JP2021142744A - Decoration sheet and decoration plate - Google Patents

Abstract

To provide a decorative sheet having excellent abrasion resistance in which whitening generated on the surface is reduced by heating a decorative sheet after construction.SOLUTION: There is provided a decorative sheet which has at least an adhesive layer, a substrate sheet and a surface protective layer in this order, wherein (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 the inorganic fillers of 90% or more of the particle diameters of the arbitrary 100 inorganic fillers, measured by observing a cross section obtained by cutting the decorative sheet in the direction parallel to a normal line on the surface of the decorative sheet, is 1 μm or more and less than 10 μm.SELECTED DRAWING: None

Description

The present invention relates to a decorative sheet and a decorative board.

Conventionally, decorative sheets have been attached to the walls of buildings and the surfaces of various articles such as building materials, furniture, and electrical appliances in order to impart design.

Various items such as building walls, building materials, furniture, and electrical appliances may be rubbed by people or objects in daily life, and the decorative sheet attached to these surfaces is scratch resistant. Is required.

In addition, a surface protective layer containing a filler such as alumina is formed on the decorative sheet in order to impart scratch resistance and the like. As a decorative material using a decorative sheet on which such a surface protective layer is formed, in a decorative material in which a pattern layer and a protective layer are formed on the surface of a base material, the protective layer is spherical alumina and an inorganic or organic spherical filler. A wear-resistant decorative material composed of an ionizing radiation-curable resin layer containing the above has been proposed (see Patent Document 1).

However, the whitening resistance of the above-mentioned decorative materials has not been studied. If the hardness of the surface protective layer is increased in order to impart scratch resistance to the surface protective layer, the decorative sheet may crack at the bent part or be spherical with the resin when it is applied to a non-flat base such as a corner of a wall surface. There is a problem that whitening occurs due to peeling from the filler. In particular, when the decorative sheet is applied to a non-flat wall surface, the adhesive layer provided on the back surface of the decorative sheet is applied to the wall surface (tacking), and the surface is heated by a dryer or the like to follow the shape of the surface to be applied. It may be constructed by a construction method that follows the shape of the wall surface. The above-mentioned whitening due to cracking of the surface protective layer occurs in a normal temperature environment or a low temperature environment when it is applied to a non-flat wall surface, and even in a decorative sheet after it is applied by following the wall surface by heating, it is also whitened. There is a problem that it exists.

Therefore, it is desired to develop a decorative sheet having excellent scratch resistance and reducing whitening generated on the surface by heating the decorative sheet after construction.

Japanese Unexamined Patent Publication No. 10-286932

An object of the present invention is to provide a decorative sheet having excellent scratch resistance and reducing whitening generated on the surface by heating the decorative sheet after construction.

As a result of diligent research, the present inventors have conducted, and as a result, at least in a decorative sheet having an adhesive layer, a base sheet, and a surface protective layer in this order, the surface protective layer contains a curable resin and a specific inorganic filler. However, they have found that the above object can be achieved by setting the particle size of 90% or more of the inorganic fillers to be 1 μm or more and less than 10 μm, and have completed the present invention.

That is, the present invention relates to the following decorative sheets and decorative boards.
1. 1. A decorative sheet having at least an 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 contains
(2) The inorganic filler is spherical alumina and other spherical inorganic fillers other than alumina.
(3) 90% or more of the inorganic filler particle diameters of any 100 inorganic fillers measured by observing a cross section obtained by cutting the decorative sheet in a direction parallel to the normal on the surface of the decorative sheet. The particle size of the filler is 1 μm or more and less than 10 μm.
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the inorganic filler has a volume-based cumulative 50% particle size (D50) of 3 to 7 μm in the particle size distribution.
3. 3. Item 2. The decorative sheet according to Item 1 or 2, wherein the inorganic filler has a volume-based cumulative 10% particle size (D10) of 1 to 2 μm in the particle size distribution.
4. Item 3. 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) of 8 to 9 μm in the particle size distribution.
5. Item 2. The decorative sheet according to any one of Items 1 to 4, wherein the surface protective layer contains a deodorant.
6. Item 5. The deodorant is an amorphous filler, and the amorphous filler is at least one selected from the group consisting of silica, a simple substance of a metal salt, a composite of a metal salt, and a zeolite. Described cosmetic sheet.
7. Item 5. The decorative sheet according to Item 5 or 6, wherein the deodorant has an average particle size of less than 1 μm.
8. Item 2. The decorative sheet according to any one of Items 1 to 7, wherein the curable resin contains a copolymer of a vinyl chloride resin and a vinyl acetate resin, and an acrylic polyol.
9. Item 8. The decorative sheet according to Item 8, wherein the curable resin contains 30% by mass or more of a vinyl chloride resin unit.
10. Item 2. 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. Item 2. The decorative sheet according to any one of Items 1 to 10, wherein the base material sheet contains 70% by mass or more of a polyvinyl chloride resin.
12. Item 2. The decorative sheet according to any one of Items 1 to 11, wherein the surface protective layer contains an antiviral agent.
13. Item 2. The decorative sheet according to any one of Items 1 to 12, wherein the pressure-sensitive adhesive layer contains an acrylic resin.
14. Item 2. 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 base material.

