JP2020100138A - Decorative sheet - Google Patents

Abstract

To provide a decorative sheet with improved scratch resistance under a high-load condition.SOLUTION: A decorative sheet includes a raw fabric layer 7, a transparent resin layer 1 and surface protective layers in this order. The surface protective layers are composed as a multilayer. If a surface protective layer located on an outermost surface among the surface protective layers is a surface protective layer 4a and a surface protective layer located in a lower layer thereof is a surface protective layer 4b, the surface protective layer 4a includes: one or more kinds of ionizing radiation-curable resin having 0.10 μm/g<E<0.45 μm/g of an erosion rate E measured using polygonal alumina powder with an average particle diameter (D50) of 1.2 μm and one or more kinds of thermosetting resin having 0.30 μm/g<E<0.6 μm/g thereof. A mass ratio of the ionizing radiation-curable resin and the thermosetting resin (ionizing radiation-curable resin/thermosetting resin) is 95/5-40/60.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet.

In recent years, for example, as shown in Patent Documents 1 to 3, as a decorative sheet replacing a decorative sheet made of polyvinyl chloride, many decorative sheets using an olefin resin have been proposed.
However, since these decorative sheets do not use vinyl chloride resin, the generation of toxic gases and the like during incineration is suppressed, but, for example, when a general polypropylene sheet or a soft polypropylene sheet is used, Scratch resistance (scratch resistance) tends to deteriorate. Therefore, a decorative sheet using an olefin resin may be inferior in scratch resistance to a conventional polyvinyl chloride decorative sheet.

Japanese Patent No. 3271022 Japanese Patent No. 3861472 Japanese Patent No. 3772634

In order to improve the scratch resistance of the decorative sheet, a method of coating and curing an ionizing radiation curable resin on the surface protective layer is known. However, there is a problem that the decorative sheet is not scratched at all, and that when the scratch resistance test is performed under a high load condition, the decorative sheet may be scratched.
Therefore, in order to improve scratch resistance under high load conditions, it has been proposed to make the surface protective layer harder and thicker, but if the surface protective layer is made too hard, the surface protective layer becomes brittle and falls. There is also a problem that impact resistance to an object or the like may be deteriorated or weather resistance may be deteriorated, and if the surface protective layer is thickened, cost may be increased.
Further, as in the case of the surface protective layer, in order to improve scratch resistance under high load conditions, it has been proposed to make the transparent resin layer located under the surface protective layer harder and thicker. , If the transparent resin layer is too hard, the transparent resin layer becomes brittle, and the impact resistance against falling objects and the like may deteriorate, or the weather resistance may deteriorate.If the transparent resin layer is thick, the cost may decrease. There were also problems such as hanging up.

Further, in order to improve scratch resistance under high load conditions, it has been proposed to add an inorganic filler to the surface protective layer, but when the inorganic filler is added to the surface protective layer, the inorganic filler is greatly increased from the surface protective layer. If there is a protrusion or a void at the interface with the surface protective layer, the inorganic filler may be damaged during the scratch resistance test, or the inorganic filler may be missing from the surface protective layer, which may cause gloss change. there were.
The present invention has been made in view of the above points, and an object thereof is to provide a decorative sheet having improved scratch resistance under a high load condition.

The present inventors, as a result of repeated intensive studies to achieve the above object, by forming at least one of a surface protective layer and a transparent resin layer having a specific erosion rate on the decorative sheet, to solve the above problems Found to get.
The decorative sheet according to one aspect of the present invention is a decorative sheet that includes an original fabric, a transparent resin layer, and a surface protective layer in this order, wherein the surface protective layer is composed of a plurality of layers, and the surface protective layer includes When the outermost surface protective layer is the first surface protective layer and the lower surface protective layer is the second surface protective layer, the first surface protective layer has an average particle diameter ( D50) one or more ionizing radiation curable resins having an erosion rate E of 0.10 μm/g<E<0.45 μm/g measured using polygonal alumina particles of 1.2 μm, and 0.30 μm/ A mass ratio of the ionizing radiation-curable resin and the thermosetting resin (ionizing radiation-curable resin/thermosetting resin) containing one or more thermosetting resins with g<E<0.6 μm/g. ) Is 95/5 to 40/60.
A decorative sheet according to another aspect of the present invention is a decorative sheet including a raw fabric, a transparent resin layer, and a surface protective layer in this order, and the transparent resin layer has an average particle diameter (D50) of 1 The erosion rate E measured using polygonal alumina particles of 0.2 μm is 0.05 μm/g<E<2 μm/g.

According to the decorative sheet according to one aspect of the present invention, it is possible to provide a decorative sheet having excellent scratch resistance even under a high load condition.

It is sectional drawing which shows an example of embodiment of the decorative sheet of this invention.

The decorative sheet according to the embodiment of the present invention will be described in detail below with reference to FIG.
Here, the drawings are schematic, and the relationship between the thickness and the plane dimension, the thickness ratio of each layer, and the like are different from the actual ones. Further, the embodiments described below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the components are as follows. It is not specific to a thing. Various changes can be added to the technical idea of the present invention within the technical scope defined by the claims described in the claims.

(Measurement of erosion rate E)
First, the "erosion rate E" defined in this embodiment will be described.
The erosion rate E in the present embodiment is, for example, a material surface precision tester (micro slurry jet erosion tester, hereinafter MSE tester, manufactured by PALMESO CO., LTD./apparatus name: nano MSE/model N-MSE). -A) is a value measured using. The specific method for measuring the erosion rate E is as follows.

Polygonal alumina powder (particles) having an average particle diameter D ₅₀ =1.2 μm is dispersed in water to prepare a slurry containing 3% by mass of polygonal alumina powder with respect to the total mass of the slurry. The decorative sheet is fixed to a table, and the projection distance between the decorative sheet and the nozzle for spraying the slurry is set to 4 mm. The nozzle diameter is 1 mm×1 mm. A slurry containing polygonal alumina powder is jetted from a nozzle, and the decorative sheet fixed to the table is sequentially cut from the surface protective layer. The jetting strength at this time is the displacement that was scraped with respect to the jetting amount of the slurry by cutting the existing Si wafer or PMMA substrate under the same experimental condition in advance (that is, the depth cut when spraying 1 g of the slurry). The standard projection force X is calculated from the above, and it is determined based on the value. In the present embodiment using the polygonal alumina powder, the projection force when the existing Si wafer is shaving 6.360 μm/g is set as the standard projection force X.

