JP6520128B2 - Decorative sheet and decorative board - Google Patents

Description

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

  Conventionally, the designability is calculated | required by the interior material used for the interior of a building, and a decorative board is used as such an interior material. In particular, on the surface of a decorative board used for a floor surface, scratch resistance as well as design is required.

  Further, in the European and American cultures, it is usual to walk on the ground in the indoor space such as a house, so in consideration of scratch resistance, low-pressure melamine floors are mainly used for indoor floors in the US and Europe. However, the low-pressure melamine floor has a problem that the sound is likely to be heard during walking, and the touch is hard and cold.

  In recent years, instead of a low-pressure melamine floor, a floor (so-called hybrid floor) in which a decorative sheet of vinyl chloride resin is laminated to a chip board generally represented by cork as an adherend is used. With chip board, wood chips, bark, small-diameter logs, construction wastes discarded at dismantling construction site, etc. discarded in lumber factory are mechanically crushed into chips, and compression molded with synthetic resin adhesive. It is a base material obtained by shaping | molding to a board | plate material.

  The above-mentioned hybrid floor is environmentally friendly, excellent in sound insulation and heat insulating effects, and soft in touch by using a chip board as an adherend, and is produced by roll lamination by further laminating a decorative sheet. The property is improved, and the variation in color at the time of construction is suppressed. However, in Europe, in consideration of environmental problems, a decorative board not using a vinyl chloride resin is required.

  On the other hand, in Japan, as a decorative board not using a vinyl chloride resin, for example, a decorative board in which a decorative sheet using an olefin resin is bonded to an adherend is used. However, when such a decorative sheet is attached to an adherend such as a chip board to make a decorative board, there is a problem that the surface irregularities of the chip board appear on the surface of the decorative sheet and the surface of the decorative board is not smooth. (In addition, the uneven | corrugated shape which exposes to the decorative sheet surface by surface uneven | corrugated shapes, such as a chip board, is also called "duct"). In addition, when the smoothness of the surface of the decorative plate is improved by increasing the thickness of the decorative sheet, the decorative sheet is thick and inferior to the embossing shapeability, and when the emboss shape is shallow, it is attached to the adherend At the same time, there is a problem that the embossing occurs and the designability is reduced. In addition, when the thickness of the decorative sheet is increased, when the decorative sheet is stored in a roll state, there is a problem that roll lamination becomes difficult due to rolling.

  As a decorative sheet using an olefin resin, for example, on a substrate sheet, a pattern pattern layer, a transparent adhesive layer, a transparent resin layer and a transparent surface protective layer are sequentially provided, and a synthetic resin is formed on the back surface of the substrate sheet A manufacturing method of a decorative sheet for floor material having a backer layer, wherein the thickness of the transparent resin layer and the decorative sheet for floor material is set as a specific range, and a pattern pattern layer, a transparent adhesive layer and the like are formed on a substrate sheet. And forming a synthetic resin backer layer by extruding a molten resin with a specific range of thickness on the back surface of the base sheet of the intermediate sheet on which the transparent resin layer and the transparent surface protective layer are formed. The decorative sheet obtained by the manufacturing method of the decorative sheet for floorings which is obtained by the above-mentioned and at least 1 sort of the above-mentioned transparency resin layer and the synthetic resin backer layer contains a thermoplastic resin as a resin component is proposed For example, see Patent Document 1).

  Although a decorative board using such a decorative sheet is also an excellent decorative board, it is not assumed to walk on earth foot, and further scratch resistance is required. In particular, in recent years, work has been carried out to unify the design of the indoor floor and the outdoor wood deck, and make the entire room appear wider by eliminating steps, and sand is brought in from outside even when used as an interior material There is a problem that the sand is rubbed against the surface of the decorative plate by walking, resulting in abrasion of the floor surface under a low load (static pressure load), resulting in a gloss change such as gloss. Therefore, static load resistance is required for such a decorative board.

  Therefore, even if it adheres to adherends, such as a chip board, the appearance to the decorative board surface of the concavo-convex shape of the adherends concerned is controlled, and it was excellent in emboss shapeability and stuck to adherends. Embossed crushing during the process is suppressed, and even under conditions of use that walk on earth foot, it is excellent in scratch resistance, so rise in appearance is suppressed, and development of a cosmetic sheet excellent in curl resistance is also possible. It is desired.

Patent No. 5045180

  The present invention can also be used in Europe where regulation of vinyl chloride resin is in progress, etc., and even if it is bonded to an adherend such as a chip board, a surface of the adherend on the surface of the decorative plate with the uneven shape. Outage is suppressed, excellent in emboss shapeability, emboss collapse at the time of bonding to the adherend is suppressed, and scratch resistance is excellent even under use conditions such as walking on earth foot, An object of the present invention is to provide a decorative sheet which is suppressed in gloss change such as surface gloss and excellent in curl resistance.

As a result of intensive studies, the present inventors have found that it is a decorative sheet in which at least a design pattern layer, a transparent resin layer and a surface protective layer are laminated in this order on a substrate sheet. The surface protective layer contains fine particles A having a particle diameter smaller than the thickness of the surface protective layer, and fine particles B having a particle diameter larger than the thickness of the surface protective layer, and the content of the fine particles A and the content of the fine particles B The base sheet and the transparent resin layer contain a non-halogen thermoplastic resin, the thickness of the base sheet is in a specific range, and the Martens hardness is 50 N / mm ² or more. The above-mentioned base material sheet has a specific thickness of 120 μm or more on the side opposite to the surface on the side of the design pattern layer of the base sheet, and is embossed from the surface protective layer side. Seeing that you can achieve your goals And it has led to the completion of the present invention.

That is, the present invention relates to the following decorative sheet and decorative plate.
1. A decorative sheet in which at least a design pattern layer, a transparent resin layer and a surface protective layer are laminated in this order on a substrate sheet,
(1) The surface protective layer contains fine particles A having a thickness of 7 to 30 μm and having a particle diameter equal to or less than the thickness of the surface protective layer, and fine particles B having a particle diameter larger than the thickness of the surface protective layer.
(2) The content of the fine particles A and the content of the fine particles B are each 5 to 30 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer, and the content of the fine particles A and The total content of the fine particles B is 15 to 35 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer,
(3) The substrate sheet and the transparent resin layer contain a non-halogen thermoplastic resin,
(4) The substrate sheet has a thickness of 180 to 350 μm, and a region with a Martens hardness of 50 N / mm ² or more is from the surface on the side opposite to the surface on the pattern side of the substrate sheet. Exists in a thickness of 120 μm or more,
(5) Embossed from the surface protective layer side,
A cosmetic sheet characterized by
2. The decorative sheet according to Item 1, wherein the ten-point average roughness Rz _jis of the surface of the decorative sheet is 60 μm or more.
3. The decorative sheet according to Item 1 or 2, wherein the 60 ° gloss of the surface of the decorative sheet is 14 or less.
4. The decorative sheet according to any one of Items 1 to 3, wherein the fine particles A and the fine particles B are silica fine particles.
5. The decorative sheet according to any one of Items 1 to 4, wherein a gloss adjustment layer is formed on the transparent resin layer, and the gloss adjustment layer is formed adjacent to the surface protective layer. .
6. The decorative sheet according to any one of Items 1 to 5, wherein the non-halogen thermoplastic resin is an olefin thermoplastic resin.
7. 7. The decorative sheet according to any one of Items 1 to 6, wherein the surface protective layer comprises an ionizing radiation curable resin layer.
8. The decorative board formed by sticking the decorative sheet in any one of said claim | item 1-7 on a covering material.
9. 9. The decorative board according to item 8, wherein the adherend is a chip board or a composite base on which the chip board is laminated.

  The decorative sheet of the present invention can also be used in Europe where regulation of vinyl chloride resin is in progress, etc. Even if it is bonded to an adherend such as a chip board, the surface of the decorative plate with the uneven shape of the adherend Is suppressed, the embossing is excellent in shape and shape, the embossing collapse when bonded to the adherend is suppressed, and the scratch resistance is excellent even under the use conditions such as walking on earth foot It is possible to suppress the change in gloss such as surface glossiness and to be excellent in the curl resistance.

It is sectional drawing which shows an example of the decorative sheet of this invention. It is a figure which shows the measuring method of Martens hardness. Specifically, it is a view showing a diamond indenter (a) used in the measurement of Martens hardness in the present specification, a schematic view (b) of pressing operation, and an example (c) of pressing load and displacement. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed an example of the decorative sheet of this invention typically. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed an example of the decorative sheet of this invention typically. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which showed an example of the decorative sheet of this invention typically.

  In the decorative sheet of the present invention, (1) the surface protective layer has a thickness of 7 to 30 μm, and fine particles A having a particle diameter smaller than the thickness of the surface protective layer and a particle diameter larger than the thickness of the surface protective layer The particles B are contained, and (2) the content of the particles A and the content of the particles B are each 5 to 30 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer, and the particles The total of the content of A and the content of the fine particles B is 15 to 35 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer. It is excellent in quality, and in particular, the surface glossiness due to abrasion at low load is suppressed.

