JP4858053B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet used for interiors, exteriors, furniture, surface decorations of furniture, interiors of vehicles, etc., and in particular, design properties having scratch resistance, contamination resistance, touch, matte feeling, glossiness, etc. The present invention relates to an excellent decorative sheet.

As surface decorative boards for interiors, exteriors, furniture, joinery, and vehicle interiors of buildings, for example, those having a structure in which a decorative sheet printed with a wood grain pattern or the like is bonded with an adhesive are used.
The decorative sheet used for such a decorative sheet is required to have various characteristics such as excellent design as well as touch, matte, gloss and stain resistance.
Among these, it has been proposed to provide a raised portion on the surface of the decorative sheet, in particular, in order to obtain a tactile sensation, matte sensation, glossiness, and design.
As such a decorative sheet, for example, Patent Document 1 discloses a decorative sheet in which a polygonal or circular regular or regular raised portion is provided on the surface of the decorative sheet, and Patent Document 2 describes the unevenness of the raised portion. A decorative sheet, in which the surface area ratio of the difference and the convex portion is limited, Patent Document 3 discloses a decorative sheet provided with a concavo-convex portion made of an ionizing radiation curable resin ink on the surface.
However, this decorative sheet does not have sufficient tactile sensation, matte sensation and glossiness as a sheet, and further improvement in design properties has been demanded.
Furthermore, since the sheet having such a raised portion is usually inferior in stain resistance, a sheet excellent in stain resistance has been demanded. Further, further improvement has been required for scratch resistance.

JP 2003-94592 A Japanese Patent No. 3334365 JP 2004-249586

  An object of the present invention is to provide a decorative sheet having excellent design properties having scratch resistance, stain resistance, touch, matte feeling, glossiness, and the like, even though it has been made to solve the above problems.

As a result of intensive studies to achieve the above object, the present inventor has achieved the above object by providing a two-step buildup on the outermost surface of the decorative sheet and providing a surface protective layer on the outermost surface. It has been found that this has been achieved, and the present invention has been completed.
That is, the present invention includes at least a colored layer on a base material, a permeation layer covering the colored layer, a first top layer formed on the permeation layer from a plurality of first tops, and the first A decorative sheet formed by laminating a plurality of second upper layers formed in this order on the upper layer, wherein the outermost surface including the second upper layer is made of ionizing radiation or an ultraviolet curable resin. coated with comprising the surface protective layer, Ri Do a material the permeation layer penetrates the ionizing radiation or ultraviolet curing resin, and in which the permeation layer provides a decorative sheet you containing a polyester urethane resin binder .

  ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet excellent in the designability which has a scratch resistance, stain resistance, a touch feeling, a mat feeling, a glossiness, etc. can be obtained.

As shown in FIG. 1, the decorative sheet 1 of the present invention includes at least a colored layer 3 on a base material 5, a permeation layer 4 that covers the colored layer 3, and a number of first raised portions 9 on the permeation layer 4. A decorative sheet 1 in which a first raised layer 10 formed from a plurality of second raised upper layers 7 formed from a plurality of second raised portions 6 are laminated in this order, The outermost surface including the two upper layers 7 is covered with a surface protective layer 12 made of ionizing radiation or ultraviolet curable resin, and the penetration layer 4 is a decorative sheet 1 made of a material that penetrates the ionizing radiation or ultraviolet curable resin.
As shown in FIG. 1, the decorative sheet 1 of the present invention may have a colored solid layer 2 between the base material 5 and the colored layer 3.

The base material 5 used in the present invention is not particularly limited as long as it is usually used as a base material for a decorative sheet. Various papers, plastic films, plastic sheets, metal foils, metal sheets, metal plates, A woody board such as wood, a ceramic material, or the like can be appropriately selected according to the application. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper or a composite of paper and a plastic film.
When using these substrates, particularly plastic films or plastic sheets, as a substrate, an oxidation method or a concavo-convex method may be applied to one or both sides as desired in order to improve the adhesion to the layer provided thereon. Physical or chemical surface treatment can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
Further, the substrate may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance.

