 particle diameters of the inorganic fillers measured by observing a cross section of the decorative sheet cut in a direction parallel to the normal to the surface of the decorative sheet is 1 μm or more and less than 10 μm.

The decorative sheet of the present invention having the above characteristics has excellent scratch resistance because (1) the surface protective layer contains a curable resin and an inorganic filler, and (2) the inorganic filler is spherical alumina and other spherical inorganic fillers other than alumina. The decorative sheet of the present invention also has (2) the inorganic filler is spherical alumina and other spherical inorganic fillers other than alumina, and (3) the particle diameter of 90% or more of any 100 particles of the inorganic filler measured by observing a cross section of the decorative sheet cut in a direction parallel to the normal to the surface of the decorative sheet is 1 μm or more and less than 10 μm, so that the decorative sheet contains the above two specific types of inorganic fillers, and the particle diameters of these inorganic fillers are within a specific range and are uniform. Therefore, even if whitening occurs due to peeling between the curable resin and the inorganic filler in the surface protection layer or cracking of the curable resin when applied to a non-flat wall surface at room temperature or in a low temperature environment, the curable resin expands easily when heated, making it easier to close gaps caused by the peeling or cracking, and whitening caused by application is reduced by heating.

In other words, the decorative sheet of the present invention has at least an adhesive layer, a base sheet, and a surface protection layer in this order, and by combining the above-mentioned configurations (1), (2), and (3), it has excellent scratch resistance and the whitening that occurs on the surface is reduced by heating.

The decorative sheet of the present invention is a decorative sheet having at least an adhesive layer, a base sheet, and a surface protective layer in this order, and is not limited in terms of layer structure, so long as it has the above-mentioned structures (1) to (3). An example of the layer structure of the decorative sheet of the present invention is, for example, a layer structure having an adhesive layer 11, a base sheet 12, a picture pattern layer 13 (solid ink layer and/or pattern ink layer), an adhesive layer (not shown), a transparent resin layer 14, and a surface protective layer 15 in this order, as shown in FIG. 1 (a doubling-type decorative sheet). Also, as shown in FIG. 2, the decorative sheet of the present invention is, for example, a layer structure having a release layer 17, an adhesive layer 11, a base sheet 12, a picture pattern layer 13 (solid ink layer and/or pattern ink layer), an adhesive layer (not shown), a transparent resin layer 14, and a surface protective layer 15 in this order. A decorative sheet having such a layer structure will be specifically described below as a representative example.

(Surface protection layer)
The surface protective layer (transparent surface protective layer) is provided to impart surface properties required for the decorative sheet, such as scratch resistance, abrasion resistance, water resistance, stain resistance, etc. The surface protective layer contains a curable resin and an inorganic filler.

<Curing Resin>
The surface protective layer contains a curable resin, such as a thermosetting resin or an ionizing radiation curable resin.

Examples of thermosetting resins include polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyacrylic resin, ester-acrylic copolymer, epoxy resin, aminoalkyd resin, phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, melamine-urea co-condensation resin, silicon resin, polysiloxane resin, etc. Among these, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, and vinyl chloride-vinyl acetate copolymer are preferred, with vinyl chloride-vinyl acetate copolymer being more preferred, in that they have even better adhesion between the curable resin and the substrate sheet.

The thermosetting resin may be used alone or in a mixture of two or more kinds. In terms of even better weather resistance, it is preferable to use a mixture of a copolymer of vinyl chloride resin and vinyl acetate resin (vinyl chloride-vinyl acetate copolymer) and an acrylic polyol. When a mixture of a copolymer of vinyl chloride resin and vinyl acetate resin and an acrylic polyol is used, the curable resin can be prepared by first preparing a mixed resin containing a copolymer of vinyl chloride resin and vinyl acetate resin and a polyol component such as an acrylic polyol. In other words, it is preferable that the curable resin is configured to contain a copolymer of vinyl chloride resin and vinyl acetate resin and an acrylic polyol. By adding an isocyanate component to the mixed resin and preparing the curable resin again, the liquid stability of the mixed resin is excellent, making it even easier to form a surface protective layer.

When the curable resin contains a copolymer of vinyl chloride resin and vinyl acetate resin (vinyl chloride-vinyl acetate copolymer) and an acrylic polyol, the curable resin preferably contains 20% by mass or more of vinyl chloride resin units, and more preferably 30% by mass or more. By containing vinyl chloride resin units in the above range, the abrasion resistance of the surface protective layer is further improved.

The above-mentioned thermosetting resin, which is a curable resin, can be added with a curing agent such as a crosslinking agent or a polymerization initiator, or a polymerization accelerator. For example, curing agents such as isocyanate and organic sulfonate can be added to unsaturated polyester resins and polyurethane resins, organic amines can be added to epoxy resins, and peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutylnitrile can be added to unsaturated polyester resins.

The ionizing radiation curable resin is not limited as long as it undergoes a crosslinking polymerization reaction upon irradiation with ionizing radiation and changes into a three-dimensional polymer structure. For example, one or more prepolymers, oligomers, and monomers having polymerizable unsaturated bonds or epoxy groups in the molecule that can be crosslinked upon irradiation with ionizing radiation can be used. Examples include acrylate resins such as urethane acrylate, polyester acrylate, and epoxy acrylate; silicon resins such as siloxane; polyester resins; and epoxy resins.

Ionizing radiation includes visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-rays, electron beams, ion beams, etc., of which ultraviolet light and electron beams are preferred, with electron beams being more preferred.

