JP2015187378A - Sheet and decorative laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet which is excellent in low glossy feeling, which enables visual recognition of a design expressed by the sheet, because reflection of light from a sheet surface is suppressed in a view from a slanting direction, and which is excellent in designability.SOLUTION: A sheet is characterized as follows: a ten-point average roughness Rzjis94 (JIS B0601: 2001) of a surface is 4 μm or more; the ratio RSm/Rzjis94 between the average length RSm (JIS B0601: 2001) of a roughness curve element of the surface and the ten-point average roughness Rzjis94 is less than 25; and reflectance at a detection angle of 45° of light incident at an incident angle of 45°and reflected from the surface is 100% or less.

Description

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

  Conventionally, sheets have been laminated on the surfaces of various articles in order to impart design properties. For example, a decorative sheet is laminated on a surface of a wall covering material used for a wall surface of a building or a floor decorative material used for a floor surface.

  The sheet laminated on the surface of the article as described above is required to suppress the gloss of the surface in order to improve the designability. When the surface has a high gloss, there is a problem in that the light from a lighting device such as a fluorescent lamp is reflected and the texture is deteriorated, and a so-called white turbidity is generated due to the reflected light.

  As a decorative sheet that solves such problems, a decorative sheet in which the outermost surface layer is formed of an ionizing radiation curable resin containing a matte filler has been proposed (see, for example, Patent Documents 1 and 2).

  Although such a decorative sheet is also a sheet that is excellent in low gloss and excellent in suppressing cloudiness, there is room for study on suppression of light reflection on the surface, and further design is required. . In particular, when the sheet is laminated on a flat adherend, when the plane is viewed obliquely, the light from the lighting fixture or the like is reflected and looks white, making it difficult to visually recognize the design represented by the sheet such as a pattern, There is a problem that the designability is lowered. For this reason, such a sheet | seat is requested | required that reflection of light is suppressed when it sees from diagonally, the surface does not look white, and the design to express can be visually recognized.

  Therefore, the design expressed by the sheet can be visually recognized because the reflection of light on the surface of the sheet is suppressed when viewed from an oblique direction, and the development of a sheet with excellent design properties is desired. ing.

JP 2012-91487 A JP 2013-31995 A

  The present invention provides a sheet that is excellent in low gloss and that can be visually recognized because the reflection of light on the surface of the sheet is suppressed when viewed from an oblique direction, and that is excellent in design. For the purpose.

  As a result of extensive research, the present inventors have found that the surface ten-point average roughness Rzjis94 (JIS B0601: 2001) is 4 μm or more, and the average length RSm of the surface roughness curve element (JIS B0601: 2001). And the ratio RSm / Rzjis94 with the ten-point average roughness Rzjis94 of the surface is less than 25, and the reflectance at the detection angle of 45 ° of the light incident at the incident angle of 45 ° and reflected by the surface is 100% or less. It has been found that the above object can be achieved by using a certain sheet, and the present invention has been completed.

That is, this invention relates to the following sheet | seat and decorative board.
1. The surface 10-point average roughness Rzjis94 (JIS B0601: 2001) is 4 μm or more,
The ratio RSm / Rzjis94 of the average length RSm (JIS B0601: 2001) of the surface roughness curve element to the ten-point average roughness Rzjis94 of the surface is less than 25,
The reflectance at a detection angle of 45 ° of light incident on an incident angle of 45 ° and reflected from the surface is 100% or less.
A sheet characterized by that.
2. Item 2. The sheet according to Item 1, wherein the outermost surface has a surface protective layer containing an ionizing radiation curable resin.
3. Item 3. The sheet according to Item 1 or 2, which has a transparent resin layer containing an olefin resin.
4). Item 4. The sheet according to any one of Items 1 to 3, which has a pattern layer.
5. Item 5. The sheet according to Item 4, wherein at least the pattern layer, the transparent resin layer, and the surface protective layer are laminated in this order on a substrate sheet.
6). Item 6. The sheet according to any one of Items 1 to 5, wherein the sheet has a thickness of 50 to 600 µm.
7). Item 7. The sheet according to any one of Items 1 to 6, which is a decorative sheet.
8). Item 7. The sheet according to any one of Items 1 to 6, which is a decorative sheet for flooring.
9. A decorative sheet obtained by laminating the decorative sheet according to Item 7 or the decorative sheet for flooring according to Item 8 on an adherend.

