JP5935911B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet.

  Gloss matte-like (colors that make glossy parts stand out and make glossy parts appear to be recessed) are used for interior and exterior of buildings, furniture, fittings, interiors of vehicles, and cosmetics for home appliances. It is used as

  Conventionally, as a method for producing the glossy matte decorative sheet, 1) a method of printing ink in which a matte material is added to a conduit portion of wood, 2) wiping for embedding the conduit portion and filling the recess with ink The method is known. Such a decorative sheet manufacturing method and a decorative sheet obtained by the method are disclosed in, for example, Patent Documents 1 to 4.

JP-A-2-151475 JP 2007-196405 A Japanese Patent Laid-Open No. 08-127109 JP 2006-95992 A

  The decorative sheet obtained by the production method 1) visually looks glossy, but lacks a three-dimensional design because there is no dent in the conduit portion.

  In addition, the decorative sheet obtained by the production method 2) can be colored because the recess is filled with ink. However, since the conduit portion is filled with ink, the unevenness has no three-dimensional effect. Moreover, since a dedicated processing machine is required, there is a problem that the cost is high.

  Accordingly, an object of the present invention is to provide a decorative sheet provided with a gloss matte tone having a high design property.

  As a result of intensive studies to achieve the above object, the present inventors have found that a decorative sheet having a specific uneven pattern can achieve the above object, and have completed the present invention.

That is, the present invention relates to the following decorative sheet.

1. At least a transparent resin layer, a gloss adjusting layer, a primer layer and a surface protective layer are laminated in order, and a decorative sheet having a concavo-convex pattern formed on the surface,
The primer layer contains a two-component curable urethane resin composed of an acrylic-urethane block copolymer and hexamethylene diisocyanate,
The concavo-convex pattern includes a recess in which the gloss adjusting layer is exposed in part or in whole.
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the gloss adjusting layer contains at least one resin component selected from the group consisting of a urethane resin, an acrylic resin, and an acrylic urethane copolymer resin.
3. Item 3. The decorative sheet according to Item 1 or 2, wherein the surface protective layer comprises an ionizing radiation curable resin or a two-component curable urethane resin.
4). The gloss adjustment layer has a 60 ° gloss of 2 or more and less than 7,
60 degree glossiness of the surface protective layer is 7 or more and 30 or less,
The decorative sheet according to any one of Items 1 to 3.
5. At least a transparent resin layer, a gloss adjusting layer, a primer layer, and a surface protective layer are sequentially laminated, and a concavo-convex pattern is formed on the surface,
The concavo-convex pattern includes a recess in which the gloss adjusting layer is exposed in part or in whole.
A method of manufacturing a decorative sheet,
A method for producing a decorative sheet comprising the following steps (i) to (v) in order:
(I) forming the transparent resin layer;
(Ii) forming the gloss adjusting layer on the transparent resin layer;
(Iii) a step of embossing from above the gloss adjusting layer;
(Iv) A step of applying a two-component curable urethane resin comprising an acrylic-urethane block copolymer and hexamethylene diisocyanate, which is a resin composition for forming the primer layer on the gloss adjusting layer. ,
(V) A step of applying a resin composition for forming the surface protective layer on the primer layer.
6). Item 5. A decorative material obtained by laminating the decorative sheet according to any one of Items 1 to 4 and an adherend.

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

1. The decorative sheet of the present invention is a decorative sheet in which at least a transparent resin layer, a gloss adjusting layer and a surface protective layer are laminated, and a concavo-convex pattern is formed on the surface,
The concavo-convex pattern includes a concave portion in which the gloss adjusting layer is exposed partly or entirely. That is, the decorative sheet of the present invention is a specific concave portion that satisfies the requirement that the gloss adjusting layer is exposed in a part or all of the concave portions included in the uneven pattern (hereinafter, the specific concave portion is gloss adjusted). A recess).