  That is, since the surface protective layer contains fine particles A having a particle diameter equal to or smaller than the thickness of the surface protective layer at a specific content, the surface gloss is low. In addition, since fine particles B having a particle diameter larger than the thickness of the surface protective layer are contained at a specific content, the fine particles B are excellent in scratch resistance by being pointed out from the surface protective layer. When the surface protective layer contains only the fine particles A, since the particle diameter is small, the resin forming the surface of the surface protective layer is easily scratched, and the scratch resistance is not sufficient. Further, when the surface protective layer contains only the fine particles B, the portion protruding from the surface protective layer of the fine particles B is rubbed and scraped off, and the gloss of the rubbed portion rises and becomes noticeable, so the scratch resistance (surface Suppression of glossiness) is not enough.

  In addition, (3) the decorative sheet contains a non-halogen thermoplastic resin in the base sheet and the transparent resin layer, so that the regulation of vinyl chloride resins is advanced in consideration of environmental problems. But it is possible to use.

In the decorative sheet, (4) the substrate sheet has a thickness of 180 to 350 μm, and a region having a martens hardness of 50 N / mm ² or more is a surface on the pattern layer side of the substrate sheet. And the surface of the adherend when the decorative sheet is adhered to an adherend such as a chip board to make a decorative board. The appearance of the shape on the surface of the decorative sheet is suppressed. For this reason, it is not necessary to increase the thickness of the decorative sheet in order to suppress the appearance of the surface irregularities of the adherend on the surface of the decorative sheet, and therefore, the emboss shape is excellent. Embossed crushing at the time of putting together is also suppressed, and the fall of the designability is suppressed. Further, as described above, since it is not necessary to increase the thickness of the decorative sheet, it is difficult to get curled even when stored in a roll state, and since it is excellent in curl resistance, roll lamination is possible.

  In addition, when the surface irregularities of the adherend are suppressed from appearing on the surface of the decorative sheet, the number of protruding portions on the surface of the decorative sheet is small, and the occurrence of scratches due to rubbing of the portions due to walking is suppressed. It will be excellent also in scratch resistance.

  Furthermore, since the decorative sheet is embossed from the side of the surface protective layer (5), the decorative sheet is excellent in design. Further, since the decorative sheet is embossed, the load is dispersed even when rubbed during walking, and the scratch resistance is also excellent.

  As mentioned above, since the decorative sheet of this invention is the above-mentioned composition, even if it sticks on adherends, such as a chip board, appearance to the decorative board surface of concavo-convex shape of the said adherends is controlled, It has excellent emboss shapeability, suppresses emboss crushing when attached to the adherend, and is excellent in scratch resistance even under conditions of walking on a foot, suppressing surface glossiness And excellent in curl resistance.

  Hereinafter, the decorative sheet of the present invention will be described in detail.

  FIG. 1 is a cross-sectional view showing an example of the decorative sheet of the present invention. In the decorative sheet 1 shown in FIG. 1, a design pattern layer 3, a transparent resin layer 4 and a surface protective layer 5 are laminated on a base sheet 2. The surface protective layer 5 contains fine particles A6 having a particle diameter equal to or less than the thickness of the surface protective layer 5, and fine particles B7 having a particle diameter larger than the thickness of the surface protective layer.

  Hereinafter, each layer which comprises the decorative sheet of this invention is demonstrated concretely.

The base sheet The base sheet is a layer in which a design pattern layer and the like are sequentially laminated on the surface (front surface). The substrate sheet contains a non-halogen thermoplastic resin.

  As the non-halogen thermoplastic resin, low density polyethylene (including linear low density polyethylene), medium density polyethylene, high density polyethylene, ethylene α-olefin copolymer, homopolypropylene, polymethylpentene, polybutene, ethylene-propylene Olefin-based thermoplastic resin such as copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, or a mixture thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene Thermoplastic ester-based resins such as naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate and polyarylate, methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, polyacrylic Thermoplastic acrylic resins butyl, nylon-6, polyamide-based thermoplastic resin such as nylon-66, or, polyimide, polyurethane, polystyrene, acrylonitrile - butadiene - styrene resin. These non-halogen thermoplastic resins may be used alone or in combination of two or more. Among them, an olefin-based thermoplastic resin is preferable in that it is excellent in printability and embossing aptitude of the image pattern layer and is inexpensive.

  The substrate sheet may be colored. In this case, a coloring material (pigment or dye) can be added to the non-halogen thermoplastic resin as described above to color it. As the colorant, for example, inorganic pigments such as titanium dioxide, carbon black, iron oxide and the like, organic pigments such as phthalocyanine blue and the like, and various dyes can also be used. One or more of these may be selected from known or commercially available products. Further, the addition amount of the coloring material may be appropriately set according to the desired color tone and the like.

  The substrate sheet may contain, if necessary, various additives such as a filler, a matting agent, a foaming agent, a flame retardant, a lubricant, an antistatic agent, an antioxidant, an ultraviolet absorber, and a light stabilizer. It may be done.

  The thickness of the substrate sheet is 180 to 350 μm. When the thickness of the substrate sheet is less than 180 μm, the appearance of the adherend on the surface of the decorative plate with the uneven shape can not be sufficiently suppressed. Moreover, when the thickness of a base material sheet exceeds 350 micrometers, when a decorative sheet is preserve | saved in a roll state, it will become difficult to roll, and roll lamination will become difficult. Although the thickness of a substrate sheet can be suitably set by the use of a final product, usage, etc. if it is in the above-mentioned range, 180-310 micrometers is preferable.

In the base sheet, a region having a Martens hardness of 50 N / mm ² or more exists with a thickness of 120 μm or more from the surface of the base sheet on the side opposite to the surface on the design pattern layer side. If the thickness of the region is less than 120 μm, the appearance of the adherend on the surface of the decorative plate with the uneven shape can not be sufficiently suppressed. It is preferable that the area | region whose said Martens hardness is 50 N / mm < ² > or more exists with a thickness of 120-250 micrometers from the surface on the opposite side to the surface by the side of the design pattern layer of a base material sheet. When the thickness of the said area | region is too thick, when a decorative sheet is preserve | saved in a roll state, there exists a possibility that roll lamination may become difficult by sticking.

The Martens hardness of the field which exists with a thickness of 120 micrometers or more from the field on the opposite side to the field by the side of the picture pattern layer of the substrate sheet is 50 N / mm ² or more in the substrate sheet.

In the present specification, Martens hardness is a value measured using a surface film physical property tester (PICODENTOR HM-500, manufactured by Fisher Instruments Inc.), and a specific measuring method is as follows. . In this measurement method, using a diamond indenter (Vickers indenter) shown in FIG. 2 (a), as shown in FIG. 2 (b), the diamond indenter is pushed into the measurement sample, and the diagonal of the pyramidal depression formed on the surface. The surface area A (mm ² ) is calculated from the length of and the hardness is determined by dividing the test load F (N). The pushing conditions are as follows: at room temperature (laboratory environment temperature), as shown in FIG. 2 (c), a load of 0 to 5 mN is first applied for 10 seconds, then held for 5 seconds with a 5 mN load, and finally 5 Perform unloading up to 0 mN in 10 seconds. And the hardness calculated | required by F / A based on the surface area A and the test load F is the said Martens hardness. In addition, in this specification, in order to avoid the influence of the hardness of layers other than a base material sheet, the Martens hardness of the cross section of a base material sheet was measured. In this case, the decorative sheet is embedded with a resin (cold-curing type epoxy two-component curing resin), allowed to stand at room temperature for 24 hours or longer and cured, and then the cured embedding sample is mechanically polished to obtain a substrate sheet The Martens hardness of the cross section was measured by exposing the cross section and pressing the diamond indenter into the cross section.

  The Martens hardness of the substrate sheet can be appropriately set by 1) mixing a plurality of resin components, 2) adding an elastomer to a resin, and the like.

The base sheet has a total thickness of 180 to 350 μm, and a region having a Martens hardness of 50 N / mm ² or more exists at a thickness of 120 μm or more from the surface of the base sheet opposite to the surface on the patterned layer side. If it is, it may be a single layer or may be formed of a plurality of layers.

As a layer configuration when the substrate sheet is formed of a plurality of layers, for example, a layer having a martens hardness of 50 N / mm ² or more is a single layer on the surface of the decorative sheet opposite to the surface on the patterned layer side. Thus, a layer having a martens hardness of less than 50 N / mm ² may be laminated on the surface of the layer on the pattern pattern layer side by a thickness of 120 μm or more. The layer having a Martens hardness of 50 N / mm ² or more may have a thickness of 120 μm or more by laminating a plurality of layers exhibiting the Martens hardness.

When the substrate sheet is a single layer, a region having a Martens hardness of 50 N / mm ² or more exists at a thickness of 120 μm or more from the surface of the substrate sheet on the opposite side to the surface on the patterned layer side The area on the pattern layer side may be configured to have an area in which the Martens hardness gradually decreases and becomes less than 50 N / mm ² .

  The substrate sheet may be subjected to a corona discharge treatment on the surface (front surface) in order to enhance the adhesion of the ink forming the design pattern layer. The method and conditions of the corona discharge treatment may be implemented according to known methods. In addition, if necessary, the back surface of the substrate sheet may be subjected to a corona discharge treatment, or a back surface primer layer described later may be formed.

Pattern-pattern layer The pattern-pattern layer is a layer for imparting a desired pattern (design) to a decorative sheet, and the type of pattern etc. is not limited. Examples include wood grain patterns, leather patterns, stone patterns, grain patterns, tile patterns, brickwork patterns, grain patterns, geometric figures, characters, symbols, abstract patterns, and the like.