Ultraviolet light sources that can be used include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, and metal halide lamps. The wavelength of ultraviolet light is approximately 190 to 380 nm.

As the electron beam source, various electron beam accelerators such as Cockcroft-Wald type, Van de Graff type, resonant transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type, etc. can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The dose of the electron beam is preferably about 2 to 15 Mrad.

Ionizing radiation curable resins are sufficiently cured when irradiated with electron beams, but if they are cured by irradiating with ultraviolet light, it is preferable to add a photopolymerization initiator (sensitizer).

In the case of a resin system having a radically polymerizable unsaturated group, the photopolymerization initiator may be, for example, at least one of acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler's benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide, diethyl oxide, triphenyl biimidazole, isopropyl-N,N-dimethylaminobenzoate, etc. In the case of a resin system having a cationic polymerizable functional group, for example, at least one of aromatic diazonium salts, aromatic sulfonium salts, metallocene compounds, benzoin sulfonate esters, furyloxysulfoxonium diallyliodosyl salts, etc. may be used.

The amount of photopolymerization initiator added is not particularly limited, but is generally about 0.1 to 10 parts by mass per 100 parts by mass of ionizing radiation curable resin.

<Inorganic filler>
The surface protective layer contains an inorganic filler. In the present invention, the inorganic filler contained in the surface protective layer is spherical alumina and other spherical inorganic fillers other than alumina.

The surface protective layer may also contain an amorphous inorganic filler, but from the viewpoint of more easily exerting the effect of the present invention, that is, the whitening that occurs on the surface is reduced by heating the decorative sheet after application, it is preferable that the surface protective layer does not substantially contain an amorphous inorganic filler. Note that, "substantially does not contain" means that the content of the amorphous inorganic filler in the surface protective layer is 10 parts by mass or less, preferably 5 parts by mass or less, and more preferably 0 parts by mass, based on 100 parts by mass of the curable resin.

In this specification, the amorphous inorganic filler is an amorphous inorganic filler having an average particle size of 1 μm or more, and is distinguished from the deodorant described below in that the average particle size of the deodorant is less than 1 μm.

In the decorative sheet of the present invention, the particle diameters of any 100 inorganic fillers measured by observing a cross section of the decorative sheet cut in a direction parallel to the normal to the surface of the decorative sheet are 90% or more. If the inorganic fillers have particle diameters of 1 μm or more and less than 10 μm, less than 90%, whitening caused by gaps between the curable resin and the inorganic filler that occur when the decorative sheet is folded is not reduced by heating. The inorganic fillers having particle diameters of 1 μm or more and less than 10 μm are preferably 92% or more, more preferably 95% or more. In addition, the upper limit of the proportion of inorganic fillers having particle diameters of 1 μm or more and less than 10 μm is not particularly limited, and may be 100% or less.

The method for measuring the particle size of the inorganic filler and the method for calculating the proportion of inorganic fillers with a particle size of 1 μm or more and less than 10 μm are as follows. That is, the decorative sheet is cut in a direction parallel to the normal line of the surface of the decorative sheet. Next, an optical microscope (manufactured by KEYENCE Co., Ltd., product name: VHX-5000) is used to adjust the magnification to 1000 times, at which the inorganic filler can be visually confirmed. The cross section of the decorative sheet is observed with the optical microscope, and the particle size is measured while counting the number of inorganic fillers observed. This operation is repeated until the number of inorganic fillers observed reaches 100. Of the measured particle sizes of the 100 inorganic fillers, the number of inorganic fillers with a particle size of 1 μm or more and less than 10 μm is counted, and the proportion of the number of inorganic fillers with a particle size of 1 μm or more and less than 10 μm out of the 100 is calculated. In the above calculation method, the deodorant described later is not measured and is not taken into consideration. The inorganic filler and the deodorant can be distinguished from each other by the fact that the deodorant is an amorphous filler with an average particle size of less than 1 μm.

The average particle size of the inorganic filler is preferably 1 to 10 μm, more preferably 2 to 7 μm, and even more preferably 3 to 5 μm. By having the average particle size of the inorganic filler within the above range, the decorative sheet of the present invention has even better scratch resistance, and whitening on the surface is further reduced by heating the decorative sheet after application.

In this specification, the average particle size of the inorganic filler is a value measured by the following measurement method. That is, the decorative sheet is cut in a direction parallel to the normal line of the surface of the decorative sheet. Next, an optical microscope (manufactured by KEYENCE Co., Ltd., product name: VHX-5000) is used to adjust the magnification to 1000 times, at which the inorganic filler can be visually confirmed. The cross section of the decorative sheet is observed with the optical microscope, and the particle size is measured while counting the number of inorganic fillers observed. This operation is repeated until the number of inorganic fillers observed reaches 100. The average particle size of the measured 100 inorganic fillers is taken as the average particle size. Note that in the above method for measuring the average particle size of the inorganic filler, the deodorant described below is not measured and is not taken into consideration. The inorganic filler and the deodorant can be distinguished from each other by the fact that the deodorant is an irregular filler with an average particle size of less than 1 μm.

There are no particular limitations on the alumina as long as it is spherical, and any conventionally known alumina that can impart abrasion resistance to the decorative sheet can be used. Examples of such alumina include α-alumina, γ-alumina, θ-alumina, and δ-alumina.