As various papers used as the substrate 5, thin paper, kraft paper, titanium paper and the like can be used. These paper base materials are used to reinforce the interlaminar strength between the fibers of the paper base material or between the other layers and the paper base material, and to prevent the occurrence of scuffing, in addition to these paper base materials, acrylic resin, styrene butadiene rubber, A resin such as a melamine resin or a urethane resin may be added (resin impregnation after paper making or embedded during paper making). For example, inter-paper reinforced paper, resin-impregnated paper, and the like.
In addition to these, various papers often used in the field of building materials such as linter paper, paperboard, base paper for gypsum board, or a vinyl wallpaper raw material in which a vinyl chloride resin layer is provided on the surface of the paper can be mentioned. Furthermore, coated paper, art paper, sulfate paper, glassine paper, parchment paper, paraffin paper, Japanese paper, or the like used in the office field or normal printing and packaging can also be used. Moreover, although distinguished from these papers, woven fabrics and non-woven fabrics of various fibers having an appearance and properties similar to paper can be used as the base material. Examples of various fibers include inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, and carbon fibers, or synthetic resin fibers such as polyester fibers, acrylic fibers, and vinylon fibers.

  As a plastic film or a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 And polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, and the like.

  As metal foil, a metal sheet, or a metal plate, what consists of aluminum, iron, stainless steel, or copper, for example can be used, and what gave these metals by plating etc. can also be used. Examples of the various wood-based boards include wood fiberboards such as wood veneer, plywood, laminated wood, particle board, or MDF (medium density fiberboard). Examples of the ceramic material include ceramic building materials such as gypsum board, calcium silicate board, and wood cement board, ceramics, glass, firewood, and fired tile. In addition to these, composites of various materials, such as fiber reinforced plastic (FRP) plates, paper honeycombs with iron plates pasted on both sides, and two aluminum plates sandwiched with polyethylene resin can also be used as the base material. .

Although there is no restriction | limiting in particular about the thickness of the base material 5, When using the sheet | seat which uses a plastic as a raw material, thickness is about 20-150 micrometers normally, Preferably it is the range of 30-100 micrometers, and a paper base material is used. When used, the basis weight is usually about ²⁰ to 150 g / m ² , preferably 30 to 100 g / m ² .

In the present invention, the colored solid layer 2 is also referred to as a concealing layer or a full surface solid layer provided as desired for the purpose of improving the design of the decorative sheet of the present invention. The colored solid layer 2 is formed when the color of the surface of the base material 5 is adjusted so that the base material 5 itself is colored or uneven in color, and gives the intended color to the surface of the base material 5 It is. Usually, it is formed with an opaque color, but it may be formed with a colored transparent color to make use of the pattern of the base. When utilizing that the base material 5 is white, or when the base material 5 itself is appropriately colored, it is not necessary to form the colored solid layer 2.
As the ink used for forming the colored solid layer 2, an ink in which a binder, a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, or a curing agent is appropriately mixed is used. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polypropylene resins, acrylic resins, and polyesters. Arbitrary resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins, cellulose acetate resins and the like may be used alone or in combination of two or more.
Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metallic pigments composed of scaly foil pieces such as aluminum and brass, pearlescent pigments composed of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.
The colored solid layer 2 is preferably a so-called solid printed layer having a thickness of about 1 to 20 μm.

In the present invention, the colored layer 3 gives decorativeness to the base material 5 and is formed by printing various patterns using ink and a printing machine. The colored layer 3 is preferably a pattern layer, It is preferable that the pattern layer is an abstract pattern. As patterns, there are stone patterns imitating the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns imitating cloth and cloth patterns, tiled patterns, brickwork patterns, etc. There are also patterns such as marquetry and patchwork that combine these. These patterns can be formed by multicolor printing with normal yellow, red, blue, and black process colors, and also by multicolor printing with special colors prepared by preparing individual color plates that make up the pattern. Is done.
The colored layer 3 may be provided on the front surface of the base material or may be provided partially as shown in FIG.
As the pattern ink used for the colored layer 3, the same ink as that used for the colored solid layer 2 can be used.
Although there is no restriction | limiting in particular about the thickness of the colored layer 3, Usually, about 1-30 micrometers, Preferably it is the range of 1-20 micrometers.