  The sheet of the present invention has a surface ten-point average roughness Rzjis94 (JIS B0601: 2001) of 4 μm or more, an average length RSm (JIS B0601: 2001) of the surface roughness curve element, and ten points on the surface. The ratio RSm / Rzjis94 to the average roughness Rzjis94 is less than 25, and the reflectance at a detection angle of 45 ° of light incident at an incident angle of 45 ° and reflected from the surface is 100% or less. The sheet of the present invention has a surface ten-point average roughness Rzjis94 (JIS B0601: 2001) of 4 μm or more, and an average length RSm (JIS B0601: 2001) of the surface roughness curve element, The ratio RSm / Rzjis94 with the ten-point average roughness Rzjis94 is less than 25. For this reason, the sheet | seat of this invention is excellent in the low glossiness. Moreover, since the sheet | seat of this invention is equipped with the above-mentioned structure, reflection of the light of the sheet | seat surface is suppressed when it sees from diagonally. Even if the sheet normally has a low gloss feeling, light is reflected when viewed from an oblique direction, and specific portions of the sheet surface appear white, and the design originally expressed by the sheet cannot be visually recognized. On the other hand, since the sheet of the present invention has the above-described configuration, combined with the reflectance at a detection angle of 45 ° of light incident at an incident angle of 45 ° and reflected from the surface being 100% or less, Reflection of light on the surface of the sheet when viewed from an oblique direction is suppressed, and the design represented by the sheet such as a pattern is visible. For this reason, the sheet | seat of this invention can show the outstanding design property.

  Hereinafter, the sheet of the present invention will be described in detail. In the sheet of the present invention, the surface is a so-called “front surface” and is opposite to the surface in contact with the adherend when the sheet of the present invention is used by being laminated on the adherend. This is a side surface that is visible after lamination. In the present specification, the direction of the surface of the sheet of the present invention may be referred to as “front” or “up”, and the opposite side may be referred to as “back” or “down”.

[Sheet]
The sheet of the present invention has a surface ten-point average roughness Rzjis94 (hereinafter also simply referred to as “Rzjis94”) measured in accordance with JIS B0601: 2001 of 4 μm or more. In this specification, Rzjis94 (ten-point average roughness) is JIS B0601 (2001) “Geometrical Product Specification (GPS) —Surface Properties: Contour Curve Method—Terms, Definitions, and Surface Property Parameters” Annex In the 1994 edition of JIS, it is the same as the ten-point average roughness Rz normally defined in JIS B0601. When the Rzjis94 is less than 4 μm, the low glossiness is lowered, it is difficult to adjust the RSm / Rzjis94 value to be less than 25, and reflection of light on the sheet surface when viewed from an oblique direction cannot be suppressed. The Rzjis 94 is preferably 5 μm or more. Moreover, although the upper limit of Rzjis94 is not specifically limited, It is preferable that Rzjis94 is 20 micrometers or less. If Rzjis94 is too large, the scratch resistance and dirt wiping property of the sheet surface may be reduced.

  The sheet of the present invention has a ratio between the average length RSm of the surface roughness curve element (hereinafter also simply referred to as RSm) and the ten-point average roughness Rzjis94 measured according to JIS B0601: 2001. RSm / Rzjis94 is less than 25. When RSm / Rzjis94 is 25 or more, the uneven shape on the sheet surface becomes flat, and reflection of light on the sheet surface cannot be sufficiently suppressed when the sheet is viewed obliquely. The RSm / Rzjis94 is preferably 20 or less. Moreover, although the minimum of RSm / Rzjis94 is not specifically limited, It is preferable that RSm / Rzjis94 is 1 or more. If RSm / Rzjis94 is too small, the scratch resistance and dirt wiping property on the sheet surface may be reduced.