In this embodiment, in the case of polygonal alumina powder, X=1/100 projection force (projection force when scraping 0.064 μm/g on an existing Si wafer).
After washing the cut portion with water, the cutting depth, that is, the erosion depth Z is measured. The erosion depth Z is, for example, a stylus type surface shape measuring instrument (manufactured by Kosaka Laboratory Ltd./model PU-EU1/tip of a stylus R=2 μm/load 100 μN/measurement magnification 10,000/measurement length 4 mm/measurement The speed is 0.2 mm/sec). In the present embodiment, the erosion rate E [μm/g] is calculated by using the projected particle amount X′ [g] calculated from the above-mentioned projection force and the erosion depth Z [μm].

It is known that the erosion rate E is not affected by the magnitude of the erosion rate E of the lower layer existing in the depth direction when the erosion rate E is measured. Therefore, when measuring the erosion rate E, the MSE test may be performed in order from the first surface protective layer located on the outermost surface.
Further, in the present embodiment, the erosion rates E of the ionizing radiation curable resin and the thermosetting resin that form the surface protective layer are formed only by the layer formed of the ionizing radiation curable resin and the thermosetting resin. The erosion rate E measured for the different layers is used.

(Structure of makeup sheet)
Below, each structure of the decorative sheet of this embodiment is demonstrated. In addition, in this embodiment, the case where the surface protective layer has two layers will be described.
The decorative sheet shown in FIG. 1 has a surface protective layer (first surface protective layer) 4a, a surface protective layer (second surface protective layer) 4b, a transparent resin layer 1, an adhesive layer 6 (in order from the upper side of the drawing). A heat-sensitive adhesive layer, an anchor coat layer, a dry laminating adhesive layer), a pattern layer 2, an original layer 7, and a primer layer 5. More specifically, in the decorative sheet of the present embodiment, the pattern layer 2 is provided on one surface of the transparent resin layer 1, and the surface protective layer (the surface protective layer 4a and the surface protective layer 4a is provided on the other surface of the transparent resin layer 1). A decorative sheet having a layer 4b).

In order to improve the design, the embossed pattern 1a may be appropriately provided on the surface of the transparent resin layer 1 on the surface protective layer 4b side.
Further, the total thickness of the decorative sheet may be in the range of 80 μm or more and 250 μm or less.
Further, the decorative sheet of the present embodiment preferably does not contain a vinyl chloride resin. By using a decorative sheet made of a non-vinyl chloride resin, it is possible to reduce the risk of generating toxic gas or the like during incineration.
Hereinafter, details of each layer constituting the decorative sheet of the present embodiment will be described.

<Fabric layer>
The original fabric layer (original fabric) 7 is, for example, paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polystyrene, when imparting designability, scratch resistance and post-processing resistance to the decorative sheet. Synthetic resins such as polybutylene, polycarbonate, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol and acrylic, or foams of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene -Diene copolymer rubber, styrene-butadiene-styrene block copolymer rubber, rubber such as polyurethane, organic or inorganic non-woven fabric, synthetic paper, metal foil such as aluminum, iron, gold and silver Good. The original fabric layer 7 may be a sheet made of the same resin composition as the transparent resin layer 1. Of the above, polyolefin-based materials such as polypropylene and polyethylene are preferable.

Examples of the polyolefin-based resin contained in the raw fabric layer 7 include, in addition to polypropylene, polyethylene, polybutene, and the like, α-olefins (eg, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1- Octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3- Methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4- Ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, etc.) were homopolymerized or copolymerized with two or more kinds. Ethylene, vinyl acetate copolymer, ethylene/vinyl alcohol copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, ethylene/butyl methacrylate copolymer, ethylene/methyl acrylate copolymer , Ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, and the like, copolymerized with ethylene or α-olefin and other monomer.

When a substrate having an inactive surface such as a polyolefin-based material is used as the raw fabric layer 7, for example, corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment is applied to the front and back of the raw fabric layer 7. It is desirable to perform dichromic acid treatment. Further, a primer layer (not shown) may be provided between the original fabric layer 7 and the picture pattern layer 2 to ensure close contact.
When it is desired to impart a concealing property to the decorative sheet, a concealing colored sheet may be used for the original fabric layer 7, or a concealing layer may be used as an upper layer of the original fabric layer 7 and a lower layer of the pattern layer 2 (see FIG. (Not shown) may be provided. When a colored sheet is used as the raw fabric layer 7, a coloring agent can be added to the resin material forming the raw fabric layer 7 for coloring. As the colorant, for example, an inorganic pigment (titanium oxide, carbon black, or the like), an organic pigment (phthalocyanine blue, or the like), or a dye can be used. The colorant of the present embodiment can be used by selecting one kind or two or more kinds from publicly known or commercially available colorants, and the addition amount can be adjusted so that desired hiding property and designability can be obtained. ..
In the raw fabric layer 7, if necessary, for example, a filler, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, a crystal nucleating agent, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a coloring agent. Various additives such as agents and matting agents may be added.
The thickness of the raw fabric layer 7 is preferably in the range of 30 μm or more and 150 μm or less in consideration of printing workability and cost.

<Picture pattern layer/Hiding layer>
As a method for providing the pattern layer 2 and the hiding layer, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing or the like may be performed on the raw fabric layer 7 or the transparent resin layer 1. is there. Further, particularly when a concealing layer is applied, for example, a comma coater, a knife coater, a lip coater, metal vapor deposition or a sputtering method may be used. The concealing layer is generally provided above the original fabric layer 7 and below the picture pattern layer 2.

When an ink is used for forming the pattern layer 2, the binder contained in the ink is, for example, nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester-based, etc. Alternatively, it may be appropriately selected from each modified product. These may be aqueous, solvent-based, or emulsion type, and may be arbitrarily selected from a one-pack type and a two-pack type using a curing agent.
Further, it is also possible to cure the ink by irradiating it with ultraviolet rays or electron beams. Among them, the most general method is a method of curing with an isocyanate using a urethane-based ink.