  The present invention is a decorative sheet that realizes a glossy tone having a high design property by having the above-described characteristics. That is, the entire surface of the gloss adjusting recess is not covered with the surface protective layer, and the gloss adjusting layer described later is exposed (that is, part or all of the recess surface is the gloss adjusting layer). There is a difference between the glossiness in the gloss adjustment recess (60 ° gloss meter) and the glossiness in the surface protective layer (60 ° gloss meter), and as a result, the gloss adjustment recess looks more three-dimensional. Therefore, the decorative sheet is more excellent in design.

  For example, the recesses as shown in FIGS. 2C and 3C correspond to the gloss adjustment recesses. In addition, as shown in FIG. 6, a recess whose side surface is a gloss adjustment layer corresponds to the gloss adjustment recess. Although not shown, a recess in which the resin for forming the surface protective layer is formed on a part of the side surface of the recess also corresponds to the gloss adjustment recess. On the other hand, as described above, the recess where the gloss adjusting layer is not exposed at all as shown in FIG. 5 does not correspond to the gloss adjusting recess.

  In addition, a concavo-convex pattern is a pattern formed on the surface of the decorative sheet by embossing, and has a plurality of concave portions. The uneven pattern may include a part of the recess that does not correspond to the gloss adjustment recess (for example, a recess in which the gloss adjustment layer is not exposed as shown in FIG. 5).

  Examples of the concavo-convex pattern include a wood grain conduit (groove) pattern, a texture pattern, a stone plate surface concavo-convex pattern, a cloth surface texturer, a satin texture, a grain texture, a hairline, and a striated groove. Specifically, there is a decorative sheet having a wood grain conduit pattern as shown in FIG. 2 and a decorative sheet having a leather pattern as shown in FIG.

  As shown in FIGS. 2 and 3, the concavo-convex pattern can identify the concave portion by the width (t) in the short side direction, the width (s) in the long side direction, and the height difference (h). In the case of a wood grain pattern, the relationship between s and t preferably satisfies t ≦ s, and more preferably 2t ≦ s.

  When the width of the concave portion in the short side direction is not constant, the width in the short side direction of every portion in the linear object is included in the width (t). The width (t) of the recess can be measured using a surface roughness profile measuring machine. Specifically, a concave portion is selected at random from the concavo-convex pattern, and the width of an arbitrary portion of the selected concave portion can be measured using the surface roughness shape measuring instrument.

  The width (s) of the recess in the long side direction is the longest distance that can be taken when the recess is viewed from above the decorative sheet, and is not limited to a straight line but may be a curve. The width (s) of the recess can be measured using an arbitrary length measuring instrument. For example, it can be measured with a caliper, a measure, a ruler or the like.

  Moreover, the height difference (h) of the said recessed part says the height from the lowest point of a recessed part to the outermost surface of an opening part as shown in FIG.1, FIG.2 (c) and FIG.3 (c). The height difference (h) can also be measured using the surface roughness shape measuring instrument. Specifically, a concave portion and a convex portion adjacent to the concave portion are randomly selected from the concave / convex pattern, and the height from the lowest point of the concave portion to the surface of the surface protective layer is measured using the surface roughness shape measuring instrument. can do.

  In addition, the width (t) and the height difference (h) of the recesses in this specification are measured using a surface roughness shape measuring machine (product name “Surfcom 120A” manufactured by Tokyo Seimitsu Co., Ltd.), with a “cutoff value: .50 mm, cutoff filter type: 2RC, tilt correction method: straight line ”.

  In the decorative sheet of the present invention, the width (t) of the recess is preferably 100 to 2000 μm, and more preferably 200 μm to 500 μm. When the width (t) is the above-described value, the design properties of the decorative sheet can be improved.

  The height difference (h) of the recesses is preferably 20 μm or more, more preferably 20 to 120 μm, and even more preferably 30 to 80 μm.

  In the gloss adjusting recess, the relationship between the width (t) and the height difference (h) of the recess is preferably t <15h. When the width (t) of the concave portion and the height difference (h) satisfy the above relationship, the exposure amount of the gloss adjusting layer in the concave portion increases, and as a result, the gloss matte feeling increases. More preferably, t ≦ 10h, and further preferably 4h ≦ t ≦ 10h.