  The sheet of the present invention has a reflectivity at a detection angle of 45 ° (hereinafter also simply referred to as “reflectance at 45 °”) of light incident on an incident angle of 45 ° and reflected from the surface thereof is 100% or less. When the reflectivity at 45 ° exceeds 100%, the reflection of light on the surface of the sheet cannot be sufficiently suppressed when the sheet is viewed obliquely, and the design expressed by the sheet cannot be visually recognized. The reflectance at 45 ° is preferably 80% or less. Further, the lower limit of the reflectance at 45 ° is not particularly limited, and it is preferably as small as possible.

  The RSm is preferably 10 to 300 μm, and more preferably 50 to 200 μm. When RSm is too small, there is a possibility that the low gloss feeling may be lowered when RSm / Rzjis94 is adjusted to less than 25. When RSm is too large, it is difficult to adjust RSm / Rzjis94 to less than 25. In addition, the uneven shape on the sheet surface becomes flat and the low glossiness is lowered, and reflection of light on the sheet surface may not be sufficiently suppressed when the sheet is viewed obliquely.

  In the sheet of the present invention, the method of making the surface shape the above uneven shape is not particularly limited, for example, a method of adding a matting agent such as silica to the outermost layer, or the above unevenness on the sheet surface The method etc. which shape a shape by an embossing plate are mentioned.

  The sheet of the present invention is provided with the above-mentioned uneven shape on the surface, but other embossed shapes such as a wood grain plate conduit groove are shaped as shown in FIG. 1 as long as the effect of the present invention is not hindered. It may be. FIG. 1 is a cross-sectional view showing an example of the sheet of the present invention. A sheet 1 of the present invention illustrated in FIG. 1 includes a flat portion 9 having the above-described uneven shape on the surface, and a wood grain plate conduit groove 10 is formed between the flat portions 9. The other embossed shapes are not limited to the wood grain plate conduit grooves, and examples thereof include stone plate surface irregularities (such as granite cleaved surfaces), cloth surface textures, satin texture, sand texture, hairlines, and ridges.

  The sheet of the present invention may be provided with a partial pattern portion on the surface protective layer as shown in FIG. 2 as long as the effect of the present invention is not hindered. FIG. 2 is a cross-sectional view showing an example of the sheet of the present invention. The sheet 1 of the present invention illustrated in FIG. 2 includes a planar portion 9 having the above-described uneven shape on the surface protective layer 8, and a wood grain plate conduit groove 10 is formed between the planar portions 9. In addition, a pattern portion 11 that partially represents a wood grain conduit pattern is formed on a part of the surface of the flat portion 9. The design expressed by the design pattern portion is not particularly limited, and examples thereof include a grain pattern, a stone pattern, a geometric pattern, and a cloth surface texture.

  The pattern part may or may not be colored. When the design pattern part is not colored, the design expressed by the design pattern part is, for example, a design expressed by the difference in gloss between the design pattern part and the part where the design pattern part of the surface protective layer is not formed. Is mentioned. In this case, the pattern part only needs to be visually recognizable in comparison with the part where the pattern part of the surface protective layer is not formed, and may be higher gloss than the part where the pattern part is not formed. However, it may be low gloss.

  In FIG. 2, the above-mentioned uneven | corrugated shape with which the plane part 9 of the sheet | seat 1 of this invention is provided may be formed in the surface of the pattern part 11, and if it is a range which does not prevent the effect of this invention, it is uneven | corrugated. The shape may not be formed. Further, another emboss shape 10 such as the wood grain plate conduit groove may be formed on the surface of the pattern part 11.

  The pattern part may also be formed by not forming the surface protective layer as shown in FIG. FIG. 3 is a cross-sectional view showing an example of the sheet of the present invention. In the sheet 1 of the present invention illustrated in FIG. 3, there is a portion where the surface protective layer 8 is not partially formed on the primer layer 7, and the portion forms the pattern portion 11. In FIG. 3, the primer layer 7 is exposed in the pattern portion 11, and the primer layer 7 is partially visible from the surface protective layer 8 side of the sheet 1 of the present invention. In the sheet of the present invention shown in FIG. 3, for example, the surface of the primer layer 7 has a high gloss, and the surface of the surface protective layer 8 has a low gloss, thereby expressing a design due to a gloss difference. There is no particular limitation on the design expressed by not forming the surface protective layer on the pattern part. Can be mentioned.