In the present invention, the penetrating layer 4 has a function of penetrating ionizing radiation or ultraviolet curable resin constituting the surface protective layer 12.
The material of the osmotic layer 4 has a property of eluting into the ionizing radiation or the ultraviolet curable resin composition forming the surface protective layer 5, and the ionizing radiation or the ultraviolet curable resin composition (uncured product) and It is appropriately selected in relation to Specifically, an ink having a non-crosslinkable resin as the binder resin is preferable, and for example, a thermoplastic (non-crosslinked type) urethane resin is preferable. If necessary, unsaturated polyester resin, acrylic resin, or vinyl chloride-vinyl acetate copolymer is used to adjust the degree of expression of the low gloss area and the contrast of the gloss difference between the low gloss area and the surrounding area. Can be mixed.
Although there is no restriction | limiting in particular about the thickness of the osmosis | permeation layer 4, Usually, about 1-20 micrometers, Preferably it is the range of 1-10 micrometers.

In the decorative sheet 1 of the present invention, a two-step raised layer composed of a first and a second raised layer is formed on the permeation layer 4.
In the two-step buildup, a first buildup layer 10 formed from a large number of first buildup portions 9 on the permeation layer 4 and a second buildup formed from a large number of second buildup portions 6 on the first buildup layer 10. By laminating the upper layer 7 in this order, the stain resistance of the decorative sheet is improved, and further, a two-level outline is expressed and a rich pattern can be expressed, and a pattern on the surface layer is formed. Since a difference in gloss occurs between the formed part and the part where it is not formed, the decorativeness or design of the decorative sheet is enhanced.

It does not specifically limit as a material of the 1st buildup layer 10 and the 2nd buildup layer 7, For example, the ink and thermosetting resin which are used for the coloring solid layer 2 can be used.
Examples of the thermosetting resin include polyester resin, urethane resin, epoxy resin, melamine resin, alkyd resin, phenol resin, and acrylic resin.
Moreover, various additives can be mix | blended with the said thermosetting resin according to the desired physical property of the cured resin layer obtained. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.

The shape of the first raised portion 9 in the present invention is not particularly limited, but is preferably an irregular shape, for example, a Voronoi-divided shape as shown in FIG. 2 is preferred.
Here, the basic concept of Voronoi division is to determine a dominating region for each of a large number of generating points M distributed in space based on a predetermined condition, and divide the space into a plurality of dominating regions. is there. As a condition for determining the dominant region, a distance (Euclidean distance) between a predetermined point on the space and the mother point is used.

The height of the first raised portion 9 is preferably 1 to 20 μm, and if it is within this range, the effects of contamination resistance, tactile sensation, matte sensation, gloss sensation, and design are sufficiently obtained.
The occupied area of the first raised portion 9 with respect to the permeation layer 4 is preferably 50 to 99%, and if it is within this range, the effects of contamination resistance, touch feeling, matte feeling, glossiness, and design properties can be sufficiently obtained. .

The shape of the second raised portion 6 in the present invention is not particularly limited, and may be a regular shape such as a regular array of circles, squares, and hexagons, or an irregular pattern as shown in FIG. Often, an irregular pattern is preferable because it is excellent in touch, matte, gloss and design.
Moreover, the real feeling of a grain is obtained by synchronizing the pattern of the 2nd overlay layer 7 with the colored layer 3. FIG.

The height of the second raised portion 6 is preferably 30 to 90 μm, and if it is within this range, the effects of contamination resistance, tactile sensation, matte sensation, gloss sensation, and design are sufficiently obtained.
The occupied area of the second raised portion 6 with respect to the permeation layer 4 is preferably 10 to 90%, and if it is within this range, the effects of contamination resistance, tactile sensation, matte sensation, glossiness and design are sufficiently obtained. .

  Moreover, as a formation method of the 1st buildup layer 10 and the 2nd buildup layer 7, for example, the 1st buildup part 9 and the 2nd buildup part 6 are used by gravure printing using the plate | plate type | mold of an irregular pattern like FIG. Can be formed simultaneously. The plate mold shown in FIG. 3 first combines a cell shape for forming the first overlay layer 10 as shown in FIG. 2 and a cell shape of a pattern corresponding to the second overlay layer 7 by image processing or the like. Can be prepared by a conventional method. The colored solid layer 2, the colored layer 3 and the protective layer 4 may be printed and laminated by a conventional method such as gravure or screen printing.