In addition to the above-mentioned binder, pigments, colorants such as dyes, extender pigments, solvents, and various additives contained in ordinary ink may be added. Particularly frequently used pigments include, for example, condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, pearl pigments such as mica. In addition to the ink application, it is also possible to apply a design by vapor deposition or sputtering of various metals.

The material used for the hiding layer may be basically the same as the material for the pattern layer 2. Since the hiding layer needs to have a hiding property for its purpose, it is preferable to use, for example, an opaque pigment, titanium oxide, iron oxide or the like as the pigment. Further, in order to improve the hiding property, it is possible to add a metal such as gold, silver, copper or aluminum. Generally, flake-shaped aluminum is often added. When the coating thickness, that is, the thickness of the hiding layer is less than 2 μm, it is difficult to impart the hiding property, and when it exceeds 10 μm, the cohesive force of the resin layer becomes weak. Therefore, it is appropriate that the thickness of the hiding layer is in the range of 2 μm or more and 10 μm or less.

<Adhesive layer>
Any material can be selected for the adhesive layer 6, and examples of the bonding method using the adhesive layer 6 include thermal lamination, extrusion lamination, and dry lamination. The adhesive contained in the adhesive layer 6 can be selected from acrylic, polyester, polyurethane, and other materials. The adhesive contained in the adhesive layer 6 is usually a two-component curing type due to its cohesive force, and it is particularly preferable to use a urethane-based material obtained by a reaction with a polyol using an isocyanate.

An adhesive resin layer (not shown) may be provided between the adhesive layer 6 and the transparent resin layer 1. The adhesive resin layer may be provided particularly when an additional laminating strength is required in the extrusion laminating method. The transparent resin layer 1 and the adhesive resin layer are generally laminated and molded by a coextrusion method.
The resin contained in the adhesive resin layer is preferably, for example, polypropylene, polyethylene, acrylic resin or the like that has been subjected to acid modification, and the thickness thereof is preferably 2 μm or more for the purpose of improving the adhesive strength. When the thickness of the adhesive resin layer is less than 2 μm, it is difficult to obtain sufficient adhesive force. Further, if the thickness of the adhesive resin layer is too thick, the softness of the adhesive resin layer itself may affect the surface hardness of the transparent resin layer 1 having high crystallinity. Therefore, it is desirable that the thickness be 20 μm or less.

<Transparent resin layer>
The transparent resin layer 1 is formed on the adhesive layer 6, and the transparent resin layer 1 of this embodiment is a single layer. Since the transparent resin layer 1 has the specific erosion rate E, it becomes possible to provide a decorative sheet having excellent scratch resistance in a high load region.
Hereinafter, the transparent resin layer will be described in detail.
The transparent resin layer 1 is composed of a resin whose erosion rate E measured using polygonal alumina particles having an average particle diameter (D ₅₀ ) of 1.2 μm is adjusted to 0.05 μm/g<E<2 μm/g. There is. When the erosion rate E of the transparent resin layer 1 is 0.05 μm/g or less, the scratch resistance is significantly reduced, which is not preferable. When the erosion rate E of the transparent resin layer 1 is 2 μm/g or more, the weather resistance and the workability are significantly deteriorated, which is not preferable. The erosion rate E of the transparent resin layer 1 measured using polygonal alumina particles having an average particle diameter (D ₅₀ ) of 1.2 μm should be within a range of 0.1 μm/g<E<2 μm/g. Is more preferable.

The transparent resin layer 1 may be a sheet formed by film formation, or may be a laminate of already formed sheets. The transparent resin layer 1 is made of, for example, a highly crystalline polypropylene resin.
Further, one surface or both surfaces of the transparent resin layer 1 may be activated by, for example, corona treatment, plasma treatment, electron beam treatment, ultraviolet ray treatment, dichromic acid treatment or the like, if necessary. Further, if there is a problem with the adhesiveness of the concealing layer to the base material (base material such as wood boards, inorganic boards, metal plates to which the above decorative sheet is attached), the primer layer 5 may be appropriately provided in layers. I don't care.

When the transparent resin layer 1 is formed into a sheet by film formation, for example, a method using an extruder is generally used.
When the transparent resin layer 1 is laminated and molded, there is no particular restriction, and for example, a method applying heat and pressure, an extrusion laminating method, a dry laminating method or the like is generally used. When the embossed pattern 1a is applied, for example, a sheet which has been laminated by various methods is embossed by hot pressing afterwards, or an uneven pattern is provided on a cooling roll, and extrusion lamination is performed using the cooling roll. There is a method of embossing at the same time. More specifically, the embossed pattern 1a is directly applied to the transparent resin layer 1, for example, a highly crystalline polypropylene sheet, and the method is to use an embossed plate having an uneven pattern on the formed sheet by heat and pressure. There are a method of providing an embossed pattern, a method of providing an embossed film at the same time as cooling by using a cooling roll having an uneven pattern when forming a film using an extruder. Here, it is also possible to embed ink in the embossed pattern 1a as the embossed portion to further improve the design.
The embossed pattern 1a may be provided if necessary, and may be omitted if unnecessary.

The thickness of the transparent resin layer 1 is preferably in the range of 40 μm or more and 170 μm or less. If the thickness of the transparent resin layer 1 is less than 40 μm, the weather resistance and scratch resistance may decrease. When the thickness of the transparent resin layer 1 exceeds 170 μm, the manufacturing cost may increase and the flexibility may decrease.
In the transparent resin layer 1, if necessary, for example, a heat stabilizer, a flame retardant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a catalyst scavenger, and within a range that does not impair the characteristics of the present embodiment, For example, various additives such as a colorant, a light scattering agent, and a gloss adjusting agent can be added.

As the heat stabilizer, for example, phenol-based, sulfur-based, phosphorus-based, hydrazine-based, etc., as the flame retardant, aluminum hydroxide, magnesium hydroxide, etc., as the ultraviolet absorber, for example, benzotriazole-based, benzoate-based, As a light stabilizer such as a benzophenone-based or triazine-based light stabilizer, for example, a hindered amine-based light stabilizer or the like is generally added in an arbitrary combination. In particular, when it is used for this purpose, it is necessary to consider the weather resistance, and in that case, an ultraviolet absorber and a light stabilizer may be added to the transparent resin layer 1, and the addition amount is 100% in the transparent resin layer 1 respectively. An appropriate amount is within the range of 0.1% by mass or more and 2.0% by mass or less.