The average particle size of the alumina is preferably 1 to 10 μm, more preferably 2 to 7 μm, and even more preferably 3 to 5 μm. By having the average particle size of the alumina in the above range, it becomes easier to adjust the particle size of the inorganic filler to 1 μm or more and less than 10 μm by the above measurement method. In addition, by having the average particle size of the alumina in the above range, when the surface protective layer contains a deodorant, as described below, it becomes even clearer to distinguish it from the deodorant, which is an amorphous filler with an average particle size of less than 1 μm.

Commercially available alumina can be used.

The content of alumina in the surface protective layer is preferably 5 to 20 parts by mass, more preferably 7 to 15 parts by mass, and even more preferably 10 to 13 parts by mass, based on 100 parts by mass of the curable resin. By having the alumina content within the above range, the abrasion resistance of the decorative sheet is further improved.

The spherical inorganic fillers other than alumina are not particularly limited as long as they are spherical, and any conventionally known inorganic fillers capable of imparting abrasion resistance to the decorative sheet can be used. Examples of such inorganic fillers include silica, silicon carbide, calcium titanate, barium titanate, magnesium pyroborate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, emerythritol, and glass fiber. Among these, silica is preferred because of its even superior abrasion resistance.

The average particle size of the spherical inorganic filler other than alumina is preferably 1 to 10 μm, more preferably 2 to 7 μm, and even more preferably 3 to 5 μm. By having the average particle size of the spherical inorganic filler other than alumina in the above range, it becomes easier to adjust the particle size of the inorganic filler to 1 μm or more and less than 10 μm by the above measurement method. In addition, by having the average particle size of the spherical inorganic filler other than alumina in the above range, when the surface protective layer contains a deodorant, as described below, it becomes even clearer to distinguish it from the deodorant, which is an amorphous filler with an average particle size of less than 1 μm.

The content of the spherical inorganic filler other than alumina in the surface protective layer is preferably 1 to 20 parts by mass, more preferably 5 to 15 parts by mass, and even more preferably 7 to 13 parts by mass, based on 100 parts by mass of the curable resin. By having the content of the spherical inorganic filler other than alumina in the above range, the abrasion resistance of the decorative sheet is further improved.

The inorganic filler (spherical alumina and other spherical inorganic fillers other than alumina) preferably has a volume-based cumulative 50% particle size (D50) in the particle size distribution of 3 to 7 μm, more preferably 4 to 6 μm. By having the volume-based cumulative 50% particle size (D50) of the inorganic filler in the above range, the whitening that occurs on the surface of the decorative sheet of the present invention is further reduced by heating.

The inorganic filler (spherical alumina and other spherical inorganic fillers other than alumina) preferably has a volume-based cumulative 10% particle size (D10) in the particle size distribution of 1 to 2.5 μm, more preferably 1 to 2 μm. By having the volume-based cumulative 10% particle size (D10) of the inorganic filler in the above range, the whitening that occurs on the surface of the decorative sheet of the present invention is further reduced by heating.

The inorganic filler (spherical alumina and other spherical inorganic fillers other than alumina) preferably has a volume-based cumulative 90% particle size (D90) in the particle size distribution of 7.5 to 9 μm, more preferably 8 to 9 μm. By having the volume-based cumulative 90% particle size (D90) of the inorganic filler in the above range, the whitening that occurs on the surface of the decorative sheet of the present invention is further reduced by heating.

The volume-based cumulative particle size in the particle size distribution of the inorganic filler is the volume-based cumulative particle size in the particle size distribution measured by a laser diffraction scattering method.

Examples of methods for forming the surface protective layer include coating a surface protective layer-forming composition containing a curable resin and an inorganic filler using a coating method such as gravure reverse coating, roll coating, or gravure coating, followed by drying and curing.

The thickness of the surface protective layer is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 3.5 μm or more. The thickness of the surface protective layer is preferably 50 μm or less, more preferably 20 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. By setting the lower limit of the thickness of the surface protective layer within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved. By setting the upper limit of the thickness of the surface protective layer within the above range, the abrasion resistance is further improved. The thickness of the surface protective layer is preferably 3 to 10 μm.

The surface protective layer may contain additives as necessary. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, UV absorbers, light stabilizers, deodorants, antibacterial agents, antiviral agents, antiallergen agents, and antifungal agents.

The surface protective layer preferably contains an antiviral agent. Antiviral agents can generally be broadly divided into organic and inorganic types. Examples of organic antiviral agents include quaternary ammonium salt-based, quaternary phosphonium salt-based, pyridine-based, pyrithione-based, benzimidazole-based, organic iodine-based, isothiazolin-based, and anion-based antiviral agents. Examples of inorganic antiviral agents include antiviral agents in which metal ions such as silver, copper, and zinc are supported on zeolite, apatite, zirconia, glass, and the like.

Among the above organic antiviral agents, benzimidazole antiviral agents or anionic antiviral agents, which are antiviral agents that maintain a particle shape, are preferably used. The antiviral agent maintains a particle shape means that the antiviral agent does not dissolve in the composition for forming the surface protective layer (ink before curing) and exists in the form of particles in the cured surface protective layer. For this reason, in the process of forming the surface protective layer, the particles of the antiviral agent tend to float up, making it easier to unevenly distribute the particles of the antiviral agent on the outermost surface side of the surface protective layer. By unevenly distributing the particles of the antiviral agent on the outermost surface side of the surface protective layer, it is possible to reduce the amount of antiviral agent added that is necessary to obtain a predetermined antiviral property, and therefore it is easier to suppress a decrease in the scratch resistance of the surface protective layer.