In the present invention, a surface protective layer 12 made of ionizing radiation or an ultraviolet curable resin is provided on the outermost surface including the second buildup layer 7, thereby improving the scratch resistance of the decorative sheet.
In the present invention, the thickness of the surface protective layer 12 is preferably 1 to 20 μm, and if it is within this range, the effects of stain resistance, tactile sensation, matte sensation, glossiness and design are sufficiently obtained. More preferably, the thickness is 2 to 15 μm.

  The ionizing radiation or ultraviolet curable resin that forms the surface protective layer 12 may be formed from an ionizing radiation or ultraviolet curable resin composition. The ionizing radiation or ultraviolet curable resin composition may be an electromagnetic wave or a charged particle beam. The resin composition having an energy quantum capable of crosslinking and polymerizing molecules, that is, a resin composition that is crosslinked and cured by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers or prepolymers conventionally used as ionizing radiation or ultraviolet curable resin compositions.

  Typically, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is suitable as the polymerizable monomer, and among them, a polyfunctional (meth) acrylate is preferable. Here, “(meth) acrylate” means “acrylate or methacrylate”. The polyfunctional (meth) acrylate is not particularly limited as long as it is a (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule. Specifically, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone-modified dicyclopentenyl di (meth) acrylate, ethylene oxide-modified phosphate di ( (Meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimethylo Propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, ethylene oxide modified dipentaerythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. Is mentioned. These polyfunctional (meth) acrylates may be used singly or in combination of two or more.

  In the present invention, a monofunctional (meth) acrylate can be used in combination with the polyfunctional (meth) acrylate as long as the object of the present invention is not impaired, for the purpose of lowering the viscosity. Examples of monofunctional (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl ( Examples include meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

  Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate, urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate The system etc. are mentioned. Here, the epoxy (meth) acrylate oligomer can be obtained, for example, by reacting (meth) acrylic acid with an oxirane ring of a relatively low molecular weight bisphenol type epoxy resin or novolak type epoxy resin and esterifying it. . Further, a carboxyl-modified epoxy (meth) acrylate oligomer obtained by partially modifying this epoxy (meth) acrylate oligomer with a dibasic carboxylic acid anhydride can also be used. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid. Examples of polyester (meth) acrylate oligomers include esterification of hydroxyl groups of polyester oligomers having hydroxyl groups at both ends obtained by condensation of polycarboxylic acid and polyhydric alcohol with (meth) acrylic acid, It can be obtained by esterifying the terminal hydroxyl group of an oligomer obtained by adding an alkylene oxide to a carboxylic acid with (meth) acrylic acid. The polyether (meth) acrylate oligomer can be obtained by esterifying the hydroxyl group of the polyether polyol with (meth) acrylic acid.

  Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak epoxy resin, bisphenol epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  Moreover, various additives can be mix | blended with the said ionizing radiation or a ultraviolet curable resin composition according to the desired physical property of the cured resin layer obtained. Examples of this additive include a weather resistance improver, an abrasion resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorber, an antistatic agent, an adhesion improver, a leveling agent, a thixotropic agent, a coupling agent, A plasticizer, an antifoamer, a filler, a solvent, a coloring agent, etc. are mentioned.

In the present invention, the polymerizable monomer or polymerizable oligomer, which is the ionizing radiation or ultraviolet curable component, and various additives are homogeneously mixed at a predetermined ratio, respectively, and the coating made of the ionizing radiation or ultraviolet curable resin composition is used. Prepare a working solution. The viscosity of the coating solution is not particularly limited as long as it is a viscosity capable of forming an uncured resin layer on the surface of the substrate by a coating method described later.
In the present invention, the coating liquid prepared in this way is applied to the surface of the substrate so that the thickness after curing is 1 to 20 μm, gravure coating, bar coating, roll coating, reverse roll coating, Coating is performed by a known method such as comma coating, preferably gravure coating, to form an uncured resin layer. When the thickness after curing is 1 μm or more, a cured resin layer having a desired function is obtained. The thickness of the surface protective layer after curing is preferably about 2 to 15 μm.