  Moreover, in the decorative sheet of the present invention, the ratio of the gloss adjustment recessed area (area) is preferably 20% or more of the entire recessed area (area) of the uneven pattern, more preferably 50% to 100%, Preferably it is 70 to 100%. In other words, the greater the proportion of the gloss adjustment recess in the decorative sheet, the greater the difference in gloss between the gloss adjustment layer existing in the gloss adjustment recess and the surface protective layer existing in the flat surface of the decorative sheet. Since it appears clearly, a decorative sheet having a gloss matte tone that is three-dimensional and highly designable is obtained.

Further, the size of the decorative sheet for confirming the effect (gross matte feeling) is about A4 size (210 mm × 297 mm), and there is no limitation on the measuring method, but it can be easily judged visually. it can.
(Composition of makeup sheet)
In the decorative sheet of the present invention, the specific configuration (layer configuration) is not limited as long as at least a transparent resin layer, a gloss adjusting layer, and a surface protective layer are laminated and a concavo-convex pattern is formed on the surface. For example, a decorative sheet formed by sequentially laminating a pattern layer, a colored hiding layer, a transparent adhesive layer, a transparent resin layer, a gloss adjusting layer, and a surface protective layer on a base material sheet.

  Hereinafter, the decorative sheet of the present invention will be specifically described with the decorative sheet having such a layer configuration as a representative example.

  Although the specific structure of a decorative sheet is demonstrated below, the total thickness of a decorative sheet is 40-500 micrometers normally, Preferably it is 100-180 micrometers.

The base material sheet has a pattern layer or the like sequentially laminated on the surface (front surface) thereof.

  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. 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 provides a desired pattern (design) to the decorative sheet, and the type of the 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 decorative 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.

Colored concealment layer In the decorative sheet of the present invention, a color concealment layer may be further formed between the base sheet and the pattern layer.

  The colored concealment layer only needs to conceal the ground color of the adherend when the decorative sheet and the adherend are joined, and is usually formed so as to cover the base sheet.

  For the formation of the colored concealing layer, a method that can be formed so as to cover the entire substrate sheet (entirely solid) is preferable. For example, the roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method, dip coating method and the like described above are preferable.

The coating amount is desirably in the range of ^{2 to} 30 g / m2.

  The thickness of the colored masking layer is usually about 0.1 to 20 μm, preferably about 1 to 10 μm.

Transparent adhesive layer A transparent adhesive layer may be formed in order to enhance the adhesion between the transparent resin layer and the pattern layer, which will be described later. The transparent adhesive layer is not particularly limited as long as it is transparent, and includes any of transparent and colorless, colored 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 a transparent 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 A transparent resin layer is formed on the transparent adhesive 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 decorative sheet.

Gloss control layer A gloss control layer is formed on the transparent resin layer.

  The gloss adjusting layer may be formed so as to be different from the surface protective layer described later in terms of gloss (60 ° gloss meter).

  The gloss adjusting layer may be adjusted to a layer having colorless and transparent, colored and transparent, as long as the design of the base is not impaired.

  Examples of the resin constituting the gloss adjusting layer include urethane resin, acrylic resin, acrylic urethane copolymer resin, and two-component curable polyurethane resin using isocyanate as a curing agent.

  The gloss adjusting layer may be a known primer agent from the viewpoint of adhesion to the transparent resin layer or the surface protective layer. In this case, the gloss adjusting layer has a primer effect as well as a gloss adjusting effect. Examples of the primer agent for forming such a layer include a urethane resin primer agent made of an acrylic-modified urethane resin and the like, a resin primer agent made of a block copolymer of acrylic and urethane, and the like.

  The resin component for forming the gloss adjusting layer can be used alone or in combination of two or more.

  The gloss adjusting layer can contain a filler for adjusting the gloss. Examples of the filler include silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. The amount of the filler is preferably 0.1 to 50 parts by weight and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the resin component.