  The sheet of the present invention preferably has a surface 60 ° gloss of 10 or less, more preferably 7 or less. By setting the 60 ° gloss on the surface of the sheet of the present invention within the above-described range, a sheet having excellent luster can be obtained. In the present specification, the 60 ° gloss is a value measured using a gloss meter (trade name: GMX-202, manufactured by Murakami Color Research Laboratory Co., Ltd.) according to a method based on JIS Z-8741. It is.

  The sheet of the present invention preferably has a thickness of 50 to 600 μm, and more preferably 100 to 250 μm. By setting the thickness within the above range, the sheet of the present invention is excellent in design and can be provided with scratch resistance.

[Sheet layer structure]
If the sheet | seat of this invention is equipped with the above-mentioned uneven | corrugated shape on the surface, the specific structure (layer structure) will not be limited. For example, when the sheet of the present invention is a decorative sheet, a sheet formed by sequentially laminating a pattern layer, a transparent adhesive layer, a transparent resin layer, a primer layer, and a surface protective layer on the base sheet is exemplified. .

  Hereinafter, each layer will be specifically described by using a sheet having such a layer structure as a representative example.

The base sheet is a layer in which a pattern layer or the like is sequentially laminated on the surface (front surface). As the base sheet, for example, a sheet (film) formed of a thermoplastic resin is suitable. Specifically, polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / acrylic acid ester copolymer Examples include polymers, ionomers, acrylic esters, and methacrylic esters. The said base material sheet is formed by using these resin individually or in combination of 2 or more types.

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

  The base sheet contains various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antistatic agents, antioxidants, UV absorbers, and light stabilizers as necessary. It may be.

  Although the thickness of a base material sheet can be suitably set with the use of a final product, a usage method, etc., generally 20-300 micrometers is preferable.

  If necessary, the base sheet may be subjected to corona discharge treatment on the surface (front surface) in order to enhance the adhesion of the ink for forming the pattern layer or the like. What is necessary is just to implement the method and conditions of a corona discharge process according to a well-known method. Moreover, you may give a corona discharge process to the back surface of a base material sheet, and may form the back surface primer layer mentioned later as needed.

Pattern pattern layer The pattern pattern layer is a layer that imparts a desired pattern (design) to the sheet, and the type of pattern is not limited. For example, a wood grain pattern, a leather pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a geometric figure, a character, a symbol, an abstract pattern, and the like can be given.

  The method for forming the 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. What is necessary is just to form on the base-material sheet | seat surface by the printing method. As the ink, an aqueous composition can be used from the viewpoint of reducing the VOC of the sheet.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, and cadmium red; azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, isoindolinone pigments, dioxazine pigments. Organic pigments such as aluminum powder, metal powder pigments such as bronze powder, pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride; fluorescent pigments; These colorants can be used alone or in admixture 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 binder resin, in addition to polyester urethane resin treated with hydrophilicity, polyester, polyacrylate, polyvinyl acetate, polybutadiene, polyvinyl chloride, chlorinated polypropylene, polyethylene, polystyrene, polystyrene-acrylate copolymer, rosin derivative Alcohol adducts of styrene-maleic anhydride copolymers, cellulose resins, and the like can also be used in combination. More specifically, for example, polyacrylamide resins, poly (meth) acrylic resins, polyethylene oxide resins, poly N-vinyl pyrrolidone resins, water-soluble polyester resins, water-soluble polyamide resins, water-soluble amino acids. Also usable are water-based resins, water-soluble phenolic resins, other water-soluble synthetic resins; water-soluble natural polymers such as polynucleotides, polypeptides, polysaccharides, and the like. Also, 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 natural rubber, etc. Resin can also be used. The said binder resin can be used individually or in combination of 2 or more types.

  The thickness of the pattern layer is not particularly limited and can be set as appropriate according to product characteristics. 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.

  In addition, when the sheet | seat of this invention is a structure which does not have a pattern pattern layer, if the layer which comprises the sheet | seat of this invention is made transparent, the pattern of adherends, such as a wooden base material, will be visible through the said sheet | seat. Thus, the pattern of the adherend can be used as a design as it is. By adopting such a configuration, the design expressed by the pattern of the adherend is excellent in low gloss by the sheet of the present invention, and reflection of light on the surface of the sheet is suppressed even when viewed from an oblique direction. Is visible and can exhibit excellent design properties.