  The formation method of the picture pattern layer is not particularly limited. For example, an ink obtained by dissolving (or dispersing) a known colorant (dye or pigment) in a solvent (or dispersion medium) together with a binder resin is used. It may be formed on the surface of the substrate sheet by a printing method. As the ink, an aqueous composition can also be used from the viewpoint of reducing the VOC of the decorative sheet.

  Examples of coloring agents include inorganic pigments such as carbon black, titanium white, zinc flower, red iron oxide, red iron oxide, azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments And organic pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxychloride; fluorescent pigments; nightlight pigments and the like. These colorants can be used alone or in combination of two or more. These colorants may be used together with fillers such as silica, extender pigments such as organic beads, neutralizing agents, surfactants and the like.

  As the binder resin, in addition to polyester-based urethane resin subjected to hydrophilic treatment, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative An alcohol adduct of a styrene-maleic anhydride copolymer, a cellulose resin and the like can also be used in combination. More specifically, for example, polyacrylamide resin, poly (meth) acrylic acid resin, polyethylene oxide resin, poly N-vinyl pyrrolidone resin, water soluble polyester resin, water soluble polyamide resin, water soluble amino Water-soluble natural polymers such as base resins, water-soluble phenolic resins and other water-soluble synthetic resins; polynucleotides, polypeptides, polysaccharides, etc. can also be used. Further, for example, natural rubber, synthetic rubber, polyvinyl acetate resin, (meth) acrylic resin, polyvinyl chloride resin, polyurethane-polyacrylic resin, etc. modified or a mixture of the above-mentioned natural rubber etc., and the like Resins can also be used. The above binder resins can be used alone or in combination of two or more.

  Examples of the solvent (or dispersion medium) include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane; ethyl acetate, butyl acetate, acetic acid-2-methoxyethyl, acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol and propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone Organic solvents; Ether solvents such as diethyl ether, dioxane, tetrahydrofuran, etc .; Dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene, etc. Containing organic solvent; inorganic solvents such as water. These solvents (or dispersion media) can be used alone or in combination of two or more.

  As a printing method used for formation of a picture pattern layer, a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, an inkjet printing method etc. are mentioned, for example. In the case of forming a solid patterned pattern layer, for example, a roll coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, a flow coating method, dip Various coating methods such as a coating method can be mentioned. In addition, the hand-painting method, the ink flow method, the photography method, the transfer method, the laser beam drawing method, the electron beam drawing method, the partial vapor deposition method such as metal, the etching method, etc. Good.

  The thickness of the image pattern layer is not particularly limited and can be set appropriately according to the product characteristics, but the layer thickness at the time of coating is about 1 to 15 μm, and the layer thickness after drying is about 0.1 to 10 μm.

Transparent Resin Layer The transparent resin layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and semitransparent. The transparent resin layer contains a non-halogen thermoplastic resin.

  As the non-halogen thermoplastic resin, low density polyethylene (including linear low density polyethylene), medium density polyethylene, high density polyethylene, ethylene α-olefin copolymer, homopolypropylene, polymethylpentene, polybutene, ethylene-propylene Olefin-based thermoplastic resin such as copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified product, or a mixture thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene Thermoplastic ester-based resins such as naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate and polyarylate, methyl polymethacrylate, ethyl polymethacrylate, ethyl polyacrylate, polyacrylic Thermoplastic acrylic resins butyl, nylon-6, polyamide-based thermoplastic resin such as nylon-66, or, polyimide, polyurethane, polystyrene, acrylonitrile - butadiene - styrene resin. These non-halogen thermoplastic resins may be used alone or in combination of two or more. Among them, an olefin-based thermoplastic resin is preferable in that it is excellent in printability and embossing aptitude of the image pattern layer and is inexpensive.

  The transparent resin layer may be colored as long as it has transparency, but it is preferable not to mix a colorant.

20-40 N / mm < ² > is preferable and, as for the Martens hardness of a transparent resin layer, 30-40 N / mm < ² > is more preferable. When the martens hardness of the transparent resin layer is too high, the decorative sheet may be inferior in curl resistance, and when too low, when the decorative sheet and the adherend are laminated to form a decorative board, the adherend The surface asperity shape may be easily exposed on the surface of the decorative plate.

  The thickness of the transparent resin layer is preferably about 20 to 200 μm, and more preferably 80 to 100 μm. The above range may be exceeded depending on the use of the decorative sheet and the like.

Surface Protective Layer The decorative sheet of the present invention has a surface protective layer formed on the surface. The thickness of the surface protective layer of the decorative sheet of the present invention is 7 to 30 μm. When the thickness of the surface protective layer is thinner than 7 μm, it becomes difficult to shape the embossed shape, and the design is inferior. In addition, when the thickness of the surface protective layer is thinner than 7 μm, the embossed shape is not sufficiently shaped, so that the load when the surface of the decorative sheet rubs is not easily dispersed, and the scratch resistance is poor. Moreover, when the thickness of a surface protective layer exceeds 30 micrometers, when a decorative sheet is preserve | saved in a roll state, it will roll, and roll lamination will become difficult. The thickness of the surface protective layer is preferably 10 to 20 μm.

  When the decorative sheet of the present invention has a gloss adjustment layer described later, the surface protective layer is formed to be adjacent to the gloss adjustment layer. Specifically, the back surface and / or the side surface of the surface protective layer are adjacent to the gloss adjusting layer. When the decorative sheet of the present invention has a gloss adjusting layer, the surface protective layer is preferably transparent.

  The surface protective layer contains fine particles A having a particle diameter equal to or less than the thickness of the surface protective layer, and fine particles B having a particle diameter larger than the thickness of the surface protective layer. In this specification, it is confirmed by SEM (scanning electron microscope) that the particle diameter of the fine particles A is equal to or less than the thickness of the surface protective layer, and the particle diameter of the fine particles B is larger than the thickness of the surface protective layer. For example, the decorative sheet can be cut in the direction perpendicular to the surface, and the location of the surface protective layer of the obtained cross section can be confirmed by observing using a SEM (scanning electron microscope).

  The particle diameter of the fine particles A is not particularly limited as long as it is equal to or less than the thickness of the surface protective layer. When the particle diameter of the fine particles A exceeds the thickness of the surface protective layer, the matting effect is not sufficient, and the fine particles A come out of the surface protective layer and come out of the surface protective layer of the fine particles A The part where it is rubbed and scraped off, the gloss of the rubbed part rises and becomes noticeable, and the scratch resistance is not sufficient.

  3-15 micrometers is preferable and, as for the particle diameter of the said microparticles | fine-particles A, 8-12 micrometers is more preferable. If the particle size of the fine particles A is too small, the matting effect may not be sufficient.

  The content of the fine particles A is 5 to 30 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer. When the content of the fine particles A is too large, the fine particles A raised from the surface protective layer increase, and when the raised portion is rubbed and scraped off, the gloss of the rubbed part is raised and becomes noticeable, and the scratch resistance is It will not be enough. If the content of the fine particles A is too small, the matting effect is not sufficient. The content of the fine particles A is preferably 10 to 20 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer.

  The particle diameter of the fine particles B is not particularly limited as long as it is larger than the thickness of the surface protective layer. When the particle diameter of the particles B is equal to or less than the thickness of the surface protective layer, the scratch resistance of the surface protective layer is not sufficient.

  8-33 micrometers is preferable and, as for the particle diameter of the said microparticles | fine-particles B, 8-20 micrometers is more preferable. If the particle diameter of the particles B is too large, it may be easily detached from the surface protective layer.

  The content of the fine particles B is 5 to 30 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer. When the content of the fine particles B is too large, when the head of the fine particles B is rubbed and scraped off, the gloss of the rubbed part is raised and becomes noticeable, and the scratch resistance is not sufficient. In addition, when the content of the fine particles B is too small, the scratch resistance of the surface protective layer is not sufficient. The content of the fine particles B is preferably 10 to 20 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer.

  In the present specification, the particle sizes of the above-mentioned fine particles A and B can be measured by SEM (scanning electron microscope), and for example, the surface of the cross section obtained by cutting the decorative sheet in the direction perpendicular to the surface It can be measured by photographing an arbitrary part of the protective layer using an SEM (scanning electron microscope) and averaging the particle diameter of the fine particles A and the particle diameter (diameter) of the fine particles B reflected.

  The total of the content of the fine particles A and the content of the fine particles B is 15 to 35 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer. When the total of the content of the fine particles A and the content of the fine particles B is too small, the surface protective layer is inferior to scratch resistance and design property (low gloss), and when the total content is too large, the fine particles A and B When the part is scuffed and scraped off, the gloss of the rubbed part rises and becomes noticeable, and the scratch resistance is not sufficient. The total content of the fine particles A and the content of the fine particles B is preferably 20 to 35 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer.

The fine particles A and B can impart scratch resistance to the surface protective layer according to the particle diameter, and are not particularly limited as long as they can exhibit a matting effect, and conventionally known particles can be used. As the fine particles A and B, for example, silica fine particles, inorganic particles such as silicone resins; crosslinked alkyl, crosslinked styrene, base Nzoguanamin resins, urea - formaldehyde resins, phenolic resins, polyethylene, organic particles such as nylon. Among these, silica fine particles are preferable.