  Furthermore, the gloss adjusting layer can contain additives such as a flame retardant, an antioxidant, a lubricant, a foaming agent, an ultraviolet absorber, and a light stabilizer, if necessary.

  The thickness of the gloss adjusting layer is not particularly limited, but is usually about 0.1 to 100 μm, preferably about 0.5 to 15 μm.

  The glossiness of the gloss adjusting layer (60 ° gloss meter) is not particularly limited as long as it is different from the glossiness of the surface protective layer described later (60 ° gloss meter), but is preferably less than 7, preferably 5 The following are more preferable, and more preferably 2-3. The glossiness (60 ° gloss meter) is a glossiness measured according to JISZ-8741, and the glossiness (60 ° gloss meter) can be measured using each glossiness meter. For example, GMX-202 manufactured by Murakami Color Research Laboratory may be used.

  Examples of a method for setting the gloss level of the gloss adjusting layer (60 ° gloss meter) to less than 7 include, for example, a method of adding the above-described filler into the resin component for forming the gloss adjusting layer, and the composition of the resin component The method of changing these suitably is mentioned.

Surface protective layer The decorative sheet of the present invention has a surface protective layer on the outermost surface.

  The surface protective layer is not limited, but preferably contains an ionizing radiation curable resin or a two-component curable urethane resin as a resin component. Substantially those formed from these resins are preferred. When the surface protective layer is formed of an ionizing radiation curable resin or a two-component curable urethane resin, it is easy to improve the abrasion resistance, impact resistance, contamination resistance, scratch resistance, weather resistance, etc. of the decorative sheet.

  The ionizing radiation curable resin is not particularly limited, and prepolymers (including oligomers) and / or monomers containing radically polymerizable double bonds capable of undergoing a crosslinking reaction upon irradiation with ionizing radiation such as ultraviolet rays and electron beams. A transparent resin containing as a main component can be used. These prepolymers or monomers can be used alone or in combination. The curing reaction is usually a cross-linking curing reaction.

  Specifically, as the prepolymer or monomer, a compound having in the molecule a radically polymerizable unsaturated group such as a (meth) acryloyl group or (meth) acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group. Is mentioned. Further, a polyene / thiol prepolymer based on a combination of polyene and polythiol is also preferable. Here, the (meth) acryloyl group means an acryloyl group or a methacryloyl group.

  Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and silicone (meth) acrylate. Etc. These molecular weights are usually preferably about 250 to 100,000.

  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. Examples of the polyfunctional monomer include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol tetra ( And (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.

  Examples of the prepolymer having a cationic polymerizable functional group include prepolymers of epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type resins such as fatty acid type vinyl ethers and aromatic vinyl ethers. Examples of the thiol include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those in which allyl alcohol is added to both ends of polyurethane by diol and diisocyanate.

  As the ionizing radiation used for curing 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 rays, or the like may be used. The details of the ultraviolet ray source and the electron beam source will be described in the item of the decorative sheet manufacturing method described later.

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

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

  Further, 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. In the case of curing the resin layer by irradiating with ultraviolet rays, as photopolymerization initiators, acetophenones, benzophenones, Michler benzoylbenzoate, α-aminoxime ester, tetramethylthiuram monosulfide, thioxanthones, aromatic diazonium salts N-butylamine, triethylamine, tri-n-butylphosphine and the like are used as photopolymerization accelerators (sensitizers) such as aromatic sulfonium salts and metallocenes.

  In addition, an antibacterial agent may be added to the surface protective layer in order to impart antibacterial properties. 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 are excellent in durability and heat resistance. Inorganic antibacterial agents are those in which antibacterial metals such as silver, copper and zinc are supported on various inorganic carriers. The addition amount of the antibacterial agent is preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin component.

  In addition, the surface protective layer may contain various additives such as colorants such as solvents, dyes and pigments, fillers such as gloss adjusters and extenders, antifoaming agents, leveling agents, and thixotropy imparting agents as necessary. Can be added.

  Any gloss adjusting agent may be used as long as the surface of the surface protective layer can be matted, and a known or commercially available one 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.