In order to improve the adhesiveness between the adhesive layer transparent resin layer and the design pattern layer, an adhesive layer may be formed on the design pattern layer. The adhesive layer is preferably a transparent adhesive layer, and the transparent adhesive layer includes any of colorless and transparent, colored and transparent, and translucent.

  It does not specifically limit as an adhesive agent, A well-known adhesive agent can be used in the field of a decorative sheet. Examples of known adhesives 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. Further, a two-component curable polyurethane resin or polyester resin using isocyanate as a curing agent can also be applied.

  Although the thickness of an adhesive bond layer is not specifically limited, The thickness after drying is about 0.1-30 micrometers, Preferably it is about 1-20 micrometers.

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 translucent. Examples of the resin constituting the transparent resin layer include polyethylene terephthalate, polybutylene terephthalate, polyamide, polyethylene, polypropylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, and ethylene / acrylic acid ester copolymer. Examples thereof include coalescence, ionomer, polymethylpentene, acrylic acid ester, methacrylic acid ester, polycarbonate, and cellulose triacetate. These resins can be used alone or in combination of two or more.

  Preferably, a polyolefin resin typified by polypropylene resin is used. Therefore, when using polyolefin-type resin as a transparent resin layer, the various polyolefin-type resin quoted as what comprises a base material sheet can be used.

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

  The thickness of the transparent resin layer is usually about 20 to 200 μm, but may exceed the above range depending on the use of the sheet.

  When the sheet of the present invention has a layer configuration without a surface protective layer, the transparent resin layer is the outermost layer of the sheet, and the uneven shape of the sheet of the present invention is formed on the surface of the transparent resin layer. It is preferable. Examples of the method for forming the uneven shape of the sheet of the present invention on the surface of the transparent resin layer include a method of forming the above uneven shape on the surface of the transparent resin layer with an embossed plate.

A primer layer may be provided on the primer layer transparent resin layer. The primer layer can be formed by applying a known primer agent to the surface of the transparent resin layer. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending 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 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

Surface protective layer The resin constituting the surface protective layer is preferably a curable resin such as a thermosetting resin or an ionizing radiation curable resin (for example, an electron beam curable resin). In particular, ionizing radiation curable resins are preferable from the viewpoint of high surface hardness, productivity, and the like.

  Examples of thermosetting resins include unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, and melamines. -Urea co-condensation resin, silicon resin, polysiloxane resin and the like.

  A curing agent such as a crosslinking agent and a polymerization initiator, and a polymerization accelerator can be added to the resin. For example, as curing agents, isocyanates, organic sulfonates, etc. can be added to unsaturated polyester resins, polyurethane resins, etc., organic amines, etc. can be added to epoxy resins, peroxides such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. A radical initiator can be added to the unsaturated polyester resin.

  Examples of the method for forming the surface protective layer with a thermosetting resin include a method in which a solution of a thermosetting resin is applied by a coating method such as a roll coating method or a gravure coating method, followed by drying and curing.

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

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

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

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald type, a bandegraft type, a resonant transformer type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type can be used. The energy of the electron beam is preferably about 100 to 1000 keV, more preferably about 100 to 300 keV. The irradiation amount of the electron beam is preferably about 2 to 15 Mrad.

  The ionizing radiation curable resin is sufficiently cured when irradiated with an electron beam, but it is preferable to add a photopolymerization initiator (sensitizer) when it is cured by irradiation with ultraviolet rays.

  Examples of the photopolymerization initiator in the case of a resin system having a radically polymerizable unsaturated group include acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide. , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used. In the case of a resin system having a cationic polymerizable functional group, for example, at least one kind such as an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonic acid ester, and a freeloxysulfoxonium diallyl iodosyl salt. Can be used.

  Although the addition amount of a photoinitiator is not specifically limited, Generally it is about 0.1-10 mass parts with respect to 100 mass parts of ionizing radiation curable resins.