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

It is a schematic diagram which shows an example of the layer structure of the decorative sheet of this invention. It is a schematic diagram which shows an example of the layer structure of the decorative sheet of this invention. It is a schematic diagram which shows an example of the layer structure of the decorative board of this invention.

Hereinafter, the decorative sheet and the decorative board of the present invention will be described in detail. The decorative sheet of the present invention has a so-called "front surface" on the side opposite to the side where the decorative sheet is laminated with the base material, and is visually recognized when it is applied to a wall surface, the surface of an article, or the like. This is the surface. Therefore, in the present specification, the direction of the surface of the decorative sheet opposite to the side to be laminated with the base material is referred to as "upper", and the direction of the opposite side, that is, the direction of the surface to be laminated with the base material is "upper". Called "back" or "bottom". Similarly, in the present specification, the direction of the surface of the decorative board on the decorative sheet side is referred to as "up", and the direction of the opposite side, that is, the direction of the surface on the base material side is referred to as "back" or "down".

Further, in the present specification, the normal temperature means 23 ° C. and the low temperature means 5 ° C. or lower.

1. 1. Decorative sheet The decorative sheet of the present invention is a decorative sheet having at least an adhesive layer, a base material 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 a spherical alumina and another spherical inorganic filler other than alumina, and (3) the decorative sheet is cut in a direction parallel to the normal line on the surface of the decorative sheet. The particle size of 90% or more of the particle size of any 100 inorganic fillers measured by observing the cross section is 1 μm or more and less than 10 μm.

In the decorative sheet of the present invention having the above characteristics, (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 particles other than alumina. Since it is a filler, it has excellent scratch resistance. Further, in the decorative sheet of the present invention, (2) the inorganic filler is spherical alumina and another spherical inorganic filler other than alumina, and (3) the decorative sheet is used on the surface of the decorative sheet. The particle size of 90% or more of the particle size of any 100 inorganic fillers measured by observing the cross section cut in the direction parallel to the normal line of the above is 1 μm or more and less than 10 μm. As a result, the above-mentioned two types of inorganic fillers are contained, and the particle size of these inorganic fillers is within a specific range and is uniform. Therefore, even if whitening occurs due to peeling of the curable resin and the inorganic filler in the surface protective layer or cracking of the curable resin when the work is applied to a non-flat wall surface in a normal temperature environment or a low temperature environment. The curable resin is easily expanded by heating, the gaps created by the peeling and cracking are easily closed, and the whitening caused by construction is reduced by heating.

That is, the decorative sheet of the present invention has at least an adhesive layer, a base material sheet, and a surface protective layer in this order, and has the above-mentioned configurations (1), (2), and (3). Therefore, it has excellent scratch resistance, and the whitening generated 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 material sheet, and a surface protective layer in this order, and the layer structure is limited as long as the above configurations (1) to (3) are provided. Not done. As an example of the layer structure of the decorative sheet of the present invention, for example, as shown in FIG. 1, the pressure-sensitive adhesive layer 11, the base material sheet 12, the pattern pattern layer 13 (solid ink layer and / or the pattern ink layer), and the adhesive layer. (Not shown), a layer structure having a transparent resin layer 14 and a surface protective layer 15 in this order can be mentioned (decorative sheet having doubling specifications). Further, as shown in FIG. 2, the decorative sheet of the present invention includes a release layer 17, an adhesive layer 11, a base sheet 12, a pattern pattern layer 13 (solid ink layer and / or a pattern ink layer), and an adhesive layer (adhesive layer). (Not shown), a layer structure having a transparent resin layer 14 and a surface protective layer 15 in this order can be mentioned. Hereinafter, a decorative sheet having such a layer structure will be specifically described as a typical example.

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

<Curing resin>
The surface protective layer contains a curable resin. Examples of the curable resin include thermosetting resins and ionizing radiation curable resins.

Examples of the thermosetting resin include polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, polyester resin, polyacrylic resin, ester-acrylic copolymer, epoxy resin, aminoalkyd resin, and phenol. Examples thereof include resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-urea cocondensate resins, silicon resins, polysiloxane resins and the like. Among these, polyvinyl chloride resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer are preferable, and vinyl chloride-vinyl acetate co-weight is preferable in that the adhesiveness between the curable resin and the base sheet is further excellent. Coalescence is more preferred.

The thermosetting resin may be used alone or in combination of two or more. From the viewpoint of further excellent weather resistance, it is preferable to use a copolymer of a vinyl chloride resin and a vinyl acetate resin (vinyl chloride-vinyl acetate copolymer) and an acrylic polyol in a mixed manner. When a copolymer of a vinyl chloride resin and a vinyl acetate resin and an acrylic polyol are mixed and used, the curable resin is a copolymer of a vinyl chloride resin and a vinyl acetate resin, an acrylic polyol, or the like. A mixed resin containing a polyol component can be prepared once, that is, the curable resin is preferably configured to contain a copolymer of a vinyl chloride resin and a vinyl acetate resin, and an acrylic polyol. By post-adding the isocyanate component to the mixed resin and preparing the curable resin again, the liquid stability of the mixed resin is excellent, so that the surface protective layer can be more easily formed.