The above-mentioned anionic antiviral agents preferably contain, for example, a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound. In addition, the above-mentioned styrene polymer derivative compound and unsaturated carboxylic acid derivative compound preferably contain at least one of the structures of styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably contain all of these structures. This is because there are two types of viruses, enveloped and unenveloped, and it is believed that the structures of antiviral agents that can effectively inhibit the activity of each type are different.

As the inorganic antiviral agent, a silver-based antiviral agent is preferred from the viewpoint of lack of biotoxicity and excellent safety, and among them, a phosphate glass-supported silver compound or a silver zeolite compound is more preferred because it exerts antiviral properties even in small amounts, and therefore the amount added can be reduced.

The above antiviral agents may be used alone or in combination of two or more.

In this specification, the deodorant is an amorphous filler having an average particle diameter of less than 1 μm. The amorphous filler is not particularly limited as long as it has an average particle diameter of less than 1 μm, is amorphous, and can exert a deodorant effect, and examples of the amorphous filler include silica, simple metal salts, metal salt composites, and zeolites. The amorphous filler formed from the above substances has an average particle diameter of less than 1 μm and is amorphous, so that it has a large surface area and can adsorb odor-causing substances in recesses and micropores, and can fully exert its function as a deodorant.

An example of a simple metal salt is zinc oxide. An example of a composite metal salt is a compound in which an organic substance such as an amine is supported on an inorganic substance such as zinc.

As the zeolite, it is preferable to use a zeolite obtained by calcining a metal salt complex, that is, the zeolite is preferably a zeolite obtained by calcining a metal salt complex. As the metal salt complex, the above-mentioned metal salt complexes can be used.

Examples of amorphous fillers capable of exerting a deodorizing effect include those that exhibit a reduction rate of 90% or more in the deodorizing property test described below.
Deodorizing test
0.1 g of the sample is placed in a bag made of polyvinyl fluoride film (hereinafter referred to as a Tedlar bag) at room temperature (23°C), and 3 L of ammonia gas (initial concentration 100 ppm) is poured in. The remaining gas concentration in the Tedlar bag after standing for 24 hours is measured with a gas detector. The ratio of the remaining gas concentration after 24 hours to the initial ammonia gas concentration is calculated and used as the reduction rate.

The average particle size of the deodorant is less than 1 μm, preferably 0.5 μm or less, and more preferably 0.3 μm or less. By setting the upper limit of the average particle size of the deodorant within the above range, the decorative sheet of the present invention has excellent scratch resistance, and the whitening on the surface can be reduced by heating the decorative sheet after application, while the deodorant function can be further enhanced. In addition, the lower limit of the average particle size of the deodorant is not particularly limited, and is, for example, 0.05 μm, 0.01 μm, etc.

In addition, since the average particle size of the deodorant is less than 1 μm, it is easy to distinguish from the inorganic filler contained in the surface protective layer of the decorative sheet of the present invention during measurement, and is unlikely to be confused with it.

In this specification, the average particle size of the deodorant is a value measured by the following measurement method. That is, the decorative sheet is cut in a direction parallel to the normal line of the surface of the decorative sheet. Next, a scanning electron microscope (Hitachi High-Technologies Corporation, product name: S-4800 type field emission scanning electron microscope) is used to adjust the magnification to 20,000 times, at which the deodorant can be confirmed. The cross section of the decorative sheet is observed with the scanning electron microscope, and the particle size is measured while counting the number of deodorant particles observed. This operation is repeated until the number of deodorant particles observed reaches 100. The average particle size of the measured 100 deodorant particles is taken as the average particle size. Note that in the measurement method of the average particle size of the deodorant, the inorganic filler described above is not measured and is not taken into consideration. The inorganic filler and the deodorant can be distinguished from each other by the fact that the inorganic filler is spherical and the deodorant is an amorphous filler.

The volume-based cumulative 50% particle size (D50) in the particle size distribution of the deodorant is preferably 0.03 to 0.5 μm, more preferably 0.05 to 0.3 μm, and even more preferably 0.08 to 0.2 μm. By being in the above range, the decorative sheet of the present invention has excellent scratch resistance, and the whitening that occurs on the surface can be reduced by heating the decorative sheet after application, while also exhibiting a deodorant function.

The volume-based cumulative 10% particle size (D10) in the particle size distribution of the deodorant is preferably 0.01 to 0.04 μm, and more preferably 0.01 to 0.03 μm. By being in the above range, the decorative sheet of the present invention has excellent scratch resistance, and whitening on the surface can be reduced by heating the decorative sheet after application, while the deodorant function can be further exerted.

The volume-based cumulative 90% particle size (D90) in the particle size distribution of the deodorant is preferably 0.6 to 1.0 μm, and more preferably 0.7 to 0.9 μm. By being in the above range, the decorative sheet of the present invention has excellent scratch resistance, and the whitening that occurs on the surface can be reduced by heating the decorative sheet after application, while also exhibiting a deodorant function.

The volume-based cumulative particle size in the particle size distribution of the above deodorant is the volume-based cumulative particle size in the particle size distribution measured by a laser diffraction scattering method.

In this specification, the thickness of the surface protective layer is measured at a location other than the protruding particles 16 when the particles 16 protrude from the surface of the surface protective layer, as shown as ts in Figures 1 and 2. Also, when a concave-convex pattern is formed on the decorative sheet by embossing as in Figures 1 and 2, the thickness of the surface protective layer is measured at a location other than the concave-convex pattern.