<Surface protection layer>
The surface protection layer of this embodiment includes a surface protection layer 4a and a surface protection layer 4b. When the surface protective layer 4a has a specific erosion rate E, it becomes possible to provide a decorative sheet having excellent surface scratch resistance.
Hereinafter, the surface protective layer will be described in detail.

The surface protective layer is composed of multiple layers. When the surface protective layer located on the outermost surface of the surface protective layer is referred to as "surface protective layer 4a" and the surface protective layer located below the surface protective layer 4a is referred to as "surface protective layer 4b", the surface protective layer 4a is , One or more ionizing radiation curable resins having an erosion rate E of 0.10 μm/g<E<0.45 μm/g measured using polygonal alumina particles having an average particle diameter (D ₅₀ ) of 1.2 μm And one or more thermosetting resins with 0.30 μm/g<E<0.6 μm/g. Further, the mass ratio of the ionizing radiation curable resin and the thermosetting resin forming the surface protective layer 4a (ionizing radiation curable resin/thermosetting resin) is 95/5 to 40/60. When the erosion rate E of the ionizing radiation curable resin is 0.10 μm/g or less, the erosion rate E of the thermosetting resin is 0.30 μm/g or less, and the ratio of the thermosetting resin is 5% or less. Is not preferable because the weather resistance is significantly reduced. When the erosion rate E of the ionizing radiation curable resin is 0.45 μm/g or more, the erosion rate E of the thermosetting resin is 0.6 μm/g or more, and the ratio of the thermosetting resin is 60% or more. Is not preferable because the scratch resistance is significantly reduced. The surface protective layer 4a and the surface protective layer 4b may be made of different resins.

The erosion rate E of the surface protective layer 4a measured using polygonal alumina particles having an average particle diameter (D ₅₀ ) of 1.2 μm is in the range of 0.2 μm/g<E<0.45 μm/g. Is more preferable. When the erosion rate E of the surface protective layer 4a is 0.2 μm/g or less, the weather resistance is significantly reduced, which is not preferable. When the erosion rate E of the surface protective layer 4a is 0.45 μm/g or more, the scratch resistance is significantly reduced, which is not preferable.
The thickness of the surface protective layer 4a may be in the range of 2 μm or more and 7 μm or less. When the thickness of the surface protective layer 4a is less than 2 μm, the coating method is limited and stable production becomes difficult, which may reduce the productivity. In addition, weather resistance and scratch resistance may decrease, and variations may increase. When the thickness of the surface protective layer 4a exceeds 7 μm, the balance between performance and cost may be lost and the cost may increase. In addition, flexibility may decrease.

The thickness of the surface protective layer 4b may be in the range of 2 μm or more and 14 μm or less. When the thickness of the surface protective layer 4b is less than 2 μm, the coating method is limited and stable production becomes difficult, which may reduce the productivity. In addition, weather resistance and scratch resistance may decrease, and variations may increase. When the thickness of the surface protective layer 4b exceeds 14 μm, the balance between performance and cost may be lost and the cost may increase. In addition, flexibility may decrease.
The thickness of the entire surface protective layer may be in the range of 4 μm or more and 21 μm or less. When the thickness of the entire surface protective layer is less than 4 μm, the coating method is limited and stable production becomes difficult, which may reduce productivity. In addition, weather resistance and scratch resistance may decrease, and variations may increase. If the total thickness of the surface protective layer exceeds 21 μm, the balance between performance and cost may be lost and the cost may increase. In addition, flexibility may decrease.

The method of providing the surface protective layer is the same as the method of providing the concealing layer and the pattern layer 2, and is not specified at all.
The surface protective layer contains a resin that is cured by irradiation with ultraviolet rays or electron beams, that is, an ionizing radiation curable resin, and a resin that is cured by heat, that is, a thermosetting resin. More specifically, the surface protective layer contains at least one ionizing radiation curable resin and at least one thermosetting resin. The content of the ionizing radiation-curable resin may be in the range of 65 parts by mass or more and 100 parts by mass or less of 100 parts by mass of the resin constituting the surface protection layer, particularly the surface protection layer 4a. When the content of the ionizing radiation curable resin is less than 65 parts by mass, the erosion rate E may increase and the scratch resistance may decrease.

The thermosetting resin can be appropriately selected from polyurethane-based, acrylic-based, acryl-silicone-based, fluorine-based, epoxy-based, vinyl-based, polyester-based, melamine-based, aminoalkyd-based, and urea-based resins, for example. The form may be any of aqueous, emulsion and solvent systems, and the curing may be a one-pack type or a two-pack type using a curing agent. Among them, urethane-based top coats utilizing the isocyanate reaction are desirable from the viewpoints of workability, cost, cohesive force of the resin itself, and the like.

Examples of the isocyanate include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), diphenylmethane diisocyanate (MDI), lysine diisocyanate (LDI), isophorone diisocyanate (IPDI), bis (isocyanate methyl). It can be appropriately selected and used from curing agents such as adducts, burettes, isocyanurates and various prepolymers, which are derivatives such as cyclohexane (HXDI) and trimethylhexamethylene diisocyanate (TMDI), but considering weather resistance. It is preferable to use a curing agent based on hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) having a linear molecular structure.

As the ionizing radiation curable resin, for example, a polyester acrylate-based resin, an epoxy acrylate-based resin, a urethane acrylate-based resin, an acrylic acrylate-based resin or the like can be appropriately selected and used. Also, it is preferable to use an acrylic acrylate type. As a method for curing the ionizing radiation curable resin, it is preferable to cure with an active energy ray such as ultraviolet ray or electron beam from the viewpoint of workability.
As the electron beam source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, and a metal halide lamp can be used. The wavelength of ultraviolet rays is preferably 180 nm to 400 nm.

