JP5145645B2 - Decorative sheet and decorative board using the same - Google Patents

Description

  The present invention relates to a decorative sheet having a visual unevenness and excellent deep design, and a decorative board using the decorative sheet.

  Conventionally, as decorative materials for furniture, cabinets, tables, desks, floors, etc., base materials for decorative boards such as wooden base materials, inorganic base materials, synthetic resin base materials, metal base materials, etc. For example, a decorative board in which a decorative sheet printed with a wood grain pattern or the like is attached to the surface with an adhesive is used. The decorative sheet used for such a decorative board is required to have flexibility, machinability and the like as post-processing suitability, and weather resistance, heat resistance, water resistance, stain resistance, and scratch resistance as suitability for use. Various aptitudes such as wear resistance are required and are configured to satisfy these aptitudes.

  In addition, due to consumer demand for luxury goods in recent years, furniture, cabinets, tables, desks, etc. have been required to have a high-class feeling, and there is a demand for an appearance that gives a high-class feeling. Various proposals have been made.

  For example, an area having different wettability with respect to an electron beam curable paint or light curable paint is formed by an application surface provided in a pattern on a substrate, and then an electron beam curable paint or light is formed. A decorative sheet has been proposed in which a curable paint is applied, the surface of the paint is depressed in an area that is easily wetted with the paint, and the surface of the paint is raised in an area that is difficult to wet (for example, patent documents) 1). However, this decorative sheet is easily wetted, i.e., when the concave portion is fine, the concave portion cannot be expressed and the boundary between the concave portion and the convex portion is rounded by the surface tension of the paint. There is a problem that sharp unevenness cannot be obtained.

  If another example is given, two kinds of pattern layers of a pattern layer made of normal ink and a convex pattern layer made of an electron beam curable composition are sequentially provided on the substrate, A cosmetic material has been proposed in which a transparent resin layer is coated, and after the coating, an electron beam is irradiated through the transparent resin layer to cure the convex pattern to express a sense of unevenness (for example, see Patent Document 2). However, since this decorative material has relatively large irregularities physically, there is a problem that the convex portion is easily damaged, and particularly when the area of the convex portion is large, it becomes prominent. Furthermore, this decorative material is, for example, when it is desired to express the strength of luster such as a wood grain pattern, that is, when a concave portion with a very narrow width is present, as in the case of a wood grain conduit groove. There is a problem that the desired design cannot be stably obtained because the concave portion is filled by the flow of the coating material constituting the transparent resin layer, and the degree of filling varies.

  As another example, after applying a synthetic resin that performs radiation polymerization to a substrate with printed paper or decorative paper, irradiation is stopped when the synthetic resin is in a semi-cured state. Then, after pressing with a cold press body such as a roll press having a concavo-convex pattern, a decorative board is proposed that expresses the concavo-convex feeling by completely curing the synthetic resin (see, for example, Patent Document 3). . However, in this decorative board, it is not easy to specify the curing conditions when the resin is stably made into a certain semi-cured state, and the synthetic resin in the semi-cured state is unstable and the curing is performed in two stages. There is a problem that it is cumbersome to carry out separately.

  As another example, an electron beam curable resin is applied on a base material using a coating apparatus, and contacted with a mold roll in an electron beam irradiator to mold the unevenness of the mold roll. However, there has been proposed a cosmetic material that expresses a feeling of unevenness by irradiating and curing an electron beam (for example, see Patent Document 4). However, this decorative material requires a special mold roll device, the problem that it is not possible to mold the unevenness with a normal printing device, the problem is that the molding speed by the mold roll is limited, and the productivity is low There is.

As another example, the surface of the substrate has a coating layer, a pattern layer, and a surface protective layer obtained by crosslinking and curing the ionizing radiation curable resin composition, and the pattern layer is compared with the coating layer. And the cosmetics which comprised highly the permeability of the ionizing radiation-curable resin composition are proposed (for example, refer patent document 5). Since this ionizing radiation curable resin composition is more easily penetrated into the part where the pattern exists, this decorative material is formed with a concave portion in the part, and a cosmetic material expressing a feeling of unevenness on the surface is obtained. If a large amount of extender pigment or porous material is added to give sufficient absorption permeability to the pattern layer, the recesses become porous or brittle, which decreases the durability and stain resistance of the recesses. In order to improve the durability and contamination resistance of the recesses, there is a problem that the recesses having sufficient depth and sharpness cannot be formed if the pattern layer is made porous.
Japanese Patent Publication No. 51-26937 Japanese Patent Publication No. 01-41505 Japanese Patent Publication No.49-28264 Japanese Examined Patent Publication No. 63-50066 JP 2001-199028 A