  The resin component contained in the surface protective layer is not limited, but preferably contains an ionizing radiation curable resin or a two-component curable urethane resin. Substantially, those formed of these resins are preferred. When the surface protective layer is formed of an ionizing radiation curable resin or a two-component curable urethane resin, the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance and the like of the decorative sheet can be easily improved. Among these, ionizing radiation curable resins are more preferable.

  The ionizing radiation-curable resin is not particularly limited, and is a prepolymer (including an oligomer) and / or a monomer containing a radically polymerizable double bond capable of undergoing a polymerization crosslinking reaction by irradiation of ionizing radiation such as ultraviolet light and electron beam. Transparency resin which has as a main component can be used. These prepolymers or monomers can be used singly or in combination of two or more. The curing reaction is usually a crosslinking curing reaction.

  Specifically, as the prepolymer or the monomer, a compound having a (meth) acryloyl group, a radically polymerizable unsaturated group such as a (meth) acryloyloxy group, a cationically polymerizable functional group such as an epoxy group or the like in the molecule Can be mentioned. Also preferred is a polyene / thiol based prepolymer which is a combination of polyene and polythiol. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  As a prepolymer having a radically polymerizable unsaturated group, for example, polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone (meth) acrylate Etc. As these molecular weight, about 250-100,000 are preferable normally.

  As a monomer which has a radically polymerizable unsaturated group, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate etc. are mentioned as a monofunctional monomer, for example. Moreover, as a polyfunctional monomer, for example, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( Examples include meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.

  Examples of prepolymers having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac epoxy compounds, and prepolymers of vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Further, examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. As polyene, what added allyl alcohol to the both ends of the polyurethane by diol and diisocyanate is mentioned, for example.

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

  The two-component curable urethane resin is not particularly limited, but among them, a polyol component having an OH group as a main component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) and an isocyanate component as a curing agent component (tolylene) What contains isocyanate, hexamethylene diisocyanate, metaxylene diisocyanate etc. can be used.

  About the resin of the said illustration, 1 type (s) or 2 or more types can be used together and used.

  It is preferable to add an ultraviolet absorber such as benzotriazole, benzophenone, salicylate or triazine to the surface protective layer in order to improve the weather resistance. When the resin layer is cured by irradiation with ultraviolet light, acetophenones, benzophenones, Michler's benzoyl benzoate, α-aminoxime esters, tetramethylthiuram monosulfide, thioxanthones, aromatic diazonium salts as photopolymerization initiators Aromatic sulfonium salts, metallocenes, etc., and n-butylamine, triethylamine, tri-n-butylphosphine, etc. can be used as photopolymerization accelerators (sensitizers).

  Further, an antibacterial agent may be added to the surface protective layer in order to impart antibacterial properties. The antibacterial agents include inorganic antibacterial agents and organic antibacterial agents. In particular, inorganic antibacterial agents are desirable because they are generally safer than organic antibacterial agents, and excellent in durability and heat resistance. The inorganic antibacterial agent is one in which antibacterial metals such as silver and other copper, zinc and the like are supported on various inorganic carriers. The addition amount of the antibacterial agent is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the resin component.

  If necessary, various additives such as solvents, colorants such as dyes and pigments, fillers such as extenders, antifoaming agents, leveling agents, and agents imparting thixotropy can be added to the surface protective layer. .

The surface protective layer is formed, for example, by applying an ionizing radiation curable resin or a two-component curable urethane resin on the transparent resin layer or on a gloss adjustment layer described later by a known coating method such as gravure coating or roll coating, It can be formed by curing the resin. Here, when forming a surface protective layer in a part of surface of the face side of a decorative sheet, the resin composition for surface protective layer formation is partially applied (for example, in the shape of a pattern), and then the above The surface protective layer can be formed by curing the ionizing radiation curable resin in the resin composition. When the surface protective layer is formed on the entire front surface side of the decorative sheet, the resin composition for forming a surface protective layer is coated on the entire surface (over the entire surface), and then ionizing radiation in the resin composition is obtained. The surface protective layer can be formed by curing the curable resin.
The gloss value of the surface protective layer can be adjusted by a method of selecting the type of each substance such as a resin component and an additive contained in the surface protective layer; a method of appropriately setting the content of each of the above substances; .

(Layer composition of makeup sheet)
The decorative sheet of the present invention is not limited as to its specific configuration (layer configuration) as long as at least a design pattern layer, a transparent resin layer and a surface protective layer are laminated in this order on the base sheet. For example, a decorative sheet formed by sequentially laminating a design pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer on a substrate sheet can be mentioned. In this specification, the direction in which the surface protective layer is laminated as viewed from the base sheet is referred to as "upper" or "front surface", and the direction in which the back surface primer layer is laminated as viewed from the base sheet It is called "below" or "back side". The "front surface (side)" or the "surface of the surface protective layer (side)" of the decorative sheet or plate means a surface visually recognized after the application of the decorative sheet or plate.

  Hereinafter, the base sheet, the pattern-patterned layer, the transparent resin layer, and the layers other than the surface protective layer described above will be specifically described using the decorative sheet having such a layer configuration as a representative example.

Transparent Adhesive Layer In order to enhance the adhesion between the transparent resin layer and the patterned layer, the transparent adhesive layer may be formed on the patterned layer. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of colorless and transparent, colored and transparent, and semitransparent.

  The adhesive is not particularly limited, and an adhesive known in the field of decorative sheets can be used. Examples of adhesives known in the field of decorative sheets include thermoplastic resins such as polyamide resins, acrylic resins and vinyl acetate resins, and thermosetting resins such as urethane resins. These adhesives can be used individually by 1 type or in combination of 2 or more types. In addition, a two-part curable polyurethane resin or polyester resin having an isocyanate as a curing agent can also be applied.

  The thickness of the transparent adhesive layer is not particularly limited, but the thickness after drying is about 0.1 to 30 μm, preferably about 1 to 20 μm.

Primer Layer The primer layer may be provided on the transparent resin layer. The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. As a primer agent, for example, a urethane resin based primer consisting of an acrylic modified urethane resin (acrylic urethane based resin) etc., a urethane-cellulose based resin (eg a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) And a resin based primer comprising a block copolymer of acryl and urethane. Additives may be added to the primer if necessary. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet light absorbers, light stabilizers and the like. The compounding amount of the additive can be appropriately set according to the product characteristics.

Although the application amount of the primer agent is not particularly limited, it is usually about 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  The thickness of the primer layer is not particularly limited, but is usually about 0.01 to 10 μm, preferably about 0.1 to 1 μm.

Gloss Adjusting Layer A gloss adjusting layer may be formed on the decorative sheet of the present invention. As a form of the decorative sheet in which the gloss adjustment layer is formed, the form of FIGS. 3-5 is mentioned, for example.

  When the gloss adjusting layer is formed on the decorative sheet of the present invention, the gloss adjusting layer is formed on the transparent resin layer so as to be adjacent to the above-mentioned surface protective layer. More specifically, the back surface of the gloss adjusting layer is adjacent to the front surface of the transparent resin layer (or, when the decorative sheet of the present invention has the primer layer, the primer layer), and The front surface and / or the side surface of the gloss adjusting layer is adjacent to the surface protective layer.

  The gloss adjustment layer may be formed on a part of the surface of the front surface side (the surface side to be visually recognized after the application of the decorative sheet or the decorative plate) from the viewpoint of the design property, (2 2.) It may be formed on the entire surface (entire surface) of the front surface side. That is, the gloss adjusting layer may be partially formed on the basis of (1) the surface on the front side, and (2) formed over the whole on the basis of the surface on the front side It may be done.

When the (1) gloss adjusting layer is formed on a part of the surface on the front side, (a) the surface protective layer may be formed on a part of the surface on the front side, The (b) surface protective layer may be formed on the entire surface on the front side. When both the gloss adjusting layer and the surface protective layer are formed on a part of the surface on the front side (in the case of (a) of the above (1)), the surface adjusting layer is formed of the gloss adjusting layer It is formed in such a way as to fill the non-existing area (the non-existent area).
In the embodiment of FIG. 3, the gloss adjustment layer is formed on a part of the surface on the front surface side, and the surface protective layer is formed on the entire surface on the front surface side ((1) form of b)). In the embodiment of FIG. 4, the gloss adjusting layer is formed on a part of the surface on the front side, and the surface protective layer is formed on a part of the surface on the front side (above (1)) Form of (a)).

  On the other hand, when the (2) gloss adjusting layer is formed on the entire surface on the front surface side, the surface protective layer is formed on a part of the surface on the front surface side. In the embodiment of FIG. 5, the gloss adjustment layer is formed on the entire surface on the front side, and the surface protective layer is formed on part of the surface on the front side (the above-mentioned embodiment (2)) ).

Here, the gloss value of the gloss adjustment layer is G _A , and the gloss value of the surface protective layer is G _P. When the decorative sheet of the present invention has a gloss adjusting layer, the relationship between the gloss value G _A of the gloss adjusting layer and the gloss value G _P of the surface protective layer described above is G _P ≠ G _A. Here, the G _P and the G _A in the present specification is a value measured according to Japanese Industrial Standard JIS Z8741. Specifically, in the present invention, the gloss value is measured under the condition of an incident angle of 60 ° using PG-3D manufactured by Nippon Denshoku Kogyo Co., Ltd. as a gloss meter. In the present specification, the gloss value is also referred to as gloss value or gloss value.