Regarding the mixture of the thermosetting resin and the ionizing radiation curable resin, for example, a urethane resin obtained by reacting an acrylic polyol as the thermosetting resin with an isocyanate, and a urethane acrylate resin as the ionizing radiation curable resin. It is preferable to mix and use. By using the mixture of the thermosetting resin and the ionizing radiation curable resin, it is possible to improve the surface hardness and suppress the curing shrinkage.
The ionizing radiation curable resin constituting the surface protective layer, particularly the surface protective layer 4a, may have one or more kinds of components having a functional group of 6 or more and a mass average molecular weight of 1,000 or more. More preferably, it has at least 6 functional groups and contains at least one component having a mass average molecular weight of 1,000 or more and 20,000 or less. When the number of the functional groups of the ionizing radiation curable resin is less than 6, the crosslink density is small and the scratch resistance is significantly lowered, which is not preferable. If the mass average molecular weight of the ionizing radiation curable resin is less than 1,000, the surface condition during coating is significantly deteriorated, which is not preferable. If the mass average molecular weight of the ionizing radiation curable resin exceeds 20,000, the viscosity of the coating liquid increases and the coating suitability remarkably decreases, which is not preferable.

Resins other than the ionizing radiation curable resin, for example, thermosetting resins, have a larger erosion rate E than the ionizing radiation curable resin.
Further, in order to further improve weather resistance, an ultraviolet absorber and a light stabilizer may be appropriately added to the surface protective layer, particularly the surface protective layer 4a. Further, functional additives such as an antibacterial agent and an antifungal agent may be optionally added to impart various functions.
It is desirable to add an inorganic filler to the surface protective layer in order to improve the scratch resistance of the surface or to adjust the gloss accompanying the design property.

Examples of the inorganic filler include alumina, silica, boehmite, iron oxide, magnesium oxide, aluminosilicate, diamond, silicon nitride, silicon carbide, glass beads, calcium titanate, barium titanate, magnesium pyroporate, zinc oxide, silicon nitride. Zirconium oxide, chromium oxide, iron oxide, glass fiber, etc. may be added. As the inorganic filler, inorganic fine particles having an average particle diameter in the range of 1 μm or more and 30 μm or less can be used, and particularly, inorganic fine particles in the range of 1 μm or more and 10 μm or less are suitable. If the average particle size of the inorganic filler is less than 1 μm, it tends to be difficult to obtain a matting effect. This is because, in order to exert the matte effect, it is ideal that the particle size is as large as or larger than the thickness of the film (layer) to which the inorganic filler is added. If the average particle size of the inorganic filler is less than 30 μm, or more reliably less than 10 μm, the inorganic filler tends to fall off from the surface protective layer under high load conditions, the gloss tends to change, and the surface tends to deteriorate. ..

For example, when gravure printing is selected, a proper coating thickness for one layer is usually 2 μm to 12 μm. In this case, as described above, it is preferable to select an inorganic filler having a similar average particle diameter from the thickness that can be applied at one time or less. However, when the surface protective layer is composed of multiple layers, it is also possible to add an inorganic filler having an average particle diameter larger than the film thickness of the surface protective layer 4b located below.
The content of the inorganic filler may be in the range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin forming the surface protective layer 4a. If the content of the inorganic filler is less than 1 part by mass, the scratch resistance may decrease. When the content of the inorganic filler exceeds 20 parts by mass, the gloss of the surface is significantly reduced, which may impair the design. In addition, weather resistance and stain resistance may decrease.

It is desirable to apply a surface treatment to the inorganic filler. By subjecting the inorganic filler to a surface treatment, it is possible to strengthen the bond with the surface protective layer. In addition, an inorganic filler whose surface is untreated may be added to a surface protective layer located below such as the surface protective layer 4b.
Further, when the surface treatment is performed, it is desirable to have a functional group that imparts hydrophobicity to the surface of the inorganic filler and reactivity with the surface protective layer.
The method for carrying out the surface treatment of the inorganic filler is not particularly limited, and a known method can be selected.

As the surface treatment agent used for the surface treatment of the inorganic filler, at least one of a surfactant, a fatty acid metal salt, a silane coupling agent, silicone, wax, and a modified resin can be used. Examples of the surface treatment agent of the present embodiment include silicone oil-based agents, alkylsilazane-based agents, trimethylsilylating agents, alkoxysilane-based agents, siloxane and silane coupling agents, titanium coupling agents and phosphoric acid-fatty acid-based surface active agents. An agent or the like can be selected, and one kind or a combination of plural kinds may be used.
Examples of the silicone oil type treating agent include straight silicone oil (dimethyl silicone oil, methylphenyl silicone oil, etc.) and modified silicone oil (amino modified, epoxy modified, carboxyl modified, carbinol modified, methacryl modified, mercapto modified, phenol modified). , One-end reactive modification, different functional group modification, polyether modification, methylstyryl modification, alkyl modification, higher fatty acid ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid-containing modification, fluorine modified silicone oil, etc.) can do.

As the alkylsilazane-based treating agent, for example, hexamethyldisilazane, vinylsilazane or the like can be selected.
As the silane coupling agent, for example, methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, trimethylethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-hexyltriethoxysilane, n-octyltriethoxysilane, n-hexyltriethoxysilane, decyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, diethoxymethylphenyl Alkoxysilane compounds such as silane, allyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane and chlorosilane compounds such as trimethylchlorosilane and diethyldichlorosilane can be selected. ..

As the trimethylsilylating agent, an alkoxysilane compound in the silane coupling agent can be selected.
Examples of titanate coupling agents include isopropyl tridecyl benzene sulfonyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, tetraisopropyl bis(dioctyl phosphite) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra (2,2 diallyloxymethyl-1 butyl)bis(ditridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, etc. can be selected.
As the aluminate-based coupling agent, for example, acetoalkoxy aluminum diisopropylate can be selected.

As the surfactant, anionic, cationic, nonionic or amphoteric surfactant can be selected.
The method of surface treatment of the inorganic filler is not particularly limited. As the surface treatment method, any of a dry method, a wet method, and an integral blending method can be generally used. In the dry method, a surface-treating agent diluted with water or an organic solvent is added to an inorganic filler whose surface is not treated by spraying or the like, followed by stirring/curing and the like, and the reaction is allowed to proceed to obtain a surface-treated filler.