  The glossiness of the surface protective layer (60 ° gloss meter) is not particularly limited as long as it is different from the glossiness of the gloss adjustment layer (60 ° gloss meter) described above, but is preferably 7 or more (more preferably). Is 10-30). The glossiness (60 ° gloss meter) of the surface protective layer is a glossiness measured in accordance with JISZ-8741, similar to the glossiness of the gloss adjusting layer described above. In particular, when the gloss (60 ° gloss meter) of the surface protective layer is 7 or more and the gloss (60 ° gloss meter) of the gloss adjusting layer is 3 or less, the surface protective layer and the gloss Since a clear difference in gloss occurs between the adjustment layer and the adjustment layer, the gloss matte tone has a higher design.

  Examples of the method for setting the glossiness (60 ° gloss meter) of the surface protective layer to 7 or more include a method of adding the above-mentioned gloss adjusting agent, filler and the like to the surface protective layer.

  The surface protective layer is formed by, for example, applying an ionizing radiation curable resin or a two-component curable urethane resin on a transparent resin layer by a known coating method such as gravure coating or roll coating, and then curing the resin. it can.

  The thickness of the surface protective layer is not particularly limited and can be appropriately set according to the characteristics of the final product, but is usually about 0.1 to 50 μm, preferably about 1 to 20 μm.

In addition to the gloss adjusting layer, a primer layer may be provided between the primer layer surface protective layer and the gloss adjusting layer.

  The primer layer can be formed by applying a known primer agent to the surface of the gloss adjusting layer. 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 primer is not specifically limited, Usually, it is 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

You may provide a back surface primer layer in the back surface of a back surface primer layer base material sheet as needed. For example, it is advantageous when a base material sheet and an adherend are bonded to produce a decorative material.

  A back surface primer layer can be formed by apply | coating a well-known primer agent to the single side | surface or both surfaces of 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 is not specifically limited, Usually, 0.01-10 micrometers, Preferably it is about 0.1-1 micrometer.

2. Manufacturing method of decorative sheet According to the manufacturing method of the decorative sheet of the present invention, (i) a step of forming a transparent resin layer, (ii) a step of forming a gloss adjusting layer on the transparent resin layer, (iii) As a result of passing through a step of embossing from above the gloss adjusting layer, and (iv) applying a resin composition for forming a surface protective layer on the gloss adjusting layer, the surface has an uneven pattern. A decorative sheet is obtained which is a formed decorative sheet and includes a concave portion in which the gloss adjusting layer is partially or entirely exposed in the uneven pattern. In addition, about the manufacturing method of an above described decorative sheet, the layer structure is not limited. For example, a decorative sheet formed by sequentially laminating a pattern layer, a colored hiding layer, a transparent adhesive layer, a transparent resin layer, a gloss adjusting layer, and a surface protective layer on a base material sheet.

  Hereinafter, each process in the manufacturing method of the decorative sheet of the present invention will be described taking the decorative sheet as an example.

(I) As a process laminating method for forming a transparent resin layer , for example, a laminating method by a dry laminating method can be mentioned. The transparent resin layer is formed so as to adhere to the transparent adhesive layer, for example, on a sheet in which a base sheet, a pattern layer, a colored hiding layer, and a transparent adhesive layer are sequentially laminated. It may be.

  First, the base sheet is obtained by forming a resin composition containing the above-described resin component or the like into a film by, for example, a calendar method, an inflation method, a T-die extrusion method, or the like.

  Thereafter, the pattern layer is formed on the base sheet by a known printing method such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, or an inkjet printing method.

  Next, a transparent adhesive layer is formed on the pattern layer by the printing method described above, and a transparent resin composed of a sheet or film formed in advance is laminated on the surface to form a transparent resin layer.

  The transparent resin layer may be formed by melt extrusion of the resin composition.

(Ii) Step of forming a gloss adjusting layer on the transparent resin layer A gloss adjusting layer is formed on the transparent resin layer.