(Base sheet)
As the base sheet, a synthetic resin sheet such as polyvinyl chloride resin, polyolefin resin, polyester resin, polyacrylic resin, polyamide resin, polyurethane resin, polystyrene resin, etc. may be used. As the base sheet, a synthetic resin sheet consisting of one of the above resins alone may be used, or a synthetic resin sheet formed by mixing two or more of the above resins may be used. Among these, a synthetic resin sheet containing polyvinyl chloride resin is preferred.

When the base sheet contains polyvinyl chloride resin, the content of polyvinyl chloride resin is preferably 60% by mass or more, and more preferably 70% by mass or more, based on 100% by mass of the base sheet. By setting the lower limit of the polyvinyl chloride resin content within the above range, the scratch resistance of the decorative sheet of the present invention is further improved.

As the polyolefin-based resin, a polyolefin-based thermoplastic resin can be used, and examples thereof include polyethylene, ethylene-α-olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, etc. Among these, polypropylene is preferred.

Examples of polyester resins include polyethylene terephthalate, highly heat-resistant polyalkylene terephthalate (for example, polyethylene terephthalate in which part of the ethylene glycol has been replaced with 1,4-cyclohexanedimethanol or diethylene glycol, known as PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, and polyethylene naphthalate-isophthalate copolymers. Among these, highly heat-resistant polyalkylene terephthalate is preferred.

The thickness of the substrate sheet is preferably 20 to 300 μm, and more preferably 40 to 200 μm. The substrate sheet may be colored as necessary. In addition, the surface may be subjected to a surface treatment such as corona discharge treatment, plasma treatment, or ozone treatment, or may be coated with a primer, which is a base paint, to improve adhesion with adjacent layers.

(Adhesive Layer)
The pressure-sensitive adhesive layer is provided on the back surface of the base sheet in order to impart adhesiveness to the decorative sheet.

The resin for forming the adhesive layer is not particularly limited as long as it can exhibit adhesiveness, and examples include acrylic resins, urethane resins, etc. Among these, it is preferable to contain an acrylic resin, since this can impart even higher adhesiveness to the decorative sheet.

The thickness of the adhesive layer is preferably 10 to 100 μm, more preferably 30 to 70 μm, and even more preferably 40 to 50 μm. By having the thickness of the adhesive layer within the above range, the adhesion between the decorative sheet and the substrate or adherend is further improved.

(Pattern layer)
The picture pattern layer is composed of a pattern ink layer and/or a solid ink layer. The picture pattern layer can be formed by a printing method such as gravure printing, offset printing, silk screen printing, etc. Examples of the pattern of the pattern ink layer include wood grain patterns, stone grain patterns, fabric patterns, leather patterns, geometric patterns, letters, symbols, line drawings, various abstract patterns, etc. The solid ink layer is obtained by solid printing of colored inks. The picture pattern layer is composed of one or both of a pattern ink layer and a solid ink layer.

The ink used for the picture pattern layer may be a mixture of one or more of the following vehicles: chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane made of isocyanate and polyol, polyacrylic, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin, etc., to which pigments, solvents, various auxiliary agents, etc. are added to make an ink. Among these, from the viewpoints of environmental issues and adhesion to the printed surface, etc., a mixture of one or more of polyester, polyurethane made of isocyanate and polyol, polyacrylic, polyamide resin, curable resin containing acrylic urethane resin, etc. is preferred, with curable resin containing acrylic urethane resin being more preferred.

(Transparent Adhesive Layer)
The transparent adhesive layer is provided between the picture pattern layer and the transparent resin layer as required. The transparent adhesive layer can be obtained, for example, by applying and drying a known adhesive for dry lamination, such as a two-component curing urethane resin.

The thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 μm, and more preferably about 1 to 5 μm.

(Transparent Resin Layer)
The transparent resin layer is not particularly limited as long as it is a transparent resin layer, and can be suitably formed from, for example, a transparent thermoplastic resin.

Specific examples of such synthetic resins include soft, semi-rigid or rigid polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ionomer, acrylic acid ester, methacrylic acid ester, etc. Among the above, polyolefin resins such as polyvinyl chloride resin and polypropylene are preferred, and polyvinyl chloride resin is more preferred.

The transparent resin layer may be colored. In this case, a colorant may be added to the thermoplastic resin. The colorant may be the same pigment or dye used in the design layer.

The transparent resin layer may contain various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, light stabilizers, radical scavengers, and soft components (e.g., rubber).

The thickness of the transparent resin layer is preferably 50 μm or more, more preferably 60 μm or more, and more preferably 80 μm or more. The thickness of the transparent resin layer is preferably 300 μm or less, and more preferably 200 μm or less.

The surface of the transparent resin layer may be subjected to a surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, or dichromate treatment, if necessary. The surface treatment may be performed according to the usual method for each treatment.

A primer layer (a primer layer to facilitate the formation of a surface protective layer) may be formed on the surface of the transparent resin layer.

The primer layer can be formed by applying a known primer agent to the transparent resin layer. Examples of primer agents include urethane resin-based primer agents made of acrylic-modified urethane resins, and resin-based primer agents made of block copolymers of acrylic and urethane.

The thickness of the primer layer is not particularly limited, but is usually about 0.1 to 10 μm, and preferably about 1 to 5 μm.

(Release Layer)
The decorative sheet of the present invention may have a release layer laminated on the back surface of the pressure-sensitive adhesive layer.