Further, when the surface of the transparent resin layer 1 on the surface protective layer side is provided with the embossed pattern 1a, the ink forming the surface protective layer 4a is embedded in the embossed pattern 1a by a wiping process to improve the design. It is also possible to let.
From the viewpoint of weather resistance, there is also a method of imparting weather resistance to the surface protective layer and the transparent resin layer 1 as described above in order to protect the transparent resin layer 1 as the base material. In addition to that, there is also a method of adding an ultraviolet absorber and a light stabilizer to the adhesive layer 6 and the pattern layer 2 itself in order to protect the pattern layer 2.
The addition amount of the photoinitiator is not particularly limited, and is preferably about 0.1 to 15 parts by mass with respect to 100 parts by mass of the base resin.

The type of photoinitiator is not particularly limited. In the case of a resin system having a radically polymerizable unsaturated group, examples of the photoinitiator include acetophenone system, benzophenone system, thioxanthones, benzoin, benzoin methyl ether, Michler benzoyl benzoate, Michler's ketone, diphenyl sulfide, dibenzyl disulfide. , Diethyl oxide, triphenylbiimidazole, isopropyl-N,N dimethylaminobenzoate and the like can be selected. Preferably, it is desirable to design by combining a plurality of types according to the light source and the production environment.
Further, in the case of a resin system having a cationically polymerizable functional group, as a photoinitiator, for example, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonate ester, a fryloxysulfoxonium diallyl iodosyl salt. At least one of these can be selected.

<Primer layer>
The material used for the primer layer 5 may be basically the same as the material for the pattern layer 2 and the hiding layer. Further, considering that the web is wound on the back surface of the decorative sheet, in order to avoid blocking and enhance the adhesion with the adhesive, the primer layer 5 is made of, for example, silica, alumina, magnesia. Inorganic fillers such as titanium oxide and barium sulfate may be added. The coating thickness, that is, the thickness of the primer layer 5 is intended to ensure close contact with the raw material layer 7 which is a base material, and therefore, it is appropriate that the thickness is within a range of 0.1 μm or more and 10.0 μm or less, and more preferable. Is in the range of 0.1 μm or more and 3.0 μm or less.
The primer layer 5 is necessary when the surface of the raw fabric layer 7 is inactive such as an olefin-based material, but is not particularly necessary when the surface is a base material having an active surface.

[Example]
(First embodiment)
Hereinafter, specific examples of the decorative sheet of the present invention will be examined.
In Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2, the same materials were used except for the surface protective layer 4a, and the surface protective layer 4b was formed by the following method.

<Preparation of transparent resin layer>
0.5 parts by mass of a hindered phenolic antioxidant (Irganox 1010; manufactured by BASF) and 100 parts by mass of a highly crystalline homopolypropylene resin, and a triazine ultraviolet absorber (CYASORB UV-1164; manufactured by SUNCHEM). And 0.5 parts by mass of a NOR type light stabilizer (Tinuvin XT850 FF; manufactured by BASF) are respectively mixed, and the resin is extruded using a melt extruder using an extruder to obtain a transparent resin layer 1 As a result, a transparent resin sheet made of highly crystalline polypropylene having a thickness of 100 μm, which was used as, was formed into a film. Subsequently, corona treatment was performed on both surfaces of the formed transparent resin sheet to adjust the surface wetting tension to 40 dyn/cm or more.

<Preparation of the pattern layer and primer layer on the original layer>
A pattern is printed on one surface of the 80 μm polyethylene sheet (raw fabric layer 7) having a hiding property by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.). The layer 2 was provided, and the primer layer 5 was provided on the other surface of the original layer 7.
<Laminating transparent resin layer and pattern layer>
Then, the transparent resin layer 1 was applied on the surface of the pattern layer 2 of the original layer 7 by applying an adhesive for dry lamination (Takelac A540; manufactured by Mitsui Chemicals, Inc.; coating amount 2 g/m ² ). It stuck by the dry laminating method through the agent layer 6.
<Preparation of embossed pattern>
The surface of the transparent resin layer 1 of this laminated sheet was pressed using a die roll for embossing to give an embossed pattern 1a.

<Preparation of Topcoat Agent D Used for Surface Protective Layer 4b>
The top coat agent D used in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 is composed mainly of the thermosetting resin D. The thermosetting resin D is an acrylic polymer having a glass transition temperature of about 100° C., a weight average molecular weight Mw of about 60,000 and a hydroxyl value of 16. The top coat agent D is based on 100 parts of the main agent, 5 parts of Tinuvin 479 (manufactured by BASF Ltd.) as an ultraviolet absorber, 3 parts of Tinuvin 123 (manufactured by BASF Ltd.) as a light stabilizer, and ethyl acetate as a diluting solvent. 50 parts, 15 parts of inorganic filler L-121 (manufactured by AGC SITEC Co., Ltd.) as a gloss adjusting agent, and 5 parts of duranate TAP-100 (manufactured by Asahi Kasei Co., Ltd.) as a curing agent were prepared.
<Preparation of surface protective layer 4b>
The top coat agent D was coated on the transparent resin layer 1 having the embossed pattern 1a at a coating amount of 10 g/m ² to form a surface protective layer 4b.

Hereinafter, the surface protective layer 4a of Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 was formed by the following method.
<Preparation of Top Coat Agents A, B, C Used for Surface Protective Layer 4a>
The top coat agents A, B and C used in Examples 1-1 to 1-4 and Comparative Example 1-2 are mainly composed of ionizing radiation curable resins A, B and C, respectively. The ionizing radiation curable resin A is a polyfunctional urethane acrylate oligomer having functional groups of 3 to 15, B to 2 to 9 and C to 1 to 6. Topcoat agents A, B, and C are 100 parts of each main agent, 5 parts of Tinuvin 479 (manufactured by BASF Ltd.) as an ultraviolet absorber, 3 parts of Tinuvin 123 (manufactured by BASF Ltd.) as a light stabilizer, and gloss. It was prepared by blending 8 parts of Silohobic 702 (manufactured by Fuji Silysia Chemical Ltd.) as a regulator and 50 parts of ethyl acetate as a diluting solvent.