A known method can be used to form the gloss adjusting layer. For example, the gloss adjusting layer resin may be applied and dried by the same method as that for forming the pattern layer. The coating amount is not particularly limited, but is usually 0.1 to 100 g / m ² , preferably about 0.1 to 50 g / m ² .

(Iii) Step of embossing from the gloss adjusting layer After forming the gloss adjusting layer, embossing from the gloss adjusting layer, the sheet obtained in (i) and (ii) above An uneven pattern is formed on the surface. Embossing can be easily performed according to a known method. For example, the embossed pattern can be shaped by pressing from the gloss adjusting layer surface to the transparent resin layer side at 120 to 160 ° C. using an embossed roll having a specific uneven pattern.

(Iv) Step of forming the surface protective layer The method for forming the surface protective layer may be a known method.

  For example, a composition (paint) containing the above ionizing radiation curable resin, two-component curable urethane resin, etc. may be prepared and applied by a known coating method such as gravure coating or roll coating.

  In particular, when the composition is applied by a gravure coating method, the composition is not applied to the concave portion of the uneven pattern formed by the step (iii), while the composition is applied to a flat portion (a portion other than the concave portion) on the surface of the gloss adjusting layer. Since an object can be more reliably applied, it is preferable.

  The conditions for forming the surface protective layer are not particularly limited. That is, it is possible to obtain a decorative sheet having a concavo-convex pattern formed on the surface by the step (iv), wherein the concavo-convex pattern includes a concave portion in which the gloss adjusting layer is partially or entirely exposed. In addition, the conditions may be set as appropriate. For example, the physical properties (viscosity, etc.) of the resin of the surface protective layer, the opening width (short side direction, long side direction) and depth (height difference) of the concave portion of the concavo-convex pattern formed by the step (iii), What is necessary is just to set suitably the pressure at the time of apply | coating a composition.

  Note that the surface protective layer is not flat, for example, as shown in FIG. 4, depending on the formation conditions (such as the state of the base), and may have a portion where the vicinity of the opening is slightly raised. In this case, the height difference h (μm) in the gloss adjusting recess becomes larger. Moreover, as above-mentioned, you may form in a part of side surface of the gloss adjustment recessed part.

  The coating amount of the composition is not particularly limited, and may be set as appropriate so that the thickness of the surface protective layer falls within the above range.

  After coating, the formed coating film may be irradiated with ionizing radiation. Ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing and crosslinking molecules, such as visible light, ultraviolet light (near ultraviolet light, vacuum ultraviolet light, etc.), X-ray, electron beam, ion beam, etc. There is. In particular, ultraviolet rays, electron beams, and the like can be used as ionizing radiation. In particular, the surface protective layer is preferably a layer formed by irradiating the coating film containing the ionizing radiation curable resin with an electron beam. By irradiating the electron beam, a surface protective layer uniformly crosslinked with resin can be obtained with certainty. Moreover, when the resin is crosslinked by electron beam irradiation, the resin can be stably crosslinked and cured without using a photopolymerization initiator, and unlike the resin crosslinking by UV irradiation, the curing reaction rate is influenced by temperature. This is advantageous in that it does not receive much.

  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, a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of about 190 to 380 nm can be used.

  As the electron beam source, various electron beam accelerators such as a cockcroft-wald 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. The acceleration voltage of the electron beam is generally about 100 to 1000 keV, preferably about 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  In the present invention, a primer layer (particularly a primer layer made of a urethane resin) may be provided on the gloss adjusting layer as a base in advance. In this case, it is preferable because the adhesion between the gloss adjusting layer and the surface protective layer is increased. The method for forming the primer layer is not limited, and any known method may be followed.

3. Decorative plate The decorative plate of the present invention is formed by laminating the decorative sheet on an adherend such that the surface protective layer of the decorative sheet is the outermost surface layer.

  The adherend is not limited, and the same materials as known decorative sheets can be used. For example, a wood material, a metal, ceramics, plastics, glass, etc. are mentioned. In particular, the decorative sheet of the present invention can be suitably used for a wood material. Specifically, 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. ) And the like.