Either (1) when the gloss adjustment layer is formed on a part of the surface on the front side, or (2) when the gloss adjustment layer is formed on the entire surface of the front side Even in the case where the decorative sheet or the decorative plate is viewed after application, both the gloss adjusting layer and the surface protective layer are visible, and the gloss value of each of the gloss adjusting layer and the surface protective layer The relationship is G _P ≠ G _A. Therefore, when the decorative sheet of the present invention is attached to an adherend, the influence of the uneven shape (duct) generated on the surface of the decorative sheet is further suppressed, and the designability of the decorative sheet or the decorative plate is improved. Therefore, the decorative sheet of the present invention in which the gloss adjusting layer is formed is a preferred embodiment of the present invention.

Next, the case where the (1) gloss adjusting layer is formed on a part of the surface on the front side (simply referred to as the case of the above (1)) will be described. In the case of the above (1), the ratio of the area of the area in which the gloss adjustment layer is formed to the area of 1 cm ² of the front surface of the decorative sheet or the decorative plate is preferably 20 to 80%. In this case, it is preferable that the gloss adjustment layer is formed so that the front surface (surface to be recognized) side of the gloss adjustment layer has a pattern. When the gloss adjustment layer is pattern-like and the ratio of the area is 20 to 80%, the gloss difference between the gloss adjustment layer and the surface protective layer becomes clearer, and as a result, the designability is further improved, and The influence of the uneven shape can be further suppressed. In addition, when a gloss adjustment layer is formed so that it may become the said pattern shape, the kind of said pattern is not specifically limited. As a specific type of the pattern, for example, those similar to various patterns exemplified in the above-mentioned pattern layer can be mentioned.

In the present specification, the ratio of the area of the area where the gloss adjustment layer is formed (the area where the gloss adjustment layer is present) to the area of 1 cm ² of the front surface of the decorative sheet or the decorative plate is It may be called an occupied area ratio. The occupied area ratio of the gloss adjusting layer is calculated from plate making data at the stage of producing a plate for forming the gloss adjusting layer. The occupied area ratio of the gloss adjusting layer can also be calculated from the shape of the plate.

For the (1), in order to the uneven shape of the impact to further suppress (the further inconspicuous irregularities), the relationship between G _A and the G _P is G _{A <G P} is preferred. More preferably, G _A <G _P and G _A ≦ 5.

  Next, the case where the (2) gloss adjusting layer is formed on the entire surface on the front side (simply referred to as the case of the above (2)) will be described. In the case of the above (2), the surface protective layer is formed on a part of the surface on the front side. In this case, it is preferable that the surface protective layer be formed such that the front surface (surface to be viewed) side of the surface protective layer has a pattern. Thereby, the gloss difference between the gloss adjustment layer and the surface protective layer becomes clearer, and as a result, the designability can be further improved and the influence of the uneven shape can be further suppressed. When the surface protective layer is formed to have the pattern shape, the type of the pattern is not particularly limited. As a specific type of the pattern, for example, those similar to various patterns exemplified in the above-mentioned pattern layer can be mentioned.

For the (2), in order to the uneven shape of the impact of further suppressing (inconspicuous further the uneven shape), the relationship of G _A and the G _P | is preferably ≧ 2 _| G _P -G A _{, | G P -G a | ≧} 10 and more preferably (in other words, it is the difference in gloss values of gloss values luster control layer and the surface protective layer is 2 or more preferably, the difference is 10 or more preferable). The relationship between the _{G A} and the _{G P may} be a G A _{<G P,} or _may be a G P _{<G A.} That is, the gloss adjusting layer may have a lower gloss than the surface protective layer, and the surface protective layer may have a lower gloss than the gloss adjusting layer (note that G _A < _GP ). In the case where the gloss adjustment layer is a low gloss layer and the surface protective layer is a low gloss layer when G _P <G _A ). In the case of the above (2), it is preferable that the ratio of the area of the area where the low gloss layer exists to the area of 1 cm ² of the front surface of the decorative sheet or the decorative plate exceeds 50%.

In the present specification, the ratio of the area of the region where the surface protective layer is formed (the region where the surface protective layer is present) to the area of 1 cm ² of the front surface of the decorative sheet or the decorative plate is It may be called an occupied area ratio. The occupied area ratio of the surface protective layer is calculated from plate making data at the stage of producing a plate for forming the surface protective layer. The occupied area ratio of the surface protective layer can also be calculated from the shape of the plate. On the other hand, the ratio of the area of the area where the low gloss layer is exposed (the exposed area ratio of the low gloss layer) to the surface area of 1 cm ^{2 of} the decorative sheet or the decorative plate is (i) low When the glossy layer is a surface protective layer, the occupied area ratio of the surface protective layer becomes the occupied area ratio of the low gloss layer as it is, and (ii) the low gloss layer is a gloss adjustment layer, the above After calculating the occupied area ratio of the surface protective layer, it can be obtained by subtracting (minus) the occupied area ratio of the surface protective layer with respect to 100 (%).

  The method of forming the gloss adjusting layer is not particularly limited, and, for example, it is dissolved (or dispersed) in a solvent (or dispersion medium) together with a known coloring agent (dye, pigment, etc.), vehicle, etc. It can be formed by the ink obtained by As the coloring agent and the solvent, the same coloring agents and solvents as exemplified for the coloring agent and the solvent in the above-mentioned pattern layer can be used, respectively.

  As a vehicle of the ink which forms a gloss adjustment layer, what contains 50 mass% or more of urethane type resin and / or polyvinyl acetal type resin is preferable. The urethane resin includes, as a polyol component, a polyol such as acrylic polyol, polyester polyol and polyether polyol, and as an isocyanate component, an aromatic isocyanate such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, Listed are urethane resins (which may be crosslinked linearly or crosslinked) which may be reacted with an isocyanate such as an aliphatic or alicyclic isocyanate such as hydrogenated tolylene diisocyanate. be able to. Moreover, polyvinyl acetal type resin is obtained by condensation (acetalization) of polyvinyl alcohol and aldehydes. Examples of polyvinyl acetal resins include polyvinyl formal (formal resin), polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral (butyral resin), polyvinyl hexial and the like. Among them, polyvinyl butyral is particularly preferable because it is soluble in a solvent, is easy to be inked, and has a good expression of visual unevenness (being visually recognized as a recess) and the like.

Moreover, in order to adjust a gloss value, you may mix and use gloss adjustment resin, such as unsaturated polyester-type resin, an acrylic resin, a vinyl chloride-vinyl acetate copolymer, as needed. When a gloss control resin is used, the mixing ratio is preferably in the range of 10 to 50% by mass with respect to the total amount of the vehicle. Further, the ink for forming the gloss control layer may be non-colored or may be colored by adding a colorant such as a pigment.
In addition, an extender pigment may be blended in the ink for forming the gloss adjustment layer. In the case of blending an extender pigment, scattering of light can be promoted and the above-mentioned uneven shape (duct) eliminating effect can be further enhanced. The extender pigment is not particularly limited, but is suitably selected from, for example, silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. Among these, silica, which is a material having a high degree of freedom in material design such as oil absorbency, particle diameter, pore volume, etc., and excellent in designability, whiteness and coating stability as an ink, is preferable, in particular Silica is preferred. In addition, as for the content, when using an extender, 5-15 mass parts is preferable with respect to 100 mass parts of ink (ink composition) other than an extender.

Gloss values G _A luster control layer, vehicle described above, luster control resin, a method for selecting a type of each substance and coloring agent (including extender pigments); and the like; how to set the contents of the above materials properly , Can be adjusted.

  As a printing method used for formation of a gloss adjustment layer, a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, an inkjet method, for example like the printing method used for formation of the above-mentioned pattern pattern layer The printing method etc. are mentioned. Moreover, when forming a solid-like gloss adjusting layer entirely, the method similar to the various coating methods in formation of a pattern pattern layer is mentioned.

  When the gloss adjustment layer is formed on a part of the surface on the front side (in the case of the above (1)), it is preferable that the gloss adjustment layer is formed in a picture shape. In particular, it is more preferable that the gloss adjusting layer is formed in a dot shape, a lattice shape, a pattern shape of wood grain conduit pattern (shape) or the like. Since the gloss adjustment layer is formed in the above-mentioned pattern, the gloss of the area with the gloss adjustment layer is different from that of the area other than the gloss adjustment layer (the area without the gloss adjustment layer). It produces an illusion of an eye as if there is a recess and is viewed as a unique three-dimensional effect. Therefore, the uneven shape (duct) becomes even less noticeable.

  When the above-mentioned pattern layer is formed on the decorative sheet of the present invention, it is preferable to form the gloss adjusting layer so as to interlock (tune) with the pattern of the pattern layer. For example, when the design pattern layer is formed in a wood grain pattern tone, a decorative sheet having more excellent design can be obtained by forming a gloss adjustment layer by pattern printing in a wood grain conduit pattern tone.

  The thickness (film thickness) of the gloss adjusting layer is preferably 0.5 μm to 5 μm in consideration of the printability and the interaction with the resin composition for forming a surface protective layer.