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

A curing agent such as a cross-linking agent or a polymerization initiator, or a polymerization accelerator can be added to the thermosetting resin which is a curable resin. For example, as a curing agent, isocyanate, organic sulfonate, etc. can be added to unsaturated polyester resin, polyurethane resin, etc., organic amine, etc. can be added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutylnitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

The ionizing radiation curable resin is not limited as long as it is a resin that undergoes a cross-linking polymerization reaction by irradiation with ionizing radiation and changes into a three-dimensional polymer structure. For example, one or more of prepolymers, oligomers and monomers having a polymerizable unsaturated bond or an epoxy group in the molecule that can be crosslinked by irradiation with ionizing radiation can be used. For example, acrylate resins such as urethane acrylates, polyester acrylates and epoxy acrylates; silicon resins such as siloxane; polyester resins; epoxy resins and the like can be mentioned.

Examples of the ionizing radiation include visible light, ultraviolet rays (near ultraviolet rays, vacuum ultraviolet rays, etc.), X-rays, electron beams, ionizing rays, etc. Among them, ultraviolet rays and electron beams are preferable, and electron beams are more preferable.

As the ultraviolet source, a light source of an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. The wavelength of ultraviolet rays is about 190 to 380 nm.

As the electron beam source, for example, various electron beam accelerators such as Cockcroft-Walt type, Van de Graaff type, resonance transformer type, insulated core transformer type, linear type, dynamitron type, and high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 2 to 15 Mrad.

The ionizing radiation curable resin is sufficiently cured by irradiating it with an electron beam, but when it is cured by irradiating it with ultraviolet rays, 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 is, for example, acetophenone, benzophenone, thioxanthone, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide. , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. Further, in the case of a resin system having a cationically polymerizable functional group, at least one of, for example, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, a freeleoxysulfoxonium diallyl iodosyl salt and the like. Can be used.

The amount of the photopolymerization initiator added is not particularly limited, but is generally about 0.1 to 10 parts by mass with respect to 100 parts by mass of the 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 the viewpoint that the whitening generated on the surface is reduced by heating the decorative sheet after construction is more easily exhibited. Therefore, it is preferable that the amorphous inorganic filler is substantially not contained. In addition, substantially not contained means that the content of the amorphous inorganic filler in the surface protective layer is 10 parts by mass or less with 100 parts by mass of the curable resin, and 5 parts by mass. The following is preferable, and 0 part by mass is more preferable.

In the present specification, the amorphous inorganic filler is an amorphous inorganic filler having an average particle diameter of 1 μm or more, and the deodorant described later is a deodorant having an average particle diameter of less than 1 μm. Distinguished.

In the decorative sheet of the present invention, the particle size of the arbitrary 100 inorganic fillers measured by observing a cross section obtained by cutting the decorative sheet in a direction parallel to the normal on the surface of the decorative sheet is 90% or more of the inorganic filler is 1 μm or more and less than 10 μm. When the amount of the inorganic filler having a particle size of 1 μm or more and less than 10 μm is less than 90%, the whitening caused by the gap between the curable resin and the inorganic filler that occurs when the decorative sheet is bent is not reduced by heating. The content of the inorganic filler having a particle size of 1 μm or more and less than 10 μm is preferably 92% or more, and more preferably 95% or more. Further, the upper limit of the proportion of the inorganic filler having a particle size of 1 μm or more and less than 10 μm is not particularly limited, and may be 100% or 100% or less.

The method for measuring the particle size of the inorganic filler and the method for calculating the ratio of the inorganic filler having a particle size of 1 μm or more and less than 10 μm are as follows in detail. That is, the decorative sheet is cut in a direction parallel to the normal on the surface of the decorative sheet. Then, using an optical microscope (product name: VHX-5000 manufactured by KEYENCE Co., Ltd.), the magnification of the inorganic filler is adjusted to 1000 times, which is a visually recognizable magnification. The cross section of the decorative sheet is observed with an optical microscope, and the particle size is measured while counting the number of observed inorganic fillers. This operation is repeated until the number of observed inorganic fillers reaches 100. Of the measured particle diameters of 100 inorganic fillers, the number of inorganic fillers having a particle size of 1 μm or more and less than 10 μm is counted, and the ratio of the number of inorganic fillers having a particle size of 1 μm or more and less than 10 μm out of 100 is calculated. .. In the above calculation method, the deodorant described later is not a measurement target and is not considered. The inorganic filler and the deodorant can be distinguished from each other by the fact that the deodorant is an amorphous filler having 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. When the average particle size of the inorganic filler is in the above range, the decorative sheet of the present invention is further excellent in scratch resistance, and the whitening generated on the surface is further reduced by heating the decorative sheet after construction.

In the present specification, the average particle size of the inorganic filler is a value measured by the following measuring method. That is, the decorative sheet is cut in a direction parallel to the normal on the surface of the decorative sheet. Then, using an optical microscope (product name: VHX-5000 manufactured by KEYENCE Co., Ltd.), the magnification of the inorganic filler is adjusted to 1000 times, which is a visually recognizable magnification. The cross section of the decorative sheet is observed with an optical microscope, and the particle size is measured while counting the number of observed inorganic fillers. This operation is repeated until the number of observed inorganic fillers reaches 100. The average particle size of the 100 measured inorganic fillers is defined as the average particle size. In the method for measuring the average particle size of the inorganic filler, the deodorant described later is not a measurement target and is not considered. The inorganic filler and the deodorant can be distinguished from each other by the fact that the deodorant is an amorphous filler having an average particle size of less than 1 μm.