  The lamination method is not limited. For example, a method of sticking a decorative sheet to an adherend with an adhesive or the like 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 of the present invention can be suitably used as a floor decorative material.

The decorative sheet of the present invention is a decorative sheet in which at least a transparent resin layer, a gloss adjusting layer and a surface protective layer are laminated, and a concavo-convex pattern is formed on the surface,
Since the concavo-convex pattern includes a concave portion in which the gloss adjusting layer is partially or entirely exposed, the glossiness in the gloss adjusting concave portion is different from the glossiness in the surface protective layer. As a result, the gloss adjustment concave portion looks more three-dimensional, and thus has a gloss matte tone with high design.

FIG. 3 is a conceptual diagram (cross-sectional view) of a layer structure of a decorative sheet produced in Example 1. It is (a) perspective view, (b) top view, (c) sectional view (an example) of the gloss adjustment recess of the decorative sheet (wooden conduit pattern) of the present invention. It is (a) perspective view, (b) top view, (c) sectional view (an example) of the gloss adjustment recess of the decorative sheet (texture pattern) of the present invention. It is sectional drawing (an example) of the gloss adjustment recessed part in the decorative sheet of this invention. It is sectional drawing of the recessed part which does not correspond to the gloss adjustment recessed part of this invention. It is sectional drawing (an example) of the gloss adjustment recessed part in the decorative sheet 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
A corona discharge treatment was applied to the front and back surfaces of a 60 μm-thick polypropylene sheet (base material sheet), and then a woodgrain pattern pattern layer was formed on the front surface by gravure printing. A primer layer (back primer layer) was formed on the back surface by a gravure printing method. Thereafter, a 2 μm-thick adhesive layer made of a two-component curable urethane resin is formed on the pattern layer surface, and a polypropylene resin is extruded onto the adhesive layer surface to apply a laminate resin. 80 μm) was formed.

  Next, 100 parts by weight of a two-part curable urethane resin composed of an acrylic-urethane block polymer (main agent) and hexamethylene diisocyanate (curing agent) on the transparent resin layer, and silica (average particle size 3 μm) 38 A resin composition containing parts by weight was applied to form a gloss adjusting layer (thickness 2 μm, gloss (60 ° gloss meter) = 3).

  Further, the front side of the gloss adjusting layer (the side opposite to the base sheet) is heated with an infrared non-contact type heater, and then immediately embossed by heat pressure from the front side of the gloss adjusting layer. Processing was performed to form a concavo-convex pattern (wood grain 1) of a wood grain conduit groove pattern.

  Finally, an ionizing radiation curable resin layer (by coating with a gravure coat a resin composition containing 100 parts by weight of urethane acrylate oligomer and 16 parts by weight of silica (average particle size 11 μm) on the gloss adjusting layer ( A thickness of 15 μm and a glossiness (60 ° gloss meter) = 10) were formed to obtain a predetermined decorative sheet.

  The glossiness (60 ° gloss meter) was measured using GMX-202 manufactured by Murakami Color Research Laboratory.

Example 2
With regard to embossing, a decorative sheet was obtained in the same manner as in Example 1 except that the concavo-convex pattern (wood grain 2) of the wood grain conduit groove pattern was used instead of the concavo-convex pattern (wood grain 1) of the wood grain conduit groove pattern.

Example 3
With regard to embossing, a decorative sheet was obtained in the same manner as in Example 1 except that the concavo-convex pattern of the wood grain conduit groove pattern (wood grain 3) was used instead of the concavo-convex pattern of the wood grain conduit groove pattern (wood grain 1).

Example 4
Regarding embossing, a decorative sheet was obtained in the same manner as in Example 1, except that the concavo-convex pattern of the wood grain conduit groove pattern (wood grain 4) was used instead of the concavo-convex pattern of the wood grain conduit groove pattern (wood grain 1).

Example 5
Regarding embossing, a decorative sheet was obtained in the same manner as in Example 1 except that the concavo-convex pattern of the wood grain conduit groove pattern (wood grain 1) was used instead of the concavo-convex pattern of the wood grain conduit groove pattern (wood grain 1).