If necessary, a back surface primer layer may be provided on the back surface of the back surface primer layer substrate sheet (the surface opposite to the surface on which the design pattern layer is to be laminated). For example, it is effective when producing a decorative board by bonding a base material sheet and an adherend.

  The back surface primer layer can be formed by applying a known primer agent to a substrate sheet. As a primer agent, for example, a urethane resin based primer consisting of an acrylic modified urethane resin (acrylic urethane based resin) etc., a urethane-cellulose based resin (eg a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) And a resin based primer comprising a block copolymer of acryl and urethane. Additives may be added to the primer if necessary. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet light absorbers, light stabilizers and the like. The compounding amount of the additive can be appropriately set according to the product characteristics.

Although the application amount of the primer agent is not particularly limited, it is usually about 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  The thickness of the back surface primer layer is not particularly limited, but is usually about 0.01 to 10 μm, preferably about 0.1 to 1 μm.

Embossed Shape The decorative sheet of the present invention is embossed from the surface protective layer side. The embossing method is not particularly limited. For example, a method of heat-softening the front surface of the surface protective layer, pressing and shaping with an embossing plate, and cooling may be mentioned as a preferred method. Depending on the material of the sheet or surface protective layer, for example, the front surface of the transparent resin layer or gloss adjustment layer is heated and softened, pressed and shaped with an embossed plate, and then a surface protective layer is formed thereon. It is also good.

  For embossing, a known sheet-fed or rotary emboss machine is used. As an uneven | corrugated shape, there exist a wood-grain board conduit groove, a stone plate surface unevenness | corrugation (a granite cleavage surface etc.), cloth surface texture, a satin, a grain, a hairline, a line streak, etc., for example.

In the decorative sheet of the present invention, the ten-point average roughness Rz _jis of the surface of the decorative sheet is preferably 60 μm or more, and more preferably 70 μm or more. The ten-point average roughness Rz _jis of the surface of the decorative sheet is preferably 150 μm or less, more preferably 120 μm or less. By subjecting the decorative sheet of the present invention to the above-mentioned embossing from the surface protective layer side, the above-mentioned ten-point average roughness Rz _jis can be adjusted to the above-mentioned range, whereby scratch resistance and _{designability} are more excellent. Can be made into a decorative sheet. In addition, in this specification, said ten-point average roughness Rz _jis is a value measured by the measuring method based on _{JISB0601-2001} .

In the decorative sheet of the present invention, the 60 ° gloss (gloss value (60 ° incident angle)) of the surface is preferably 14 or less, and more preferably 10 or less. The 60 ° gloss of the surface of the decorative sheet is not particularly limited, but is preferably 3 or more. By setting the 60 ° gloss of the surface of the decorative sheet of the present invention to the above-mentioned range, it is possible to make the decorative sheet more excellent in designability and inconspicuous even when rubbed, so that the decorative sheet is more excellent in scratch resistance can do. In the present specification, the 60 ° gloss is a flow of a decorative sheet using a gloss meter (trade name: GMX-202, manufactured by Murakami Color Research Laboratory, Inc.) according to a method in accordance with Japanese Industrial Standard JIS Z-8741. It is a value measured by measuring along the direction. Further, 60 ° gloss of the decorative sheet surface of the present invention, the same as G _A and the G _P, can be measured using a Nippon Denshoku Industries Co., Ltd. PG-3D.

Decorative Plate By laminating the decorative sheet of the present invention on the adherend, a decorative plate can be obtained. The decorative board of the present invention is obtained by laminating the decorative sheet of the present invention on an adherend so that the surface protective layer of the decorative sheet of the present invention is the outermost surface layer.

  The adherend is not limited, and the same ones as those used for known decorative boards can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, glass and the like. In particular, the decorative sheet of the present invention can be suitably used for wood materials. Specific examples of wood materials include veneers made of various materials such as cedar, mulberry, mulberry, pine, rawan, teak and melapy, wood veneer, wood plywood, particle board, medium density fiber board (MDF) , Chip board, or a composite substrate on which the chip board is laminated. As the wood material, it is preferable to use a chip board or a composite substrate on which the chip board is laminated.

  The lamination method of laminating the decorative sheet and the adherend is not limited, and for example, a method of adhering the decorative sheet to the adherend with an adhesive can be adopted. The adhesive may be appropriately selected from known adhesives according to the type of adherend and the like. For example, in addition to polyvinyl acetate, polyvinyl chloride, a vinyl chloride / vinyl acetate copolymer, an ethylene / acrylic acid copolymer, an ionomer, etc., butadiene / acryl nitrile rubber, neoprene rubber, natural rubber and the like can be mentioned. These adhesives are used individually or in combination of 2 or more types.

  The decorative board manufactured in this manner is, for example, an interior material of a building such as a wall, a ceiling, or a floor; an exterior material such as a balcony or a veranda; a surface decorative board or furniture of a fitting such as a window frame, a door or a handrail; Alternatively, it can be used as a surface decorative plate of a cabinet such as a weak electric power or an OA device. In particular, the decorative board can be suitably used as a floor decorative material.

  Hereinafter, the present invention will be specifically described by showing Examples and Comparative Examples. However, the present invention is not limited to the examples.

Example 1 (A base sheet has a two-layered decorative sheet)
A 60 μm thick polypropylene film (manufactured by Mitsubishi Resins Co., Ltd .: Art Ply) was prepared as the base sheet 1, and a 2 μm thick pattern layer was formed by gravure printing on the front surface of the polypropylene film. An adhesive layer of 2 μm in thickness made of urethane resin (made by Dainichi Seika Kogyo Co., Ltd .: Seika Bond E-263 / C-75N) was formed on the picture pattern layer. On the adhesive layer, a sheet of transparent polypropylene-based resin having a thickness of 100 μm (manufactured by Nippon Polypropylene Corporation: Novatec PP) was extrusion laminated and laminated to form a transparent resin layer.

  Subsequently, the surface was subjected to a corona discharge treatment, and then a two-component curable urethane resin was applied to form a primer layer (a primer layer for forming a surface protective layer, thickness 2 μm).

  A urethane acrylate electron beam curable resin (EB resin) is coated on the front surface of the primer layer by a gravure coating method so that the thickness (layer thickness) after curing becomes 15 μm, and then the oxygen concentration is 200 ppm. The surface protection layer was formed by curing the above-mentioned electron beam-curable resin by irradiating an electron beam under the conditions of an acceleration voltage of 175 KeV and 5 Mrad using an electron beam irradiation apparatus under the following environment.

  The electron beam curable resin contains 30 parts by mass of fine particles 1 (particle diameter 6 to 8 μm) shown in Table 10 with respect to 100 parts by mass of the electron beam curable resin as the silica fine particles A having a particle diameter smaller than the coating film thickness. And, 5 parts by mass of fine particles 2 (particle diameter: 18 to 20 μm) shown in Table 10 were contained with respect to 100 parts by mass of the electron beam curable resin as the silica fine particles B having a particle diameter larger than the coating film thickness.

The composition of the electron beam-curable resin is as follows.
-Bifunctional urethane acrylate (Tg = 25 (° C), molecular weight 1500) 80 parts by mass · 6 -functional urethane acrylate (Tg = 200 (° C) or higher, molecular weight 1500) 20 parts by mass The surface protective layer formed as described above The substrate sheet 1 and the transparent resin layer are softened by heating them with an infrared non-contact heater, and embossing is immediately carried out by heat and pressure, and a textured pattern of wood grain on the surface protective layer (grain 1 Formed.

Finally, a backer layer as the substrate sheet 2 was formed by laminating a resin layer made of polypropylene resin on the back surface of the substrate sheet 1 by a melt extrusion laminating method. Furthermore, after giving a corona discharge treatment to the back surface of the said backer layer, the back surface primer layer (2 micrometers in thickness) was formed, and the decorative sheet was prepared. The thickness of the backer layer was 120 μm, and the Martens hardness (measured in the cross-sectional direction of the backer layer) was 50 to 60 N / mm ² . The ten-point average roughness Rz _jis (measurement distance: 2 cm) of the surface of the decorative sheet on which the above-mentioned concavo-convex pattern was formed was 71 μm. Moreover, when the gloss value (60 degrees of incident angles) of the surface protective layer was measured using PG-3D manufactured by Nippon Denshoku Kogyo Co., Ltd., the gloss value ( _Gp ) was 13.

Examples 2 to 10, Comparative Examples 1 to 12
Examples 2 to 10 are the same as Example 1, except that the surface protective layer, the content of the fine particles A and B, the configuration of the transparent resin layer, the base sheet, and the embossed shape are changed as shown in Tables 1 to 5. And the decorative sheet of Comparative Examples 1-12 was prepared.

Examples 11 and 12 and Comparative Examples 13 to 16 (A base sheet is a single layer decorative sheet)
Example except that the backer layer as the substrate sheet 2 is not formed, and the content of the surface protective layer, the fine particles A and B, the configuration of the transparent resin layer, the substrate sheet, and the embossed shape are changed as shown in Table 5 In the same manner as in Example 1, decorative sheets of Examples 11 and 12 and Comparative Examples 13 to 16 were prepared.