The alumina is not particularly limited as long as it is spherical, and conventionally known alumina that can impart wear resistance to the decorative sheet can be used. Examples of such alumina include α-alumina, γ-alumina, θ-alumina, δ-alumina and the like.

The average particle size of alumina is preferably 1 to 10 μm, more preferably 2 to 7 μm, and even more preferably 3 to 5 μm. When the average particle size of alumina is in the above range, the particle size of the inorganic filler according to the above measuring method can be further adjusted to 1 μm or more and less than 10 μm. Further, since the average particle size of alumina is in the above range, as will be described later, when the surface protective layer contains a deodorant, the deodorant is an amorphous filler having an average particle size of less than 1 μm. The distinction between is even clearer.

As the alumina, a commercially available product 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, with the curable resin as 100 parts by mass. When the alumina content is in the above range, the abrasion resistance of the decorative sheet is further improved.

The spherical other inorganic filler other than alumina is not particularly limited as long as it is spherical, and a conventionally known inorganic filler capable of imparting wear resistance to the decorative sheet can be used. Examples of such inorganic fillers include silica, silicon carbide, calcium titanate, barium titanate, magnesium pyrobolate, zinc oxide, silicon nitride, zirconium oxide, chromium oxide, iron oxide, boron nitride, diamond, gold sand, and glass. Examples include fibers. Among these, silica is preferable because it is more excellent in wear resistance.

The average particle size of other spherical inorganic fillers other than alumina is preferably 1 to 10 μm, more preferably 2 to 7 μm, and even more preferably 3 to 5 μm. When the average particle size of the spherical other inorganic filler other than alumina is within the above range, it becomes easier to further adjust the particle size of the inorganic filler by the above measuring method to 1 μm or more and less than 10 μm. Further, since the average particle size of other spherical inorganic fillers other than alumina is within the above range, as will be described later, when the surface protective layer contains a deodorant, the average particle size is less than 1 μm. The distinction from the deodorant, which is the filler of the above, becomes clearer.

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 further 7 to 13 parts by mass, with the curable resin as 100 parts by mass. preferable. When the content of the spherical inorganic filler other than alumina is within 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) has a volume-based cumulative 50% particle size (D50) of 3 to 7 μm, more preferably 4 to 6 μm in the particle size distribution. When the volume-based cumulative 50% particle size (D50) of the inorganic filler is within the above range, the whitening generated 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) of 1 to 2.5 μm, more preferably 1 to 2 μm in the particle size distribution. .. When the volume-based cumulative 10% particle size (D10) of the inorganic filler is within the above range, the whitening generated 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) of 7.5 to 9 μm, more preferably 8 to 9 μm in the particle size distribution. .. When the volume-based cumulative 90% particle size (D90) of the inorganic filler is within the above range, the whitening generated 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 the laser diffraction / scattering method.

As a method for forming the surface protective layer, for example, a composition for forming a surface protective layer containing a curable resin and an inorganic filler is applied by a coating method such as a gravure reverse method, a roll coating method, or a gravure coating method, and dried. Examples include a method of 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, further preferably 10 μm or less, and particularly preferably 5 μm or less. When the lower limit of the thickness of the surface protective layer is within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved. Further, when the upper limit of the thickness of the surface protective layer is within the above range, the wear resistance is further improved. The thickness of the surface protective layer is preferably 3 to 10 μm.

The surface protective layer may contain additives, if necessary. Examples of additives include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, light stabilizers, deodorants, antibacterial agents, and antiviruses. Examples include agents, anti-allergen agents, antifungal agents and the like.

The surface protective layer preferably contains an antiviral agent. Antiviral agents can be broadly classified into organic and inorganic agents. Examples of the organic antiviral agent include quaternary ammonium salt-based, quaternary phosphonium salt-based, pyridine-based, pyrithione-based, benzimidazole-based, organic iodine-based, isothiazoline-based, and anionic antiviral agents. .. Examples of the inorganic antiviral agent 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 the particle shape, are particularly preferably used. When the antiviral agent retains its particle shape, it means that the antiviral agent does not dissolve in the composition (ink before curing) for forming the surface protective layer, but in the state of particles in the surface protective layer after curing. It means that it exists. Therefore, in the process of forming the surface protective layer, the particles of the antiviral agent are likely to emerge, and the particles of the antiviral agent can be easily unevenly distributed 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 suppress the amount of the antiviral agent added in order to obtain a predetermined antiviral property. It is possible to easily suppress a decrease in scratch resistance.

As the anionic antiviral agent, for example, those containing a styrene polymer derivative compound and an unsaturated carboxylic acid derivative compound are preferable. Further, the styrene polymer derivative compound and the 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 may include all the structures. More preferred. This is because there are two types of viruses with and without envelope, and it is considered that the structures of antiviral agents that can effectively inhibit the activity of each type are different.

As the above-mentioned inorganic antiviral agent, a silver-based antiviral agent is preferable from the viewpoint of non-biotoxicity and excellent safety, and among them, a phosphoric acid-based glass-silver-supporting compound or a silver zeolite compound exhibits antiviral performance even in a small amount. Therefore, the amount of addition can be suppressed, which is more preferable.