Example 6
A back primer layer, a base sheet, a pattern layer, a transparent resin layer, and a gloss adjusting layer were formed in the same manner as in Example 1. Next, after embossing by heat pressure from the front side surface of the gloss adjusting layer to form a concavo-convex pattern (grain 1) of a wood grain conduit groove pattern, a flat portion (part other than the concave portion) of the gloss adjusting layer ) Was provided with a primer layer (a two-component curable urethane resin composed of acrylic-urethane block polymer (main agent) and hexamethylene diisocyanate (curing agent), thickness 1 μm). Finally, a resin composition containing 100 parts by weight of a urethane acrylate oligomer and 16 parts by weight of silica (average particle size 11 μm) is applied on the primer layer by gravure coating, whereby an ionizing radiation curable resin layer (thickness) 15 μm and glossiness (60 ° gloss meter) = 10) were formed to obtain a predetermined decorative sheet.

  For the decorative sheets obtained in Examples 1 to 6, A4 size surfaces were selected at random, and then the selection part was cut out. And with respect to the A4 size decorative sheets of Examples 1 to 6, the height difference of the concave portions on the surface of the laminate composed of the transparent resin layer and the gloss adjusting layer, the width of the concave portions in the short side direction, t / h The range and the ratio of the area of the gloss adjustment recess to the entire recess area were measured or calculated. The results are shown in [Table 1].

Test method ≪Designability test≫
The design properties of the decorative sheets prepared in Examples 1 to 6 were confirmed.

  Specifically, 15 adult males and females in their 20s and 40s feel the gloss matte of the decorative sheet (both A4 size) (the glossy part is raised and the glossy part is retracted (recessed)) The color appearance to be seen) was visually evaluated.

  Those having 10 or more people who feel that they have excellent gloss mat feeling are ◎, those having 8-9 people are ◯, those having 6-7 people are △, those having 5 people or less are × did. Note that Δ, ○, and ◎ are levels that can be put to practical use as gloss matte designs, and x is a level that cannot be put to practical use.

  The results are shown in Table 1 below.

Claims (6)

At least a transparent resin layer, a gloss adjusting layer, a primer layer and a surface protective layer are laminated in order, and a decorative sheet having a concavo-convex pattern formed on the surface,
The primer layer contains a two-component curable urethane resin composed of an acrylic-urethane block copolymer and hexamethylene diisocyanate,
The concavo-convex pattern includes a recess in which the gloss adjusting layer is exposed in part or in whole.
A decorative sheet characterized by that.   The decorative sheet according to claim 1, wherein the gloss adjusting layer contains at least one resin component selected from the group consisting of a urethane resin, an acrylic resin, and an acrylic urethane copolymer resin.   The decorative sheet according to claim 1 or 2, wherein the surface protective layer comprises an ionizing radiation curable resin or a two-component curable urethane resin. The gloss adjustment layer has a 60 ° gloss of 2 or more and less than 7,
60 degree glossiness of the surface protective layer is 7 or more and 30 or less,
The decorative sheet according to any one of claims 1 to 3. At least a transparent resin layer, a gloss adjusting layer, a primer layer, and a surface protective layer are sequentially laminated, and a concavo-convex pattern is formed on the surface,
The concavo-convex pattern includes a recess in which the gloss adjusting layer is exposed in part or in whole.
A method of manufacturing a decorative sheet,
A method for producing a decorative sheet comprising the following steps (i) to (v) in order:
(I) forming the transparent resin layer;
(Ii) forming the gloss adjusting layer on the transparent resin layer;
(Iii) a step of embossing from above the gloss adjusting layer;
(Iv) A step of applying a two-component curable urethane resin comprising an acrylic-urethane block copolymer and hexamethylene diisocyanate, which is a resin composition for forming the primer layer on the gloss adjusting layer. ,
(V) A step of applying a resin composition for forming the surface protective layer on the primer layer. A decorative material obtained by laminating the decorative sheet according to any one of claims 1 to 4 and an adherend.

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