  As a method of forming the surface protective layer with an ionizing radiation curable resin, for example, a solution of an ionizing radiation curable resin may be applied by a coating method such as a gravure coating method or a roll coating method.

  The thickness of the surface protective layer is usually about 0.1 to 50 μm, preferably about 1 to 20 μm.

  If necessary, various additives such as solvents, dyes, pigments and other colorants, matting agents, fillers such as extenders, antifoaming agents, leveling agents, thixotropic agents are added to the surface protective layer. be able to.

  The matting agent added to the surface protective layer is not particularly limited as long as it does not impair the design properties expressed by the sheet of the present invention, and known or commercially available ones can be used. Examples thereof include inorganic particles such as silica and silicone resin; organic particles such as crosslinked alkyl, crosslinked styrene, inzoguanamine resin, urea-formaldehyde resin, phenol resin, polyethylene, and nylon.

  10-50 mass parts is preferable with respect to 100 mass parts of resin solid content of resin which forms a surface protective layer, and, as for the addition amount of the matting agent added to the said surface protective layer, 20-40 mass parts is more preferable. By making the addition amount of a matting agent into the above-mentioned range, the shape of the surface of the sheet of the present invention can be made the above-mentioned uneven shape.

  The average particle size of the matting agent is preferably 3 to 20 μm, more preferably 4 to 14 μm. By setting the average particle diameter of the matting agent in such a range, the surface of the surface protective layer can be formed into an uneven shape with which the sheet of the present invention is provided, and the surface of the surface protective layer has a low gloss feeling. And can have the stain resistance and scratch resistance required for the surface of the sheet.

  If the surface protective layer has a configuration that does not contain a matting agent, the surface shape of the sheet of the present invention is made the above-mentioned uneven shape by a method of forming the above-mentioned uneven shape with an embossed plate on the sheet surface. Good.

If necessary, a back primer layer may be provided on the back surface of the back primer layer substrate sheet (the surface opposite to the surface on which the pattern layer is laminated). For example, when the sheet of the present invention is a decorative sheet, it is effective when a decorative sheet is produced by laminating the decorative sheet and an adherend.

  A back surface primer layer can be formed by apply | coating a well-known primer agent to a base material sheet. Examples of the primer agent include a urethane resin-based primer agent made of an acrylic-modified urethane resin (acrylic urethane-based resin), a urethane-cellulose resin (for example, a resin obtained by adding hexamethylene diisocyanate to a mixture of urethane and nitrified cotton) ), A resinous primer agent made of a block copolymer of acrylic and urethane, and the like. You may mix | blend an additive with a primer agent as needed. Examples of the additive include fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending 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 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

  Although the thickness of a back surface primer layer is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

[Decorative sheet]
The sheet of the present invention is excellent in low gloss, and the design expressed by the sheet is visible even when viewed from an oblique direction, and exhibits excellent design properties, and therefore can be suitably used as a decorative sheet. The use of such a decorative sheet is not particularly limited and can be used for various applications requiring design properties. For example, a decorative sheet for flooring used for flooring or a wall used for wall covering It is useful as a decorative sheet for equipment.

  By laminating the decorative sheet on the adherend, a decorative board can be obtained. For example, a decorative sheet that can be used as a flooring material can be obtained by laminating the decorative sheet for flooring material on an adherend. The adherend is not limited, and the same materials as those used for known decorative panels can be used. Examples of the adherend include wood materials, metals, ceramics, plastics, and glass. In particular, the decorative sheet can be suitably used for a wood material. Specific examples of wood materials include veneer, wood veneer, wood plywood, particle board, medium density fiberboard (MDF) made from various materials such as cedar, firewood, firewood, pine, lawan, teak, and melapie. , Chip boards, or composite substrates on which chip boards are laminated. As the wood material, wood plywood, particle board, medium density fiber board (MDF) is preferably used.

  The lamination method of laminating the decorative sheet and the adherend is not limited, and for example, a method of sticking the decorative sheet to the adherend with an adhesive can be employed. What is necessary is just to select an adhesive agent suitably from well-known adhesive agents according to the kind etc. of to-be-adhered material. Examples thereof include polyvinyl acetate, polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ionomer, butadiene / acrylonitrile rubber, neoprene rubber, natural rubber and the like. These adhesives are used alone or in combination of two or more.