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

As used herein, the deodorant is an amorphous filler having an average particle size of less than 1 μm. The amorphous filler is not particularly limited as long as it has an average particle size of less than 1 μm, is amorphous, and can exhibit a deodorizing effect, and examples thereof include silica, a simple substance of a metal salt, a composite of a metal salt, and zeolite. .. The amorphous filler formed by the above substance has an average particle size of less than 1 μm and has a large surface area due to its irregular shape, and can adsorb a substance that causes an odor to recesses and micropores. It can fully exert its function as a deodorant.

Examples of the simple substance of the metal salt include zinc oxide and the like. Moreover, as a composite of a metal salt, a compound in which an organic substance such as amines is supported on an inorganic substance such as zinc can be mentioned.

As the zeolite, it is preferable to use a zeolite obtained by calcining a composite of metal salts, that is, as the zeolite, a zeolite obtained by calcining a composite of metal salts is preferable. As the metal salt composite, the above-mentioned metal salt composite can be used.

Examples of the amorphous filler capable of exerting the deodorizing effect include those having a reduction rate of 90% or more by the following deodorizing property test.
Deodorant test Under normal temperature environment (23 ° C), 0.1 g of a sample is placed in a bag (hereinafter referred to as a tedler bag) prepared using a polyvinyl fluoride film, and 3 L of ammonia gas (initial concentration 100 ppm) is injected. The residual gas concentration in the tedler bag after standing for 24 hours is measured with a gas detector tube. The ratio of the residual gas concentration after 24 hours to the initial concentration of ammonia gas 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 in the above range, the decorative sheet of the present invention has excellent scratch resistance, and the whitening generated on the surface is reduced by heating the decorative sheet after construction. While demonstrating, the deodorant function can be further exhibited. 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, or the like.

Since the average particle size of the deodorant is less than 1 μm, it is easy to distinguish it from the inorganic filler contained in the surface protective layer of the decorative sheet of the present invention at the time of measurement, and it is difficult to be confused.

In the present specification, the average particle size of the deodorant is a value measured by the following measuring method. That is, the decorative sheet is cut in a direction parallel to the normal on the surface of the decorative sheet. Next, use a scanning electron microscope (Hitachi High-Technologies Corporation, product name: S-4800 type field emission scanning electron microscope) to adjust the magnification to 20000 times, which is the magnification at which the deodorant can be confirmed. The cross section of the decorative sheet is observed with a scanning electron microscope, and the particle size is measured while counting the number of deodorants observed. This operation is repeated until the number of deodorants observed reaches 100. The average particle size of the 100 measured deodorants is defined as the average particle size. In the method for measuring the average particle size of the deodorant, the above-mentioned inorganic filler is not a measurement target and is not considered. 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. .. Within the above range, the decorative sheet of the present invention has excellent scratch resistance, and the whitening generated on the surface is reduced by heating the decorative sheet after construction, while exhibiting a deodorizing function. be able to.

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

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

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

In the present specification, the thickness of the surface protective layer is as shown as ts in FIGS. 1 and 2, when the fine particles 16 are cueed from the surface of the surface protective layer, the cueed fine particles are used. A portion other than 16 is measured as the surface of the surface protective layer. Further, as shown in FIGS. 1 and 2, when the decorative sheet is embossed to form an uneven pattern, the thickness of the surface protective layer is measured at a portion other than the uneven pattern.

(Base sheet)
As the base material sheet, a synthetic resin sheet such as a polyvinyl chloride resin, a polyolefin resin, a polyester resin, a polyacrylic resin, a polyamide resin, a polyurethane resin, or a polystyrene resin can be used. As the base material sheet, a synthetic resin sheet made of only one of the above resins 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 a polyvinyl chloride resin is preferable.

When the base sheet contains a polyvinyl chloride resin, the content of the polyvinyl chloride resin is preferably 60% by mass or more, more preferably 70% by mass or more, with the base sheet as 100% by mass. When the lower limit of the content of the polyvinyl chloride resin is 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 polyethylene, ethylene-α-olefin copolymer, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene. -Vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer and the like can be mentioned. Among these, polypropylene is preferable.

Examples of the polyester resin include polyethylene terephthalate and polyalkylene terephthalate having high heat resistance [for example, polyethylene terephthalate in which a part of ethylene glycol is replaced with 1,4-cyclohexanedimethanol, diethylene glycol, etc., so-called trade name PET-G ( (Manufactured by Eastman Chemical Company)], polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer and the like. Among these, polyalkylene terephthalate having high heat resistance is preferable.

The thickness of the base sheet is preferably 20 to 300 μm, more preferably 40 to 200 μm. The base sheet may be colored if necessary. Further, the surface may be subjected to surface treatment such as corona discharge treatment, plasma treatment, ozone treatment, or may be coated with a primer which is a base coating material for enhancing adhesion with an adjacent layer.

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

The resin for forming the pressure-sensitive adhesive layer is not particularly limited as long as it can exhibit adhesiveness, and examples thereof include acrylic resins and urethane resins. Among these, it is preferable to contain an acrylic resin in that a decorative sheet can impart even higher adhesiveness.