The release layer is not particularly limited as long as it can cover the adhesive layer and exhibit releasability, and examples of the release layer include release paper; release sheets containing silicone resins, etc.

The thickness of the release layer is not particularly limited, but is usually about 50 to 200 μm, and preferably about 100 to 150 μm.

The layers described above can be laminated, for example, by forming a picture pattern layer (solid ink layer, pattern ink layer) on one side of a base sheet by printing, laminating a transparent resin layer on the picture pattern layer via a known dry lamination adhesive such as a two-component curing urethane resin by dry lamination method, T-die extrusion method, or the like, forming a surface protection layer, applying a resin for forming an adhesive layer to the back side of the base sheet and drying it to form an adhesive layer, and laminating a release layer on the adhesive layer.

The total thickness of the decorative sheet (excluding the release layer) is preferably 160 μm or more, and more preferably 200 μm or more. The total thickness of the decorative sheet is preferably 250 μm or less, more preferably 230 μm or less, and even more preferably 210 μm or less. By setting the lower limit of the total thickness of the decorative sheet within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved. By setting the upper limit of the total thickness of the decorative sheet within the above range, the whitening resistance of the decorative sheet is further improved.

In this specification, the total thickness of the decorative sheet is measured at the surface of the decorative sheet other than the exposed fine particles 16 when the fine particles 16 protrude from the surface of the surface protection layer as shown as td in Figures 1 and 2. Also, when a concave-convex pattern is formed on the decorative sheet by embossing as shown in Figures 1 and 2, the total thickness of the decorative sheet is measured at the surface other than the concave-convex pattern.

The decorative sheet may be embossed from the surface protection layer side (upper side of the decorative sheet) to form a concave-convex pattern. The concave-convex pattern can be formed by heat pressing, hairline processing, etc. Examples of the concave-convex pattern include vessel grooves, uneven stone slab surface, cloth surface texture, matte finish, sand grain, hairline, and stripe grooves.

In this specification, the thickness of each layer of the decorative sheet is measured at a location where the uneven pattern is not formed.

It is preferable that the various additives (spherical alumina contained in the surface protective layer, other spherical inorganic fillers other than alumina, deodorants, etc.) added to each of the above-mentioned layers of the decorative sheet of the present invention are vesiculated. The method for vesiculating the various additives is not particularly limited, and they can be vesiculated by known methods, among which supercritical reverse phase evaporation is preferred.

The supercritical reverse phase evaporation method is described in detail below. The supercritical reverse phase evaporation method is a method in which a mixture in which a substance forming the outer membrane of a vesicle is uniformly dissolved in carbon dioxide in a supercritical state or at a temperature or pressure condition above the supercritical point is added with an aqueous phase containing various additives as water-soluble or hydrophilic encapsulation substances to form a capsule-like vesicle containing various additives as encapsulation substances in a single layer of membrane. Note that carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at or above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa), and carbon dioxide under a temperature or pressure condition above the critical point means carbon dioxide under conditions in which only the critical temperature or only the critical pressure exceeds the critical condition. This method can obtain unilamellar vesicles with a diameter of 50 to 800 nm. In general, a vesicle is a general term for a small vesicle with a spherical, closed membrane structure that contains a liquid phase inside, and in particular, a liposome is one whose outer membrane is composed of biological lipids such as phospholipids.

The above phospholipids include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, yolk egg lecithin, hydrogenated yolk egg lecithin, soybean lecithin, and hydrogenated soybean lecithin, and sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

The substance that constitutes the outer membrane can also be a dispersant such as a nonionic surfactant or a mixture of a nonionic surfactant with cholesterol or triacylglycerol.

As the nonionic surfactant, one or more of the following can be used: polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly 2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc.

As the cholesterols, one or more of the following can be used: cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadiene-3β-ol), sodium cholate, cholecalciferol, etc.

The outer membrane of the liposome may be formed from a mixture of phospholipids and a dispersing agent. In the decorative sheet of the present invention, by using a liposome having an outer membrane formed from phospholipids, it is possible to improve the compatibility between the resin composition, which is the main component of each layer, and various additives.

The decorative sheet of the present invention has the above-mentioned configuration, and therefore has excellent scratch resistance, and the whitening that occurs on the surface is reduced by heating. This allows it to be applied suitably to non-flat substrates such as wall surfaces. For this reason, the decorative sheet of the present invention can be suitably used as a decorative sheet for interior materials, in particular as a decorative sheet for wall materials.

2. Decorative Board The decorative board of the present invention is a decorative board having the above-mentioned decorative sheet on a substrate.

(decorative sheet)
As the decorative sheet constituting the decorative board of the present invention, the decorative sheet of the present invention explained above can be used.

(Substrate)
The material of the substrate is not particularly limited, and examples thereof include wood boards and hot-dip galvanized steel sheets that are commonly used for decorative panels.

The thickness of the substrate is not particularly limited, but is preferably 0.1 to 1.0 mm, and more preferably 0.3 to 0.7 mm.

There are no particular limitations on the method for laminating the decorative sheet onto the front surface of the substrate, and the laminate can be laminated by a conventionally known method, such as laminating the front surface of the substrate and the adhesive layer of the decorative sheet, followed by curing.

The decorative board of the present invention has the above-mentioned configuration, and therefore has excellent scratch resistance, and whitening on the surface is reduced by heating. Furthermore, even if whitening occurs due to folding the substrate after laminating the decorative sheet on the substrate, the whitening is reduced by heating the decorative sheet on the substrate. For this reason, the decorative board of the present invention can be suitably used as a decorative board for interior materials, in particular as a decorative board for wall materials.