  The decorative board manufactured in this way includes, for example, interior materials for buildings such as walls, ceilings, and floors; exterior materials such as balconies and verandas; surface decorative boards and furniture for furniture such as window frames, doors, and handrails; Alternatively, it can be used for a surface decorative plate of a cabinet such as a light electric or OA device. In particular, the decorative board can be suitably used as a floor decorative material.

  The sheet of the present invention has a specific range of ten-point average roughness Rzjis94 (JIS B0601: 2001) on the surface of the sheet, the average length RSm (JIS B0601: 2001) of the surface roughness curve element, and the surface Since the ratio RSm / Rzjis94 to the ten-point average roughness Rzjis94 is in a specific range and the reflectance at 45 ° is in a specific range, it is excellent in low gloss and when viewed from an oblique direction. Since the reflection of light on the surface of the sheet is suppressed, the design expressed by the sheet is visible, and the design is excellent.

It is sectional drawing which shows an example of the sheet | seat of this invention. It is sectional drawing which shows an example of the sheet | seat of this invention. It is sectional drawing which shows an example of the sheet | seat of this invention.

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

Example 1
An 80 μm thick polyethylene film was prepared as a base sheet. A back primer layer having a thickness of 2 μm was formed by applying a two-component curable urethane resin to the back surface of the polyethylene film.

  A pattern layer having a thickness of 2 μm was formed on the front surface of the polyethylene film by gravure printing. An adhesive layer having a thickness of 2 μm made of a two-component curable urethane resin was formed on the pattern layer. On the adhesive layer, a transparent polypropylene resin having a thickness of 100 μm was laminated by extrusion lamination to form a transparent resin layer.

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

  A urethane acrylate electron beam curable resin (EB resin) is applied to the front surface of the primer layer by a gravure coating method so that the thickness (layer thickness) after curing is 15 μm, and then an oxygen concentration of 200 ppm. Under the following environment, an electron beam was irradiated using an electron beam irradiation device under the conditions of an acceleration voltage of 175 KeV and 5 Mrad, and the surface protection layer was formed by curing the electron beam curable resin.

  The surface protective layer side is heated with an infrared non-contact heater to soften the base sheet and the transparent resin layer, and then immediately embossed with hot pressure to create a grainy uneven pattern (wood grain plate conduit groove). Molded and created a sheet.

  The ten-point average roughness Rzjis94 (JIS B0601: 2001) of the plane portion other than the wood grain pattern (wood grain plate conduit groove) of the sheet surface is 17.8 μm, and the average length RSm (JISB0601: 2001) of the surface roughness curve element. ) And Rzjis94, the ratio RSm / Rzjis94 was 5.5, and the reflectance at the detection angle of 45 ° of the light incident on the incident angle of 45 ° and reflected from the surface was 26%.

Examples 2-4, Comparative Example 1
Sheets of Examples 2 to 4 and Comparative Example 1 were prepared in the same manner as in Example 1 except that the configuration of the surface protective layer and the uneven shape of the sheet surface were changed as shown in Table 1.

Example 5
The structure of the surface protective layer was changed as shown in Table 1, a matte flat uneven pattern was formed instead of the embossed wood grain uneven pattern, and the uneven surface shape was changed as shown in Table 1. A sheet of Example 5 was prepared in the same manner as Example 1 except for the above.

Example 6 and Comparative Example 2
Instead of forming the primer layer (primer layer for forming the surface protective layer) and the surface protective layer, a matte flat concavo-convex pattern is formed instead of the embossed grain pattern concavo-convex pattern, and the sheet surface (transparent resin layer) The sheets of Example 6 and Comparative Example 2 were prepared in the same manner as in Example 1 except that the uneven shape of the surface) was changed as shown in Table 1.

Example 7
After forming the surface protective layer, the surface of the surface protective layer is subjected to corona discharge treatment, and using a colored resin made of a two-component curable urethane resin, the surface of the surface protective layer is partially gravure-printed to form a wood grain conduit pattern. A pattern part was formed. After forming the pattern part, the surface protective layer side is heated with an infrared non-contact type heater to soften the base sheet and the transparent resin layer, and then immediately embossed with heat pressure to create a grainy uneven pattern. Was shaped. Otherwise in the same manner as in Example 1, a sheet of Example 7 was prepared.