The thickness of the pressure-sensitive adhesive layer is preferably 10 to 100 μm, more preferably 30 to 70 μm, and even more preferably 40 to 50 μm. When the thickness of the pressure-sensitive adhesive layer is within the above range, the adhesiveness between the decorative sheet and the base material or the adherend is further improved.

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

As the ink used for the pattern layer, as a vehicle, chlorinated polyethylene such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, polyacrylic, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate A copolymer, a cellulose-based resin, a polyamide-based resin, or the like is used by mixing one or more kinds, and a pigment, a solvent, various auxiliary agents, and the like are added thereto to form an ink. Among these, one or more of polyester, polyurethane composed of isocyanate and polyol, polyacrylic, polyamide resin, acrylic urethane resin-containing curable resin, etc. from the viewpoint of environmental problems and adhesion to the surface to be printed. Is preferable, and a curable resin containing an acrylic urethane resin is more preferable.

(Transparent adhesive layer)
The transparent adhesive layer is provided between the pattern layer and the transparent resin layer, if necessary. The transparent adhesive layer can be obtained by applying and drying a known dry lamination adhesive such as a two-component curable urethane resin.

The thickness of the transparent adhesive layer after drying is preferably about 0.1 to 30 μm, 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 preferably formed by, for example, a transparent thermoplastic resin.

Specifically, both soft, semi-hard or hard polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, and ethylene-acrylic acid ester. Examples thereof include synthetic resins such as polymers, ionomers, acrylic acid esters, and methacrylic acid esters. Among the above, polyolefin-based resins such as polyvinyl chloride resin and polypropylene are preferable, and polyvinyl chloride resin is more preferable.

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

The transparent resin layer includes a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, a light stabilizer, a radical scavenger, a soft component (for example, rubber), etc. Various additives may be included.

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

If necessary, the surface of the transparent resin layer may be subjected to surface treatment such as corona discharge treatment, ozone treatment, plasma treatment, ionizing radiation treatment, and heavy chromic acid treatment. The surface treatment may be performed according to the conventional method of each treatment.

A primer layer (a primer layer for facilitating the formation of the 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 the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin and the like, a resin-based primer agent made of a block copolymer of acrylic and urethane, and the like.

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

(Release layer)
In the decorative sheet of the present invention, a release layer may be 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 pressure-sensitive adhesive layer and can show releasability, and examples thereof include a release paper; a release sheet containing a silicon-based resin or the like.

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

In the lamination of each layer described above, for example, a pattern pattern layer (solid ink layer, pattern ink layer) is formed by printing on one surface of the base material sheet, and then a two-component curable urethane resin or the like is known on the pattern pattern layer. A resin for forming an adhesive layer on the back surface of a base sheet after laminating a transparent resin layer via a dry lamination adhesive by a dry lamination method, a T-die extrusion method, or the like to further form a surface protective layer. Is applied and dried to form a pressure-sensitive adhesive layer, and a release layer is laminated on the pressure-sensitive adhesive layer.

The total thickness of the decorative sheet (excluding the release layer) is preferably 160 μm or more, 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. When the lower limit of the total thickness of the decorative sheet is within the above range, the scratch resistance and abrasion resistance of the decorative sheet are further improved. Further, when the upper limit of the total thickness of the decorative sheet is within the above range, the whitening resistance of the decorative sheet is further improved.

In the present specification, the total thickness of the decorative sheet is, as shown as td in FIGS. 1 and 2, when the fine particles 16 are cueed from the surface of the surface protective layer, the cueed fine particles are used. A portion other than 16 is measured as the surface of the decorative sheet. Further, as shown in FIGS. 1 and 2, when the decorative sheet is embossed to form an uneven pattern, the total thickness of the decorative sheet is measured at a portion other than the uneven pattern.

The decorative sheet may be embossed from the surface protective layer side (upper side of the decorative sheet) to form an uneven pattern. The uneven pattern can be formed by heat pressing, hairline processing, or the like. Examples of the uneven pattern include a conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, and a perforated groove.

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

The various additives added to the above-mentioned layers of the decorative sheet of the present invention (spherical alumina contained in the surface protective layer, other spherical inorganic fillers other than alumina, deodorants, etc.) are vesicles of the various additives. It is preferable that it is made. The method for vesicle-forming various additives is not particularly limited, and vesicles can be formed by a known method, and the supercritical reverse-phase evaporation method is particularly preferable.

Hereinafter, the supercritical reverse phase evaporation method will be described in detail. The supercritical reverse phase evaporation method is water-soluble or hydrophilic in a mixture in which a substance forming an outer film of a vesicle is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure conditions above the supercritical point. This is a method in which an aqueous phase containing various additives as an encapsulating substance is added to form a capsule-shaped vesicle containing various additives as an encapsulating substance in a single layer film. The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state having a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and is a temperature above the critical point or higher. Carbon dioxide under pressure conditions means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained. In general, vesicles are a general term for vesicles having a spherical shell-like closed membrane structure containing a liquid phase, and in particular, liposomes whose outer membrane is composed of biolipids such as phospholipids. ..

Examples of the phospholipids include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, yellow egg lecithin, hydrogenated yellow egg lecithin, soybean lecithin, hydrogenated soybean lecithin and other glycerophospholipids, and sphingomyelin. , Ceramide phosphorylethanolamine, ceramide phosphorylglycerol and other sphingolin lipids.