<Comparative Example 1-1>
A thermosetting topcoat D agent was applied on the surface of the surface protective layer 4b at a coating amount of 5 g/m ² to form the surface protective layer 4a of Comparative Example 1-1.
<Comparative Example 1-2>
Ionizing radiation-curable top coat agent A and agent B and heat-curable top coat agent D were blended on the surface of the surface protective layer 4b at 24:6:70 and coated at a coating amount of 5 g/m ² for comparison. The surface protective layer 4a of Example 1-2 was formed.

<Example 1-1>
Ionizing radiation-curable top coat agent A and agent B and heat-curable top coat agent D were mixed on the surface of the surface protective layer 4b at 40:10:50 and coated at a coating amount of 5 g/m ² The surface protective layer 4a of Example 1-1 was formed.

<Example 1-2>
Ionizing radiation-curable top coat agent A and agent B and heat-curable top coat agent D were mixed on the surface of the surface protective layer 4b at a ratio of 64:16:20 and coated at a coating amount of 5 g/m ² The surface protective layer 4a of Example 1-2 was formed.
<Example 1-3>
On the surface of the surface protective layer 4b, an ionizing radiation-curable topcoat A agent and a thermosetting topcoat D agent were blended at 80:20, and coated at a coating amount of 5 g/m ² to obtain the composition of Example 1-3. The surface protection layer 4a was formed.
<Example 1-4>
The surface protection layer 4b of Example 1-4 was prepared by blending an ionizing radiation-curable top coat C agent and a thermosetting top coat D agent at 80:20 on the surface of the surface protective layer 4b and coating the mixture at 5 g/m ² . Layer 4a was formed.

Each of the decorative sheets obtained in Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-2 was attached to a wooden base material using a urethane adhesive, and then subjected to a Hoffman scratch test. -The surface hardness was determined by a coin scratch test and a steel wool rubbing test. The evaluation results are shown in Tables 1 to 3 below.

The test method of each evaluation test will be briefly described below.
<Hoffman scratch test>
The Hoffman scratch test is performed by using a Hoffman scratch hard nester (manufactured by BYK-Gardner) at a constant speed of 200 g for each 200 g and a test length of 5 cm for each load of 200 g to 2000 g. The load at which scratches and scratches on the surface of the decorative sheet occurred was shown.
◎: Hoffman scratch 1600 g or more ○: Hoffman scratch 1200 g or more and less than 1600 g △: Hoffman scratch 600 g or more and less than 1200 g ×: Hoffman scratch 600 g or less In this Hoffman scratch test, "◎", "○", and "△" were passed. did.

<Coin scratch test>
In the coin scratch test, a 100-yen or 10-yen coin is used, the angle of the coin is fixed to 45±1° with respect to the decorative sheet, and the coin is 1 kg to 5 kg (1 to 4 kg is 10 yen coin, 5 kg is 100 It is determined whether or not a scratch of 3 mm or more is formed on the decorative sheet by sliding it for 5 cm with a load of (yen coin) applied, and the load at which the scratch is formed is shown as the surface hardness of the decorative sheet.
⊚: Coin scratch 3 kg or more ◯: Coin scratch 2 kg or more, coin scratch less than 3 kg △: Coin scratch 1 kg or more, coin scratch less than 2 kg ×: Coin scratch less than 1 kg In this coin scratch test, “◎”, “○”, “△” Was accepted.

<Steel wool rubbing test>
The steel wool rubbing test is carried out by fixing a surface of each decorative sheet attached to a wooden base material with a jig while the steel wool is in contact with the surface, and applying a load of 500 g/cm ^{2 to} the jig. The surface of the decorative sheet was visually inspected for scratches by rubbing it at a constant speed and a distance of 50 mm for 50 reciprocations. As the steel wool, Bonster #0 (manufactured by Japan Steel Wool Co., Ltd.) was rolled into a 1 cm square and used.
⊚: No gloss change and scratches ◯: Slight gloss change can be confirmed, but no scratches Δ: Gloss change causes slight scratches ×: Gloss change causes numerous scratches In the steel wool rubbing test , "◎", "○", "△" were passed.
As is clear from Tables 2 to 3, the decorative sheets according to Examples 1-1 to 1-4 of the present invention have excellent balance in scratch resistance.
When the resin composition of the surface protective layer 4a contained 80% or more of the ionizing radiation-curable resin or contained a resin having a high crosslinking density, the erosion rate was small by E, and the result was particularly excellent in scratch resistance.

(Second embodiment)
Hereinafter, specific examples of the decorative sheet of the present invention will be examined.
In Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-2, the same materials were used except for the transparent resin layer, and they were formed by the following method.
<Preparation of transparent resin layer>
0.5 parts by mass of a hindered phenolic antioxidant (Irganox 1010; manufactured by BASF) and 100 parts by mass of a highly crystalline homopolypropylene resin, and a triazine ultraviolet absorber (CYASORB UV-1164; manufactured by SUNCHEM). And 0.5 parts by mass of a NOR type light stabilizer (Tinuvin XT850 FF; manufactured by BASF) are respectively mixed, and the resin is extruded using a melt extruder using an extruder to obtain a transparent resin layer 1 As a result, a transparent resin sheet made of highly crystalline polypropylene having a thickness of 100 μm, which was used as, was formed into a film. At this time, the crystallinity of the highly crystalline polypropylene was controlled to form the transparent resin sheets A, B, C and D in which the erosion rate E was adjusted.

Hereinafter, Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-2 were formed by the following method.
<Comparative Example 2-1>
A transparent resin sheet A having an erosion rate E adjusted to 0.047 μm/g was formed into a film.
<Example 2-1>
A transparent resin sheet B having an erosion rate E adjusted to 0.52 μm/g was formed into a film.
<Example 2-2>
A transparent resin sheet C having an erosion rate E adjusted to 1.4 μm/g was formed into a film.
<Comparative Example 2-2>
A transparent resin sheet D having an erosion rate E adjusted to 2.1 μm/g was formed.
Subsequently, corona treatment was applied to both surfaces of each film-formed transparent resin sheet to adjust the surface wetting tension to 40 dyn/cm or more.