The present invention will be described in more detail below with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
(Manufacturing of decorative sheets)
A colored polyvinyl chloride film having a thickness of 80 μm was prepared as the substrate sheet. Next, an acrylic urethane resin-containing printing ink, which is a printing ink for polyvinyl chloride film, was applied to the front surface of the substrate sheet to a thickness of 2 μm by gravure printing to form a picture pattern layer. A transparent polyvinyl chloride resin sheet having a thickness of 80 μm was laminated on the picture pattern layer by a thermal lamination method as a transparent resin layer, and an embossed shape was formed from the front surface of the transparent resin layer. Next, a surface protection layer forming composition prepared as follows was applied to the front surface of the transparent resin layer by a gravure reverse method, and the composition was dried by air drying with a dryer and heated with hot air to harden, forming a surface protection layer having a thickness of 3.8 μm.

(Composition for forming surface protective layer)
The following components were mixed together to prepare a resin mixture.
Copolymer of vinyl chloride resin and vinyl acetate resin: 100 parts by mass Acrylic polyol: 300 parts by mass The following acrylic polyol was added to 100 parts by mass of the above mixed resin to prepare a resin component.
Isocyanate: 10 parts by mass The resin component prepared as described above was mixed with the inorganic filler shown below to prepare a composition for forming a surface protective layer having the following composition.
Resin component: 100 parts by weight Inorganic filler Spherical alumina: 12 parts by weight (average particle size 5 μm)
Spherical silica: 5 parts by mass (average particle size 5 μm)
The inorganic filler has a volume-based cumulative 50% particle size (D50) of 5 μm, a volume-based cumulative 10% particle size (D10) of 1 μm, and a volume-based cumulative 90% particle size (D10) of 1 μm in the particle size distribution measured by a laser diffraction scattering method. The diameter (D90) was 9 μm.

Next, an acrylic resin was applied to the back surface of the base sheet using a comma coater method to a thickness of 45 μm, and then dried to form an adhesive layer. Next, a release paper having a thickness of 125 μm was laminated onto the adhesive layer to form a release layer, and a decorative sheet was manufactured. When the particle diameter of the inorganic filler was measured using the measurement method described below, the particle diameter of 90% of the inorganic filler was 1 μm or more and less than 10 μm.

The total thickness of the decorative sheet in Example 1 (excluding the release paper) was 200 μm.

(Manufacturing of decorative panels)
A hot-dip galvanized steel sheet having a thickness of 0.5 mm was prepared as a substrate. The adhesive layer of the decorative sheet was bonded to the substrate to produce a decorative sheet.

Example 2
Decorative sheets and decorative panels were manufactured in the same manner as in Example 1, except that the inorganic fillers listed below were used and the particle diameter of 95% of the inorganic fillers was adjusted to be 1 μm or more and less than 10 μm.
Inorganic filler: spherical alumina: 12 parts by mass (average particle size: 3 μm)
Spherical silica: 5 parts by mass (average particle size 3 μm)

Example 3
Decorative sheets and decorative panels were manufactured in the same manner as in Example 1, except that the inorganic fillers and deodorants listed below were used and the particle diameter of 90% of the inorganic fillers was adjusted to be 1 μm or more and less than 10 μm.
Inorganic filler: spherical alumina: 12 parts by mass (average particle size: 5 μm)
Spherical silica: 5 parts by mass (average particle size 5 μm)
Deodorant: amorphous silica: 10 parts by weight (average particle size 0.1 μm)

Comparative Example 1
Decorative sheets and decorative panels were manufactured in the same manner as in Example 1, except that the inorganic fillers listed below were used and the particle diameter of 85% of the inorganic fillers was adjusted to be 1 μm or more and less than 10 μm.
Inorganic filler: spherical alumina: 12 parts by mass (average particle size: 8 μm)
Spherical silica: 5 parts by mass (average particle size 8 μm)

Comparative Example 2
Decorative sheets and decorative panels were manufactured in the same manner as in Example 1, except that the inorganic fillers listed below were used and the particle diameter of 90% of the inorganic fillers was adjusted to be 1 μm or more and less than 10 μm.
Inorganic filler: spherical alumina: 12 parts by mass (average particle size: 5 μm)

Comparative Example 3
Decorative sheets and decorative panels were manufactured in the same manner as in Example 1, except that the inorganic fillers listed below were used and the particle diameter of 90% of the inorganic fillers was adjusted to be 1 μm or more and less than 10 μm.
Inorganic filler: spherical silica: 5 parts by mass (average particle size: 5 μm)

Comparative Example 4
Decorative sheets and decorative panels were manufactured in the same manner as in Example 1, except that the inorganic fillers listed below were used and the particle diameter of 90% of the inorganic fillers was adjusted to be 1 μm or more and less than 10 μm.
Inorganic filler: amorphous silica: 7 parts by mass (average particle size: 5 μm)

(evaluation)
The decorative sheets and decorative boards of the Examples and Comparative Examples produced as described above were evaluated by the following methods.