In the present invention, the uncured resin layer thus formed is irradiated with an electron beam, ultraviolet rays, or the like to cure the uncured resin layer. Here, when an electron beam is used as ionizing radiation or ultraviolet rays, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. It is preferable.
In electron beam irradiation, the transmission capability increases as the acceleration voltage increases. Therefore, when using a base material that deteriorates due to the electron beam as the base material, the transmission depth of the electron beam and the thickness of the resin layer are substantially equal. By selecting the accelerating voltage so as to be equal to each other, it is possible to suppress the irradiation of the electron beam to the base material, and to minimize the deterioration of the base material due to the excessive electron beam.
The irradiation dose is preferably such that the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
Further, the electron beam source is not particularly limited. For example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type. Can be used.
When ultraviolet rays are used, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.
The cured resin layer thus formed has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, and anti-fouling coat having high hardness and scratch resistance. A function, an antiglare coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can also be imparted.

The decorative sheet 1 of the present invention can be attached to various substrates and used as a decorative board. The board | substrate used as a to-be-adhered body is not specifically limited, A plastic board, a metal board, woody board | plates, such as a timber, a ceramic material, etc. can be selected suitably according to a use. When these substrates, particularly plastic sheets, are used as substrates, a physical or chemical surface treatment such as an oxidation method or a concavo-convex method is applied to one or both sides as desired in order to improve adhesion to the decorative sheet. Can be applied.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.

  As a plastic sheet, what consists of various synthetic resins is mentioned. Synthetic resins include polyethylene resin, polypropylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-vinyl. Representative examples include alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or nylon 66 And polyamide resin, cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, polyimide resin, and the like.

As a metal plate, what consists of aluminum, iron, stainless steel, or copper can be used, for example, and what gave these metals by plating etc. can also be used.
Examples of wood-based boards include veneer of various materials such as cedar, firewood, firewood, pine, lawan, teak and melapie, and wood materials such as wood veneer, wood plywood, particle board, and medium density fiber board (MDF). . These can be used alone or in a stacked manner. The wooden board includes not only a wooden board but also a plastic board containing paper powder and reinforced paper having strength.
Examples of the ceramic material include ceramic building materials such as a gypsum plate, a calcium silicate plate, and a wood piece cement plate, ceramics, glass, firewood, fired tiles, plates made mainly of volcanic ash, and the like.
In addition to these, composites of various materials, such as fiber reinforced plastic (FRP) plates, paper honeycombs with iron plates pasted on both sides, and two aluminum plates sandwiched with polyethylene resin can also be used as the base material. .

Further, the substrate may be subjected to a treatment such as forming a primer layer, or a coating for adjusting the color or a pattern from a design viewpoint may be formed in advance. As a substrate to be an adherend, plate materials such as flat plates and curved plates of various materials, or three-dimensional shaped articles (molded products) in which the above materials are used alone or in combination are targeted.
A backing material such as Japanese paper, Western paper, synthetic paper, non-woven fabric, woven fabric, cold paper, impregnated paper, synthetic resin sheet, or the like may be attached to the decorative sheet. By sticking the backing material, it acts to reinforce the decorative sheet itself, prevent cracking and tearing of the decorative sheet, prevent bleeding of the adhesive to the decorative sheet surface, and prevent the occurrence of defective products, Handling becomes easy and productivity can be improved.
Thus, a substrate on which a decorative sheet is placed every leaf or continuously via an adhesive is attached to a cold press, a hot press, a roll press, a laminator, a lapping, an edge pasting machine, a vacuum press, etc. The decorative sheet is bonded to the substrate surface by pressing with an apparatus to obtain a decorative plate.

The adhesive is applied using an application device such as a spray, spreader, or bar coater. As the adhesive, vinyl acetate resin-based, urea resin-based, melamine resin-based, phenol resin-based, isocyanate-based adhesives, etc., are used alone or as a mixed adhesive obtained by arbitrarily mixing them. As needed, talc, calcium carbonate, clay, titanium white and other inorganic powders, wheat flour, wood flour, plastic powder, coloring agents, insect repellents, fungicides and the like can be added and mixed in the adhesive. . In general, the adhesive is applied to the substrate surface with a solid content of 35 to 80% by mass and an application amount of 50 to 300 g / m ² .
Adhesion of the decorative sheet on the substrate is usually performed by forming an adhesive layer on the back surface of the decorative sheet of the present invention and adhering the substrate or applying an adhesive on the substrate and adhering the decorative sheet. Etc.