  About the sheet | seat of the Example and comparative example prepared as mentioned above, each following evaluation item was evaluated by each evaluation method.

(Evaluation method)
Rzjis94 (10-point average roughness)
Rzjis94 (10-point average roughness) was measured from the roughness curve by a measuring method based on JIS B0601: 2001. The measurement was performed on three arbitrary points on the surface of the sheet using SURFCOM FLEX-50A (manufactured by Tokyo Seimitsu Co., Ltd.), and the average value was evaluated. The Rzjis94 (ten-point average roughness) referred to here is defined in JIS B0601 (2001) “Product Geometric Specification (GPS) —Surface Property: Contour Curve Method—Terminology, Definition, and Surface Property Parameter”, Annex 1. In the 1994 edition of JIS, it is the same as the ten-point average roughness Rz that is normally defined in JIS B0601.

RSm (average length of roughness curve element)
It measured using SURFCOM FLEX-50A (made by Tokyo Seimitsu Co., Ltd.) by the measuring method based on JIS B0601: 2001. Measurements were made on three arbitrary points on the surface of the sheet, and the average value was evaluated.

Gloss (60 ° gloss)
The 60 ° gloss on the surface of the sheet was measured by a method based on JIS Z8741. The 60 ° gloss measurement was performed using a glossiness measuring instrument (trade name: GMX-202, manufactured by Murakami Color Research Laboratory Co., Ltd.).

Using a reflectivity goniophotometer (trade name: GC5000L, manufactured by Nippon Denshoku Industries Co., Ltd.) at 45 °, incident light at an incident angle of 45 ° and reflected at the surface of the sheet at a detection angle of 45 ° The reflectance was measured.

The appearance of the design visibility sheet was visually observed from various angles and evaluated according to the following evaluation criteria.
○: The surface of the sheet is not brightened by oblique light, and the pattern can be visually recognized.
(Triangle | delta): Although the sheet | seat surface is slightly white by oblique light, a pattern can be visually recognized.
X: The sheet surface is whitened by oblique light, and the pattern cannot be visually recognized.

The surface of the scratch-resistant sheet was rubbed with steel wool (# 0000) at a load of 300 g / cm ² with an upper limit of 20 reciprocations, and the number of reciprocations in which the appearance changed visually was measured. In addition, about the sheet | seat of Example 7, the location where the pattern part of the wood grain conduit pattern was not formed in the sheet | seat surface was measured.

  The results are shown in Table 1 below.

1. Sheet 2. 2. Back primer layer Base sheet 4. Pattern layer 5 5. Adhesive layer 6. Transparent resin layer Primer layer 8. 8. Surface protective layer 9. Planar portion having an uneven shape on the surface. Wood grain plate conduit groove 11. Pattern part

Claims (9)

The surface 10-point average roughness Rzjis94 (JIS B0601: 2001) is 4 μm or more,
The ratio RSm / Rzjis94 of the average length RSm (JIS B0601: 2001) of the surface roughness curve element to the ten-point average roughness Rzjis94 of the surface is less than 25,
The reflectance at a detection angle of 45 ° of light incident on an incident angle of 45 ° and reflected from the surface is 100% or less.
A sheet characterized by that.   The sheet according to claim 1, comprising a surface protective layer containing an ionizing radiation curable resin on the outermost surface.   The sheet according to claim 1 or 2, comprising a transparent resin layer containing a polyolefin-based resin.   The sheet | seat in any one of Claims 1-3 which has a pattern pattern layer.   The sheet according to claim 4, wherein at least the pattern layer, the transparent resin layer, and the surface protective layer are laminated in this order on a base sheet.   The sheet | seat in any one of Claims 1-5 whose thickness is 50-600 micrometers.   The sheet according to any one of claims 1 to 6, which is a decorative sheet.   The sheet according to any one of claims 1 to 6, which is a decorative sheet for flooring.   A decorative sheet obtained by laminating the decorative sheet according to claim 7 or the decorative sheet for flooring according to claim 8 on an adherend.

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