Example 13
First, a substrate sheet, a pattern layer, an adhesive layer, a transparent resin layer and a primer layer were formed. Each of the layers was formed by the same method as in Example 1.
Then, the ratio of the area of the gloss adjustment layer per 1 cm ² of the surface on the surface protective layer side of the decorative sheet is 50% of the front surface of the primer layer (finally prepared makeup The gloss adjusting layer in a pattern was formed so that the occupied area ratio of the gloss adjusting layer when viewed from the front surface of the sheet was 50%. In addition, the said gloss adjustment layer is a printing ink which mix | blended 10 mass parts of silica particles with respect to 100 mass parts of polyester urethane type printing inks of a number average molecular weight 3000 and glass transition temperature (Tg) -62.8 degreeC of matting ink. The composition was formed by applying a wood grain conduit pattern so that the thickness of the gloss adjustment layer after drying was 2 μm by the gravure printing method.
Next, after forming a surface protection layer on the whole surface on the said gloss adjustment layer, the embossing pattern was further formed with respect to the said surface protection layer side. The surface protective layer and the embossed pattern were formed in the same manner as in Example 1, respectively.
Next, after forming a backer layer as the base sheet 2 on the back side of the base sheet, a back side primer layer was formed on the back side of the backer layer. The backer layer and the back surface primer layer were formed in the same manner as in Example 1, respectively.
Thus, the decorative sheet of Example 13 was obtained.
Incidentally, prior to applying the surface protective layer-forming resin composition was measured for a gloss value when the light enters at an incident angle of 60 ° relative to the luster control layer, the luster value (G _A) 2 Met. Further, apart from the decorative sheet, a decorative sheet similar to the decorative sheet of Example 13 was produced for measuring the gloss value of the surface protective layer except that the gloss adjusting layer was not formed. The gloss value (G _P ) was 13 when the gloss value was measured when light was incident on the surface protective layer of the decorative sheet for measurement at an incident angle of 60 °. The gloss value (60 ° incident angle) of the gloss adjusting layer and the surface protective layer in the decorative sheet of Example 13 was determined with the above gloss value. The gloss value (60 ° incident angle) was measured using PG-3D manufactured by Nippon Denshoku Kogyo Co., Ltd.

Example 14
First, a substrate sheet, a pattern layer, an adhesive layer, a transparent resin layer and a primer layer were formed. Each of the layers was formed by the same method as in Example 1.
Next, a gloss adjusting layer (thickness after drying: 2 μm) was formed on the entire surface of the front surface of the primer layer. In addition, in the formation of the said gloss adjustment layer, the ink similar to the matte ink used in Example 13 was used.
Next, on the gloss adjustment layer, the ratio of the area of the surface protection layer per 1 cm ² of the surface protection layer side of the decorative sheet is 30% (in the area where the gloss adjustment layer is exposed) A patterned surface protective layer was formed such that the percentage of the area (the percentage of exposed area of the low gloss layer) was 70%. In addition, in the case of formation of the said surface protective layer, the resin composition similar to the surface protective layer formation resin composition used in Example 1 was used. Further, the curing of the electron beam curable resin was also performed by the same method as in Example 1.
Next, an embossed pattern was formed on the surface protective layer side. The embossed pattern was formed by the same method as in Example 1.
Next, after forming a backer layer as the base sheet 2 on the back side of the base sheet, a back side primer layer was formed on the back side of the backer layer. The backer layer and the back surface primer layer were formed in the same manner as in Example 1, respectively.
Thus, the decorative sheet of Example 14 was obtained.
Incidentally, prior to applying the surface protective layer-forming resin composition was measured for a gloss value when the light enters at an incident angle of 60 ° relative to the luster control layer, the luster value (G _A) 2 Met. Further, apart from the decorative sheet, a decorative sheet similar to the decorative sheet of Example 14 except that the gloss adjusting layer was not formed was prepared for measuring the gloss value of the surface protective layer. The gloss value (G _P ) was 13 when the gloss value was measured when light was incident on the surface protective layer of the decorative sheet for measurement at an incident angle of 60 °. The gloss value (60 ° incident angle) of the gloss adjusting layer and the surface protective layer in the decorative sheet of Example 14 was determined with the above gloss value. The gloss value (60 ° incident angle) was measured using PG-3D manufactured by Nippon Denshoku Kogyo Co., Ltd.

Examples 15 to 21
As fine particles used for the surface protective layer, fine particles 1 to 6 shown in Table 10 were used. Moreover, it was set as the grain 1-5 which shows the embossing pattern of embossing shape in Table 11. The decorative sheets of Examples 15 to 21 were prepared in the same manner as in Example 1 except that the surface protective layer, the content of fine particles, and the embossed shape were changed as shown in Tables 7-9.

  The following evaluation items were evaluated by each evaluation method about the decorative sheet of the Example and comparative example prepared as mentioned above, and the decorative board prepared as follows using the said decorative sheet. In addition, in the following evaluation methods, "scale angle" shows the area of the plane represented by length 303 mm x width 303 mm.

(Evaluation method)
Surface condition of decorative plate 1 (Evaluation of surface irregularities on the adherend)
Apply 6 to 7 g of a water-based emulsion adhesive (Likabond BA-10L (main agent): BA-11B (hardening agent) manufactured by Chuo Rika Kogyo Co., Ltd.) on a cork board, and laminate the decorative sheet, A decorative board was produced by curing for a day. The surface condition of the decorative board was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of A or more, it is a surface state without a problem in an actual use condition.
A: The unevenness of the adherend is not exposed B: The unevenness of the adherend is slightly exposed C: The unevenness of the adherend is clearly exposed

Embossed condition of decorative sheet (emboss shape evaluation)
The state of the embossed pattern of the decorative sheet was visually observed and evaluated according to the following evaluation criteria. In addition, if it is evaluation of A or more in the following evaluation criteria, it is the embossing state which does not have a problem in an actual use condition.
A: Embossed pattern is clearly left B: Embossed pattern is slightly lost C: Embossed pattern is almost lost

Embossed condition of decorative board (embossed evaluation)
The embossed state of the decorative plate, that is, the embossed failure after laminating the decorative sheet to the adherend was evaluated. Specifically, 6 to 7 g of a water-based emulsion adhesive (Licabond BA-10L (main agent): BA-11B (hardening agent) manufactured by Chuo Rika Kogyo Co., Ltd.) is applied on a particle board, and a decorative sheet is laminated. Then, the decorative board was produced by curing at room temperature for 3 days. The embossed state of the decorative board was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of B or more, it is the embossing state which does not have a problem in an actual use condition.
A: Embossed pattern is not crushed B: Embossed pattern is slightly crushed C: Embossed pattern is almost crushed

Curl Resistance of Decorative Sheet The decorative sheet was wrapped around a 3-inch diameter paper tube and left at room temperature for 1 week. The decorative sheet was unwound, and the state of curl was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of A or more, it has the curling resistance which does not have a problem in an actual use condition.
A: Almost no curling of the decorative sheet occurs B: The decorative sheet slightly curls C: The decorative sheet apparently curls

Static pressure load resistance (gradation evaluation under static pressure load conditions)
Apply 6 to 7 g of a water-based emulsion adhesive (Ricabond BA-10L (main agent): BA-11B (hardener)) on a 4 cm × 4 cm MDF substrate, and laminate the decorative sheet Then, the decorative board was produced by curing at room temperature for 3 days. After applying a load of 5 kg / cm ² (80 kg to 4 cm × 4 cm) for 24 hours to the surface of the decorative plate (the decorative sheet side), the gloss change on the surface of the decorative plate was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of B or more, static pressure load resistance which does not have a problem in an actual use condition is provided, and glossiness can be suppressed even if it uses under the conditions which static pressure load is applied.
A: Gloss is not changed B: Gloss is slightly changed C: Gloss is clearly changed

Micro-Scratch Test The following test was conducted using a JamesHeal Martindale tester.
[Gloss test (A test)]
The surface of the decorative sheet was polished using an abrasive material (Scotch Brite Fleece SB7447 manufactured by Sumitomo 3M Ltd.). Specifically, the surface of the decorative sheet was subjected to a test by applying a load of 6 N to a circular scotch brite having a diameter of 9 cm (load 9 g / cm ² ) and polishing under the conditions of 80 rotations (5 resurrection loci) The rate of change of 60 ° gloss value before and after the test was measured and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of B or more, the result in which there is no problem in the actual use condition is shown.
A: The rate of change of the gloss value is less than 20% B: The rate of change of the gloss value is 20% or more and less than 30% C: The rate of change of the gloss value is 30% or more

[Blemish test (B test)]
The surface of the decorative sheet was polished using an abrasive material (Scotch Brite Fleece SB7440 manufactured by Sumitomo 3M Ltd.). Specifically, the surface of the decorative sheet was subjected to a test by applying a load of 4 N to a circular scotch brite of 9 cm in diameter (load 6 g / cm ² ) and polishing under the conditions of 160 rotations (10 Lissajous trajectories) The scratches on the surface of the decorative sheet after the test were visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of B or more, it has the flaw resistance which does not have a problem in an actual use condition.
A +: no scratches on the surface of the decorative sheet A: slight scratches on the surface of the decorative sheet
B: Many scratches on the surface of the decorative sheet C: Many scratches on the surface of the decorative sheet