(1) Measurement of particle size and calculation of ratio The decorative sheet was cut in a direction parallel to the normal line of the surface of the decorative sheet. Next, an optical microscope (manufactured by KEYENCE Co., Ltd., product name: VHX-5000) was used to adjust the magnification to 1000 times, at which spherical inorganic fillers could be visually confirmed. The cross section of the decorative sheet was observed with the optical microscope, and the particle size was measured while counting the number of inorganic fillers observed. This operation was repeated until the number of inorganic fillers observed reached 100. Of the 100 inorganic fillers measured for particle size, the number of inorganic fillers with a particle size of 1 μm or more and less than 10 μm was counted, and the ratio of the number of inorganic fillers with a particle size of 1 μm or more and less than 10 μm out of the 100 was calculated.

(2) Scratch Resistance Test A steel wool (Bonstar #0000) was placed in contact with the surface of the decorative sheet under a load of 500 g/ ^m2 , and a rubbing test was performed 50 times. The surface of the decorative sheet was then wiped with ethanol, and the degree of gloss was visually observed and evaluated according to the following evaluation criteria.
+: No glossing was observed. -: Slight glossing was observed. - -: Significant glossing was observed.

(3) Bending whitening resistance test (room temperature)
The decorative sheet was rapidly bent at an angle of 90° in a room temperature environment (23° C.), and the state of whitening at the bent portion was visually observed and evaluated according to the following evaluation criteria.
+: No whitening was observed -: Slight whitening was observed - -: Significant whitening was observed

(4) Bending whitening resistance test (after heating)
The decorative board that had been subjected to the above-mentioned room temperature folding whitening resistance test was heated at the surface of the folded part of the decorative board for 30 seconds from a position 5 cm away using a Leister (manufactured by Ishizaki Electric Works, Ltd., product name: PJ-208A1) at a set temperature of 100°C. The condition of the folded part after heating was visually observed, and the reduction in whitening due to heating was evaluated according to the following evaluation criteria.
+: Whitening improved (decreased) -: Whitening improved (decreased), but the degree of improvement was slight - -: Whitening did not improve (decreased)

(5) Deodorizing Test The decorative sheet was cut to a size of 10 cm x 20 cm under normal temperature (23°C) to prepare a sample. The sample was placed in a bag (hereinafter referred to as a Tedlar bag) made of polyvinyl fluoride film, and 3 L of ammonia gas (initial concentration 100 ppm) was poured in. The residual gas concentration in the Tedlar bag after standing for 24 hours was measured with a gas detector tube. The ratio of the residual gas concentration after 24 hours to the initial concentration of ammonia gas was calculated and used as the reduction rate. Considering whether the target reduction rate of 70% or more was met, the evaluation was performed according to the following evaluation criteria. The detector tube used was No. 3M series (for ammonia gas) manufactured by Gastec Corporation. The lower detection limit was approximately 2 ppm.
++: The reduction was greater than the target reduction rate, and the reduction rate was 90% or more. +: The reduction was greater than the target reduction rate, and the reduction rate was 70% or more but less than 90%. -: The reduction was less than the target reduction rate.

The results are shown in Tables 1 and 2.

1. Decorative sheet 11. Adhesive layer 12. Base sheet 13. Picture pattern layer 14. Transparent resin layer 15. Surface protective layer 16. Fine particles 17. Release layer 2. Base

Claims (14)

A decorative sheet having at least a pressure-sensitive adhesive layer, a base sheet, and a surface protective layer in this order,
(1) The surface protective layer contains a curable resin and an inorganic filler, and the curable resin contains a copolymer of a vinyl chloride resin and a vinyl acetate resin, and an acrylic polyol;
(2) The inorganic filler is spherical alumina and another spherical inorganic filler other than alumina,
(3) The particle diameter of 90% or more of the inorganic filler particles out of any 100 particles of the inorganic filler particles, which is measured by observing a cross section of the decorative sheet cut in a direction parallel to the normal line of the surface of the decorative sheet, is 1 μm or more and less than 10 μm.
A decorative sheet characterized by: The decorative sheet according to claim 1, wherein the inorganic filler has a volume-based cumulative 50% particle size (D50) in the particle size distribution of 3 to 7 μm. The decorative sheet according to claim 1 or 2, wherein the inorganic filler has a volume-based cumulative 10% particle size (D10) in the particle size distribution of 1 to 2 μm. The decorative sheet according to any one of claims 1 to 3, wherein the inorganic filler has a volume-based cumulative 90% particle size (D90) in the particle size distribution of 8 to 9 μm. The decorative sheet according to any one of claims 1 to 4, wherein the surface protective layer contains a deodorant. The decorative sheet according to claim 5, wherein the deodorant is an amorphous filler, and the amorphous filler is at least one selected from the group consisting of silica, a simple metal salt, a metal salt complex, and zeolite. The decorative sheet according to claim 5 or 6, wherein the average particle size of the deodorant is less than 1 μm. The decorative sheet according to any one of claims 1 to 7 , wherein the curable resin contains 30% by mass or more of vinyl chloride resin units. The decorative sheet according to any one of claims 1 to 8 , wherein the surface protective layer has a thickness of 3 to 10 µm. The decorative sheet according to any one of claims 1 to 9 , wherein the base sheet contains 70% by mass or more of a polyvinyl chloride resin. The decorative sheet according to any one of claims 1 to 10 , wherein the surface protective layer contains an antiviral agent. The decorative sheet according to any one of claims 1 to 11 , wherein the pressure-sensitive adhesive layer contains an acrylic resin. The decorative sheet according to any one of claims 1 to 12 , which is a decorative sheet for wall materials. A decorative board having a decorative sheet according to any one of claims 1 to 13 on a substrate.

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