As the substance constituting the outer membrane, a nonionic surfactant or a dispersant such as a mixture thereof with cholesterol or triacylglycerol can also be used.

Examples of the nonionic surfactant include polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, and polybutadiene-. One or two types such as polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. The above can be used.

Examples of the cholesterol include one or more of cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholic acid, choleciferol and the like. Can be used.

The outer membrane of the liposome may be formed from a mixture of a phospholipid and a dispersant. In the decorative sheet of the present invention, by forming the outer membrane into liposomes formed from phospholipids, the compatibility between the resin composition which is the main component of each layer and various additives can be improved.

Since the decorative sheet of the present invention has the above-mentioned structure, it is excellent in scratch resistance and whitening generated on the surface is reduced by heating. As a result, it can be suitably applied to a non-planar adherend such as a wall surface. Therefore, the decorative sheet of the present invention can be suitably used as a decorative sheet for interior materials, particularly 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 base material.

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

(Base material)
The material of the base material is not particularly limited, and examples thereof include a wood board usually used for a decorative board, a hot-dip galvanized steel sheet, and the like.

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

The method of laminating the decorative sheet on the front surface of the base material is not particularly limited, and a conventionally known method such as laminating and curing the front surface of the base material and the adhesive layer of the decorative sheet is used. Can be laminated.

Since the decorative board of the present invention has the above-mentioned structure, it is excellent in scratch resistance and the whitening generated on the surface is reduced by heating. Further, even when whitening occurs by bending the base material after laminating the decorative sheet on the base material, heating the decorative sheet on the base material reduces the whitening. Therefore, the decorative board of the present invention can be suitably used as a decorative board for interior materials, particularly as a decorative board for wall materials.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1
(Manufacturing of decorative sheets)
As a base sheet, a colored polyvinyl chloride film having a thickness of 80 μm was prepared. Next, an acrylic urethane resin-containing printing ink, which is a printing ink for a polyvinyl chloride film, is applied to the front surface of the base sheet by a gravure printing method to form a pattern layer. bottom. A transparent polyvinyl chloride resin sheet having a thickness of 80 μm was laminated on the pattern layer by a heat laminating method as a transparent resin layer, and at the same time, an embossed shape was formed from the front surface of the transparent resin layer. Next, the front surface of the transparent resin layer is coated with the composition for forming a surface protective layer prepared as follows by a gravure reverse method, and heated with hot air by air drying with a dryer to cure. A surface protective layer having a thickness of 3.8 μm was formed.

(Composition for forming a surface protective layer)
The following components were kneaded to prepare a mixed resin.
-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 mixed resin to prepare a resin component.
-Isocyanate: 10 parts by mass The resin component prepared as described above and the following inorganic filler were mixed to prepare a composition for forming a surface protective layer having the following composition.
-Resin component: 100 parts by mass-Inorganic filler Spherical alumina: 12 parts by mass (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 diameter (D50) of 5 μm, a volume-based cumulative 10% particle diameter (D10) of 1 μm, and a volume-based cumulative 90% particle in the particle size distribution measured by the laser diffraction / scattering method. The diameter (D90) was 9 μm.

Next, an acrylic resin was applied to the back surface of the base material sheet by a comma coater method so as to have a thickness of 45 μm, and dried to form an adhesive layer. Next, a release paper having a thickness of 125 μm was laminated on the pressure-sensitive adhesive layer to form a release layer, and a decorative sheet was manufactured. When the particle size of the inorganic filler was measured by the measuring method described later, the particle size of 90% of the particle size of the inorganic filler was 1 μm or more and less than 10 μm.

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

(Manufacturing of decorative boards)
As a base material, a hot-dip galvanized steel sheet having a thickness of 0.5 mm was prepared. A decorative board was manufactured by laminating the adhesive layer of the decorative sheet and the base material.

Example 2
Using the following inorganic filler, a decorative sheet and a decorative board were manufactured in the same manner as in Example 1 except that the particle size of 95% of the particle size of the inorganic filler was adjusted to be 1 μm or more and less than 10 μm. bottom.
-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
Using the following inorganic filler and deodorant, the decorative sheet and the decorative sheet and the same as in Example 1 except that the particle size of 90% of the particle size of the inorganic filler was adjusted to be 1 μm or more and less than 10 μm. Manufactured a veneer.
-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 mass (average particle size 0.1 μm)

Comparative Example 1
Using the following inorganic filler, a decorative sheet and a decorative board were manufactured in the same manner as in Example 1 except that the particle size of 85% of the particle size of the inorganic filler was adjusted to be 1 μm or more and less than 10 μm. bottom.
-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
Using the following inorganic filler, a decorative sheet and a decorative board were manufactured in the same manner as in Example 1 except that the particle size of 90% of the particle size of the inorganic filler was adjusted to be 1 μm or more and less than 10 μm. bottom.
-Inorganic filler Spherical alumina: 12 parts by mass (average particle size 5 μm)

Comparative Example 3
Using the following inorganic filler, a decorative sheet and a decorative board were manufactured in the same manner as in Example 1 except that the particle size of 90% of the particle size of the inorganic filler was adjusted to be 1 μm or more and less than 10 μm. bottom.
-Inorganic filler Spherical silica: 5 parts by mass (average particle size 5 μm)