  The decorative board manufactured as described above can be arbitrarily cut and subjected to optional decoration such as grooving and chamfering on the surface and the end of the cut using a cutting machine such as a router or a cutter. And various uses, for example, interior or exterior materials of buildings such as walls, ceilings, floors, window frames, doors, handrails, skirting boards, surrounding edges, surface decorative boards for fittings such as malls, kitchens, furniture or light electrical appliances, It can be used for surface decorative boards of cabinets such as OA equipment, interiors and exteriors of vehicles.

EXAMPLES Next, although an Example demonstrates this invention further in detail, it is not limited at all by these.
In the examples and comparative examples, the occupied area of the conduit portion and the upper portion, the touch feeling, the matte feeling, the glossiness, and the design (the unevenness feeling, the fine feeling of rise and the wood grain design feeling (random feeling)) are as follows. Measured.
(1) Measuring method of occupied area of conduit part and top part Olympus Optical Co., Ltd. non-contact surface roughness meter “three-dimensional measuring microscope” STM6ZP (trade name), magnification 50 times, measuring pitch 0.1010 mm, The driving speed was measured under high speed conditions.
(2) Contamination resistance It evaluated based on the JAS special plywood contamination A test.
○: No contamination remains △: Some contamination remains ×: Remarkably contamination remains (3) Marling resistance Steel wool manufactured by Bonstar Sales Co., Ltd. is attached to the end of the weight (300 g / cm ² ), and the sample surface is attached. The appearance after 50 reciprocations was evaluated.
○: No change in appearance Δ: Surface changes in gloss ×: The coating film is scratched

(4) Tactile Feel (i) Elevated Feel The feel touched by human hands was evaluated according to the following criteria.
○: There is a great feeling of elevation Δ: There is a slight feeling of elevation ×: There is almost no feeling of elevation (ii) Feeling of fine irregularities The feeling of contact with human hands was evaluated according to the following criteria.
○: Each raised shape is small and has a feeling of delicate unevenness. Δ: There is a slight feeling of unevenness. ×: Each raised shape is large and there is no feeling of delicate unevenness. (5) Visual decoration feeling.
(iii) Wood grain design (randomness)
The results of visual observation were evaluated according to the following criteria.
○: The upper part is a random shape and close to the main wall ×: The upper part is a fixed shape, not a random shape, and there is no real feeling
(iv) Glossiness The results of visual observation were evaluated according to the following criteria.
○: Shine changes depending on the viewing angle Δ: Although there is shimmering, there is almost no change depending on the viewing angle ×: No shimmering

Examples 1-2
As the base material 5, a reinforced paper between building materials with a weight of 30 g / m ² of rice is used, and acrylic resin and nitrified cotton are used as binders on one side, and ink containing titanium white, petal, and chrome lead as colorants is used. A (solid entire surface) layer having a coating amount of 5 g / m ² was applied by gravure printing to obtain a colored solid layer 2. A woodgrain colored layer 3 was formed by gravure printing using an ink containing nitrified cotton as a binder and a colorant mainly composed of a dial.
Subsequently, 10% by mass of silica particles having an average particle diameter of 1.5 μm was blended with a transparent ink having a polyester urethane resin having a number average molecular weight of 30,000 and a glass transition temperature (Tg) of −62.8 ° C. as a binder. The penetration layer 4 was formed by gravure printing using the ink composition.
Thereafter, a plate of an irregularly shaped pattern shown in FIG. 3 was used using an ink for raising the main component of acrylic resin (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: KKB Cure U Semi Matte Medium). A two-stage upper layer composed of the first upper layer 10 and the second upper layer 7 was formed using a mold (50% Voronoi of the first upper layer 10). The plate depth corresponding to the first raised layer 10 is as shown in Table 1. Further, the occupied area of the plate mold corresponding to the non-conduit portions of the first raised portion 9 and the second raised portion 6 with respect to the protective layer 4 is as shown in Table 1.
Next, 60 parts by mass of ethylene oxide-modified trimethylolpropane ethylene oxide triacrylate, which is a trifunctional acrylate monomer, and 40 parts by mass of dipentaerythritol hexaacrylate, which is a hexafunctional acrylate monomer, are formed on the upper part of the two-tiered structure. An electron beam curable resin composition comprising 2 parts by mass of 5 μm silica particles and 1 part by mass of a silicone acrylate prepolymer was applied at a coating amount of 5 g / m ² by a gravure offset coater method. After coating, an electron beam with an acceleration voltage of 175 kV and an irradiation dose of 30 kGy (3 Mrad) was irradiated to cure the electron beam curable resin composition, thereby forming the surface protective layer 12. Next, curing was performed at 70 ° C. for 24 hours to produce a decorative sheet 1. The thickness of the surface protective layer 12 was 5 μm.
Table 1 shows the results of measuring the occupied areas of the first and second upper portions 9 and 6 on the permeation layer 4 of the decorative sheet 1 obtained. The results of the evaluations (2) to (5) are shown in Table 1.
In Table 1, the maximum height is the maximum height of the peak, and the height peak is the maximum occupied area when the height distribution of the peak is represented by a histogram (see FIG. 5). It is the height that becomes.