<Preparation of the pattern layer and primer layer on the original layer>
A pattern is printed on one surface of the 80 μm polyethylene sheet (raw fabric layer 7) having a hiding property by a gravure printing method using a two-component urethane ink (V180; manufactured by Toyo Ink Co., Ltd.). The layer 2 was provided, and the primer layer 5 was provided on the other surface of the original layer 7.
<Laminating transparent resin layer and pattern layer>
The transparent resin sheets A, B, C, and D each having an adjusted erosion rate E on the surface of the pattern layer 2 of the raw fabric layer 7 are used for dry laminating adhesive (Takelac A540; manufactured by Mitsui Chemicals, Inc.; coating amount). 2 g/m ² ) was applied by the dry laminating method with the adhesive layer 6 interposed therebetween.

<Preparation of embossed pattern>
The surface of the transparent resin layer 1 of this laminated sheet was pressed using a die roll for embossing to give an embossed pattern 1a.
<Preparation of Topcoat Agent X Used for Surface Protective Layer 4b>
The top coat agent X is mainly composed of the thermosetting resin X. The thermosetting resin X is an acrylic polymer having a glass transition temperature of about 100° C., a weight average molecular weight Mw of about 60,000 and a hydroxyl value of 16. The topcoat agent X is based on 100 parts of the main agent, 5 parts of Tinuvin 479 (manufactured by BASF Ltd.) as an ultraviolet absorber, 3 parts of Tinuvin 123 (manufactured by BASF Ltd.) as a light stabilizer, and ethyl acetate as a diluent solvent. 50 parts, 15 parts of inorganic filler L-121 (manufactured by AGC SITEC Co., Ltd.) as a gloss adjusting agent, and 5 parts of duranate TAP-100 (manufactured by Asahi Kasei Co., Ltd.) as a curing agent were prepared.

<Preparation of surface protective layer 4b>
The top coat agent X was coated on the transparent resin layer 1 having the embossed pattern 1a at a coating amount of 10 g/m ² to form a surface protective layer 4b.
<Preparation of Topcoat Agent Y Used for Surface Protective Layer 4a>
The top coat agent Y is mainly composed of an ionizing radiation curable resin X. The ionizing radiation curable resin X is a polyfunctional urethane acrylate oligomer having 3 to 15 functional groups.
Topcoat agent Y is 100 parts of the main agent, 5 parts of Tinuvin 479 (manufactured by BASF Ltd.) as an ultraviolet absorber, 3 parts of Tinuvin 123 (manufactured by BASF Ltd.) as a light stabilizer, and Silopho as a gloss adjusting agent. 8 parts of Vic 702 (manufactured by Fuji Silysia Chemical Ltd.) and 50 parts of ethyl acetate as a diluent solvent were prepared.
<Preparation of surface protection layer 4a>
The top coat agent Y was applied on the surface of the surface protective layer 4b at a coating amount of 5 g/m ² to form the surface protective layer 4a.

Each of the decorative sheets obtained in Examples 2-1 to 2-2 and Comparative Examples 2-1 to 2-2 was attached to a wooden base material using a urethane adhesive, and then subjected to a Hoffman scratch test. -The surface hardness was determined by the coin scratch test. Further, the weather resistance was judged by a metal weather test. The evaluation results are shown in Table 4 below.
Since the Hoffman scratch test and the coin scratch test are described in the first embodiment, the description thereof will be omitted here.

The test method of the evaluation test regarding weather resistance will be briefly described below.
<Weather resistance test>
Using a weather resistance tester (Sunshine Weather Meter (SWOM): manufactured by Suga Test Instruments Co., Ltd.), a carbon arc weather resistance test according to JIS B 7753 was performed. Then, the time until cracks and whitening occurred on the surface of each decorative sheet was measured.
◎: weather resistance tester 2500 hours or more ○: weather resistance tester 2000 hours or more and less than 2500 hours △: weather resistance tester 1500 hours or more and less than 2000 hours ×: weather resistance tester less than 1500 hours In this weather resistance test, “⊚”, “∘”, and “Δ” were accepted.
As is clear from Table 4, the decorative sheets according to Examples 2-1 and 2-2 of the present invention have excellent balance of scratch resistance and weather resistance.
The decorative sheet of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the features of the invention.

DESCRIPTION OF SYMBOLS 1 Transparent resin layer 1a Embossed pattern 2 Design pattern layer 4a Surface protective layer 4b Surface protective layer 5 Primer layer 6 Adhesive layer 7 Original layer

Claims (6)

A decorative sheet comprising an original fabric, a transparent resin layer, and a surface protective layer in this order,
The surface protective layer is composed of a plurality of layers,
When the outermost surface protective layer of the surface protective layer is the first surface protective layer and the lower surface protective layer is the second surface protective layer,
The first surface protective layer is a kind in which the erosion rate E measured using polygonal alumina particles having an average particle diameter (D50) of 1.2 μm is 0.10 μm/g<E<0.45 μm/g. Containing the above ionizing radiation curable resin and one or more thermosetting resins in which 0.30 μm/g<E<0.6 μm/g,
A decorative sheet, characterized in that a mass ratio of the ionizing radiation curable resin and the thermosetting resin (ionizing radiation curable resin/thermosetting resin) is 95/5 to 40/60. The decorative sheet according to claim 1, wherein the erosion rate E of the first surface protective layer is 0.2 μm/g<E<0.45 μm/g. The ionizing radiation-curable resin of the first surface protective layer contains one or more kinds of components having a functional group of 6 or more and a mass average molecular weight of 1,000 or more. The decorative sheet according to 2. A decorative sheet comprising an original fabric, a transparent resin layer, and a surface protective layer in this order,
The transparent resin layer has an erosion rate E of 0.05 μm/g<E<2 μm/g measured using polygonal alumina particles having an average particle diameter (D50) of 1.2 μm. .. The erosion rate E of the transparent resin layer measured using polygonal alumina particles having an average particle diameter (D50) of 1.2 μm is 0.05 μm/g<E<2 μm/g. The decorative sheet according to any one of claims 1 to 3. The decorative sheet according to claim 4, wherein the erosion rate E of the transparent resin layer is 0.1 μm/g<E<2 μm/g.

Images