Comparative Example 4
Using the following inorganic filler, a decorative sheet and a decorative board were manufactured in the same manner as in Example 1 except that the particle size of 90% of the particle size of the inorganic filler was adjusted to be 1 μm or more and less than 10 μm. bottom.
-Inorganic filler amorphous silica: 7 parts by mass (average particle size 5 μm)

(evaluation)
The decorative sheets and decorative boards of 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 on the surface of the decorative sheet. Then, using an optical microscope (product name: VHX-5000 manufactured by KEYENCE Co., Ltd.), the magnification was adjusted to 1000 times, which is a magnification at which the spherical inorganic filler can be visually confirmed. The cross section of the decorative sheet was observed with an optical microscope, and the particle size was measured while counting the number of observed inorganic fillers. This work was repeated until the number of observed inorganic fillers reached 100. The number of inorganic fillers having a particle size of 1 μm or more and less than 10 μm was counted from the measured particle diameters of 100 inorganic fillers, and the ratio of the number of inorganic fillers having a particle size of 1 μm or more and less than 10 μm out of 100 was calculated. ..

(2) Scratch resistance test Steel wool (# 0000 manufactured by Bonstar Co., Ltd.) ^{was brought into contact with the surface of the decorative sheet so as to apply a load of 500 g / m 2} , and a rubbing test of 50 reciprocations was performed. Next, the surface of the decorative sheet was wiped with ethanol, the degree of glossiness was visually observed, and the evaluation was made according to the following evaluation criteria.
+: No gloss was observed-: Slight gloss was observed-: Significant gloss was observed

(3) Bending whitening resistance test (normal temperature)
The decorative board was sharply bent at an angle of 90 ° under a normal temperature environment (23 ° C.), and the whitening condition of 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 above-mentioned decorative board subjected to the bending whitening resistance test at room temperature was subjected to a set temperature of 100 ° C. from a position 5 cm away using a ryster (product name: PJ-208A1 manufactured by Ishizaki Electric Mfg. Co., Ltd.). The surface of the bent portion of the veneer was heated for 30 seconds. The state of the bent portion after heating was visually observed, and the decrease 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 (decrease)

(5) Deodorant Test A sample was prepared by cutting a decorative sheet into a size of 10 cm × 20 cm under a normal temperature environment (23 ° C.). The sample was placed in a bag (hereinafter referred to as a tedler bag) prepared using a polyvinyl fluoride film, and 3 L of ammonia gas (initial concentration 100 ppm) was injected. The residual gas concentration in the tedler 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. The evaluation was made according to the following evaluation criteria in consideration of whether or not the target reduction rate of 70% or more was satisfied. The detector tube is made by Gastec Co., Ltd., No. A 3M system (for ammonia gas) was used. The lower limit of detection is about 2 ppm.
++: Reduced from the target reduction rate and the reduction rate was 90% or more +: Reduced from the target reduction rate and the reduction rate was 70% or more and less than 90%-: Not reduced from the target reduction rate

The results are shown in Tables 1 and 2.

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

Claims (15)

A decorative sheet having at least an 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 contains
(2) The inorganic filler is spherical alumina and other spherical inorganic fillers other than alumina.
(3) 90% or more of the inorganic filler particle diameters of any 100 inorganic fillers measured by observing a cross section obtained by cutting the decorative sheet in a direction parallel to the normal on the surface of the decorative sheet. The particle size of the filler is 1 μm or more and less than 10 μm.
A decorative sheet characterized by that. The decorative sheet according to claim 1, wherein the inorganic filler has a volume-based cumulative 50% particle size (D50) of 3 to 7 μm in the particle size distribution. The decorative sheet according to claim 1 or 2, wherein the inorganic filler has a volume-based cumulative 10% particle size (D10) of 1 to 2 μm in the particle size distribution. 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) of 8 to 9 μm in the particle size distribution. The decorative sheet according to any one of claims 1 to 4, wherein the surface protective layer contains a deodorant. 5. The deodorant is an amorphous filler, and the amorphous filler is at least one selected from the group consisting of silica, a simple substance of a metal salt, a composite of a metal salt, and a zeolite. Cosmetic sheet described in. The decorative sheet according to claim 5 or 6, wherein the deodorant has an average particle size of less than 1 μm. The decorative sheet according to any one of claims 1 to 7, wherein the curable resin contains a copolymer of a vinyl chloride resin and a vinyl acetate resin, and an acrylic polyol. The decorative sheet according to claim 8, wherein the curable resin contains 30% by mass or more of a vinyl chloride resin unit. The decorative sheet according to any one of claims 1 to 9, wherein the surface protective layer has a thickness of 3 to 10 μm. The decorative sheet according to any one of claims 1 to 10, wherein the base material sheet contains 70% by mass or more of a polyvinyl chloride resin. The decorative sheet according to any one of claims 1 to 11, wherein the surface protective layer contains an antiviral agent. The decorative sheet according to any one of claims 1 to 12, wherein the pressure-sensitive adhesive layer contains an acrylic resin. The decorative sheet according to any one of claims 1 to 13, which is a decorative sheet for wall materials. A decorative board having the decorative sheet according to any one of claims 1 to 14 on a base material.

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