Comparative Examples 1-3
In Examples 1 and 2, the first build-up layer 10 in FIG. 1 is formed under the conditions shown in Table 1 using the plate shape of the irregular shape shown in FIG. 4 without forming the first build-up layer. A non-existing decorative sheet was produced. The thickness of the surface protective layer was 4 μm.
Table 2 shows the measurement results of the occupied area of the upper portion and the occupied area according to the height of the upper portion on the permeation layer of the obtained decorative sheet. The results of the evaluations (2) to (5) are shown in Table 1.

Comparative Example 4
A decorative sheet was produced in the same manner as in Example 1 except that the surface protective layer 12 was not formed.
Table 1 shows the results of measuring the occupied areas of the first and second upper portions 9 and 2 on the permeation layer of the decorative sheet obtained. The results of the evaluations (2) to (5) are shown in Table 1.

ADVANTAGE OF THE INVENTION According to this invention, the decorative sheet excellent in the designability which has a scratch resistance, stain resistance, a touch feeling, a mat feeling, a glossiness, etc. can be obtained.
In particular, when it is used for a wood grain pattern, it is possible to realistically express the unevenness of the raised portion, and it is possible to obtain the same texture as a material using actual wood. Moreover, it is suitable for the interior of a building, exterior, furniture, surface makeup of joinery, interior of a vehicle, and the like.

It is a schematic diagram which shows the cross section of the decorative sheet of this invention. It is a photograph which shows the shape of the 1st embankment divided | segmented by Voronoi. It is a photograph which shows the surface shape of the plate type used in the Example. It is a photograph which shows the surface shape of the printing plate used in the comparative example. It is the histogram used when measuring the occupation area according to height in an Example and a comparative example.

Explanation of symbols

1. Cosmetic sheet 2. Colored solid layer 3. Colored layer Penetration layer 5. Base material 6. Second upper part 7. Second upper layer 9. First top 10. First upper layer 12. Surface protective layer

Claims (8)

At least a colored layer on the base material, a permeation layer covering the colored layer, a first top layer formed on the permeation layer from a number of first tops, and a number of tops on the first top layer A decorative sheet formed by laminating a second upper layer formed from the second upper layer in this order,
The top-surface containing the second Sheng upper is coated with a surface protective layer made of ionizing radiation or ultraviolet-curable resin, Ri Do a material the permeation layer penetrates the ionizing radiation or ultraviolet-curable resin, and the permeation layer decorative sheet but you containing a polyester urethane resin binder.   The decorative sheet according to claim 1, wherein the colored layer is a pattern layer.   The decorative sheet according to claim 1 or 2, wherein the first raised portion has an irregular shape, and the second raised portion has an irregularly shaped pattern.   The decorative sheet according to any one of claims 1 to 3, wherein the first raised portion has an irregular shape obtained by Voronoi division. The decorative sheet according to any one of claims 1 to 4, wherein the first overlay layer and the second overlay layer are formed from the same ink. The decorative sheet according to any one of claims 1 to 5 , wherein the surface protective layer has a thickness of 1 to 20 µm. The decorative sheet according to any one of claims 2 to 6 , wherein the pattern layer is an abstract pattern. The decorative sheet according to any one of claims 1 to 7 , further comprising a colored solid layer between the substrate and the colored layer.

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