Surface condition 2 of decorative sheet (Evaluation of surface roughness of surface roughness rougher to suppress surface roughness)
An adherend having a surface roughness rougher than that of a cork board (adherent having a surface roughness Rz twice or more than that of a normal adherend) was prepared. Next, an aqueous emulsion adhesive (Likabond BA-10L (main agent): BA-11B (hardening agent) manufactured by Chuo Rika Kogyo Co., Ltd.) is applied on the adherend in an amount of 6 to 7 g / size and then Example Each decorative sheet was produced by laminating each decorative sheet of 1, 13 and 14 and curing at room temperature for 3 days. The surface condition of each decorative board was visually observed and evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of B or more, it is a surface state without a problem in an actual use condition.
A +: The concavo-convex shape of the adherend is not exposed A: the concavo-convex shape of the adherend is slightly exposed B: the concavo-convex shape of the adherend is slightly revealed C: the concavo-convex shape of the adherend Is more exposed than in the case of the B rating

Evaluation of Designability of Decorative Sheet First, each decorative board was produced by the same method as the method described in the above-mentioned "surface state of decorative board part 2". Subsequently, 20 men and women observed the appearance of each said decorative board, and the following evaluation criteria evaluated whether the texture of wood could be expressed. In addition, in the following evaluation criteria, if it is evaluation of B or more, it is a surface state without a problem in an actual use condition.
A +: 90% or more of adult men and women who were judged to be able to express the texture of wood A: 70% or more of adult men and women who were judged to be able to express the texture of wood B: It was judged that the texture of wood was able to be expressed Less than 50% of the adult males and females who have made up C: Less than 50% of the adult males and females who have judged that the texture of the wood can be expressed

Hoffman scratch test (light load scratch resistance evaluation)
The test was performed using a Hoffman scratch tester manufactured by BYK-GARDNER, USA. Specifically, the scratch blade (cylindrical blade of φ7) was set so as to contact with the surface of the decorative sheet at an angle of 45 °, and the tester was moved on the decorative material. The load (weight) was gradually increased, and the test was repeated until scratches, indentations and the like were formed on the surface of the floor decorative sheet. It evaluated according to the following evaluation criteria. In addition, in the following evaluation criteria, if it is evaluation of B or more, it has the light load scratch resistance which does not have a problem in an actual use condition.
A +: no damage is observed when the load is 500 g or more A: no damage is observed when the load is 400 g or more and less than 500 g load B: no damage is observed when the load is 300 g or more and less than 400 g C: 300 g Wounds occurred below load

  The results are shown in Tables 1 to 6 below.

  As is clear from the above results, Examples 1 to 12 have all the requirements of the present invention, so the surface state of the decorative plate (the surface roughness of the adherend is evaluated and suppressed) and the embossed state of the decorative sheet (Embossed formability evaluation), Embossed state of decorative plate (embossed evaluation), curl resistance of decorative sheet, static pressure load resistance (gloss evaluation under static pressure load condition), gloss test (A test) And scratch test (B test) results are excellent, and when exposed to an adherend such as a chip board, the surface appearance of the uneven shape of the adherend on the surface of the decorative plate is suppressed; It was found that the gloss increase was suppressed because the scratch resistance was excellent even under the use conditions such as walking. Moreover, Examples 1 to 12 are excellent in emboss shapeability, emboss crushing at the time of being attached to an adherend is suppressed, and excellent in curl resistance, and for floors, particularly, earth foot It has been found that a decorative sheet for a floor and a decorative sheet suitable for use as a decorative material for a floor, which are used under such use conditions as walking, are obtained.

  In addition, in Examples 1, 13 and 14, when the sticking material having a rough surface is attached, the appearance of the uneven shape of the adhering material on the surface of the decorative plate is suppressed, and the designability is improved. It turned out to be excellent.

  Furthermore, in Examples 9 and 15 to 21, the result of the Hofmann scratch test is B or more, and it was found that, in addition to the above-mentioned performance, the light load scratch resistance was also excellent.

  On the other hand, in Comparative Example 1, since the surface protective layer does not contain fine particles B having a particle diameter larger than the thickness of the surface protective layer, the results of the gloss test (A test) and the scratch test (B test) are inferior. Since 40 parts by mass of fine particles A having a particle diameter equal to or less than the thickness of the surface protective layer is contained, the fine particles A protruding from the surface of the surface protective layer are pushed into the surface protective layer by static pressure load, It had a gloss and was inferior in static pressure load resistance.

  In Comparative Example 2, since the total content of the fine particles A and B is large, the fine particles A protruding from the surface of the surface protective layer are pressed into the surface protective layer due to static pressure load, and the surface protection is The glossiness due to scraping of the fine particles B protruding from the surface of the layer was noticeable, and the static pressure load resistance was inferior, and the result of the gloss test (A test) was inferior.

  In Comparative Example 3, the surface protective layer contains a large amount of fine particles B having a particle diameter larger than the thickness of the surface protective layer, and does not contain fine particles A having a particle diameter smaller than the thickness of the surface protective layer. Because the fine particles B protruding from the surface of the surface protective layer are scraped, the gloss is noticeable, the static pressure resistance is inferior, and the results of the gloss test (Test A) and the scratch test (Test B) are inferior. The

  In Comparative Examples 4 and 6, the surface protective layer did not contain the fine particles B having a particle diameter larger than the thickness of the surface protective layer, and thus was inferior in scratch resistance, and the result of the scratch test (B test) was inferior.

  Comparative Examples 5 and 7 do not contain fine particles A having a particle diameter equal to or less than the thickness of the surface protective layer, so that fine particles B protruding from the surface of the surface protective layer are scraped, so that glossiness is noticeable and static resistance The pressure loadability was inferior, and the result of the gloss test (A test) was inferior.

  In Comparative Examples 8 to 10, since the total content of the fine particles A and B is small, the scratch resistance and the matting effect by the fine particles can not be sufficiently exhibited, and the static pressure load resistance is inferior, and the gloss test (Test A) and The result of the wound test (B test) was inferior.

  Comparative Example 11 was inferior in scratch resistance because the thickness of the surface protective layer was thin, and the result of the scratch test (B test) was inferior.

  In Comparative Example 12, since the thickness of the surface protective layer was large, it was difficult to form an embossed shape on the decorative sheet, and the evaluation of the embossed state of the decorative sheet was inferior.

  In Comparative Example 13, since the Martens hardness of the substrate sheet was low, the surface asperity shape of the adherend appeared on the surface of the decorative sheet, and the evaluation of the surface state of the decorative board was inferior.

  In Comparative Example 14, since the thickness of the base sheet was large, it was difficult to form an embossed shape on the decorative sheet, and the evaluation of the embossed state of the decorative sheet was inferior. Moreover, since the thickness of the base material sheet is thick, the decorative sheet is easily rolled, which is inferior to the evaluation of the curl resistance.

  In Comparative Example 15, since the described sheet was thin, the surface asperity shape of the adherend appeared on the surface of the decorative sheet, and the evaluation of the surface state of the decorative board was inferior.

  In Comparative Example 16, the thickness of the base material sheet is large, and the Martens hardness of the base material sheet is low, it is difficult to form an embossed shape on the decorative sheet, and the evaluation of the embossed state of the decorative sheet is inferior. In addition, the decorative sheet was likely to be rolled, and was inferior to the evaluation of curl resistance.

1. Cosmetic sheet 2. Base sheet 3. Pattern layer 4. Transparency resin layer5. Surface protective layer6. Particulate A
7. Particulate B
8. Gloss adjustment layer

Claims (9)

A decorative sheet in which at least a design pattern layer, a transparent resin layer and a surface protective layer are laminated in this order on a substrate sheet,
(1) The surface protective layer contains fine particles A having a thickness of 7 to 30 μm and having a particle diameter equal to or less than the thickness of the surface protective layer, and fine particles B having a particle diameter larger than the thickness of the surface protective layer.
(2) The content of the fine particles A and the content of the fine particles B are each 5 to 30 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer, and the content of the fine particles A and The total content of the fine particles B is 15 to 35 parts by mass with respect to 100 parts by mass of the resin component of the surface protective layer,
(3) The substrate sheet and the transparent resin layer contain a non-halogen thermoplastic resin,
(4) The substrate sheet has a thickness of 180 to 350 μm, and a region with a Martens hardness of 50 N / mm ² or more is from the surface on the side opposite to the surface on the pattern side of the substrate sheet. Exists in a thickness of 120 μm or more,
(5) Embossed from the surface protective layer side,
A cosmetic sheet characterized by The decorative sheet according to claim 1, wherein the ten-point average roughness Rz _jis of the surface of the decorative sheet is 60 μm or more.   The decorative sheet according to claim 1, wherein the 60 ° gloss of the surface of the decorative sheet is 14 or less.   The decorative sheet according to any one of claims 1 to 3, wherein the fine particles A and the fine particles B are silica fine particles.   The decorative sheet according to any one of claims 1 to 4, wherein a gloss adjusting layer is formed on the transparent resin layer, and the gloss adjusting layer is formed adjacent to the surface protective layer. .   The decorative sheet according to any one of claims 1 to 5, wherein the non-halogen thermoplastic resin is an olefin thermoplastic resin.   The decorative sheet according to any one of claims 1 to 6, wherein the surface protective layer comprises an ionizing radiation curable resin layer.   A decorative board formed by sticking the decorative sheet according to any one of claims 1 to 7 to an adherend.   The decorative board according to claim 8, wherein the adherend is a chip board or a composite substrate on which the chip board is laminated.