  Therefore, the present invention has been made in view of the above problems, and the object of the present invention is to provide the pattern printing layer and the pattern-like low gloss of the pattern printing layer in which the pattern printing layer and the solid pattern printing layer are sequentially formed. It is to provide a decorative sheet having an excellent design that expresses a feeling of unevenness and depth (depth) that are visually recognized as recesses by synchronizing with the printing layer. By synchronizing with the pattern-like low gloss printing layer, it is to provide a decorative sheet having an excellent design in terms of three-dimensional effect, and resistance during use such as contamination resistance, weather resistance adhesion, and abrasion resistance. Is to provide an excellent decorative sheet, and furthermore, to provide a decorative board using the decorative sheet.

In order to achieve the above object, the inventor of the present invention provides a pattern printing layer in which a pattern printing layer and a solid pattern printing layer are sequentially formed on one surface side of a synthetic resin transparent layer. A decorative sheet provided with a surface protective layer on the entire surface of the other side after providing a patterned low gloss printing layer formed with a printing ink containing fine particles on the other side of the transparent layer made of synthetic resin The surface protective layer is made of a curable resin, and the patterned low gloss printing layer is provided in synchronization with the pattern printing layer, and the patterned low gloss printing layer is viewed from the surface protective layer side. ink There further interaction with the resin component in the uncured product of the curable resin for forming the surface protective layer and the resin component in the ink forming the pattern low gloss printing layer forming the patterned low gloss printing layer Fine particles blended in It is characterized in being recognized as a visual recess by the effect of promoting the scattering of light.

By adopting the structure according to claim 1, it is possible to express a deeper and more complex expression in terms of design such as a sense of transparency and a sense of depth as compared with the case of not synchronizing, and a more realistic wood texture and texture. It can be set as a decorative sheet .

Moreover, the present invention according to claim 2 is the decorative sheet according to claim 1, wherein a synthetic resin colored layer is provided on one surface side of the synthetic resin transparent layer so as to sandwich the pattern printing layer. It is a feature.

Further, the present invention according to claim 3, in the decorative sheet of claim 1, is characterized in that formed by providing a recess pattern on the surface protective layer side.

According to a fourth aspect of the present invention, in the decorative sheet according to the third aspect , the concave pattern is provided in synchronism with the patterned low-gloss printing layer .

The present invention according to claim 5 is the decorative sheet according to claim 1 , characterized in that the curable resin is an ionizing radiation curable resin.

The present invention according to claim 6 is the decorative sheet according to any one of claims 3 and 4, wherein the pattern print layer is a woodgrain print layer, and the patterned low gloss print layer is a conduit pattern print. It is a layer and the said recessed pattern is a conduit groove pattern, It is characterized by the above-mentioned.

Further, the decorative plate of the present invention according to claim 7, characterized in that it has adhered to the decorative plate substrate through an adhesive layer a decorative sheet according to any one of claims 1 to 6 is there.

  The decorative sheet of the present invention and the decorative plate using the same are obtained by synchronizing the patterned print layer and the patterned low-gloss printed layer of the patterned print layer in which the patterned print layer and the solid printed layer are formed in order, It has an excellent design effect that expresses the unevenness and depth (depth) that are visually recognized as recesses. Also, the concave pattern can be further synchronized with the patterned low-gloss printing layer to achieve a three-dimensional effect. It exhibits excellent design effects, and also exhibits excellent effects in resistance during use, such as contamination resistance, weather resistance adhesion, and wear resistance.

The present invention will be described in detail below with reference to the drawings.
FIG. 1 is a layer configuration diagram schematically illustrating a basic form of a decorative sheet according to the present invention, and FIG. 2 is a layer configuration diagram schematically illustrating an embodiment of the decorative sheet according to the present invention. 1, 1 ′ is a decorative sheet, 2 is a transparent layer made of synthetic resin, 2 ′ is a colored layer made of synthetic resin, 3, 3 ′ is a primer layer, 4 is a patterned low gloss printing layer, 5 is a surface protective layer, 6 is The pattern print layer, 7 is a concave pattern, 8 is an adhesive layer, 61 is a pattern print layer, and 62 is a solid pattern print layer.

  FIG. 1 is a layer configuration diagram schematically showing a basic form of a decorative sheet according to the present invention. The decorative sheet 1 has a pattern print layer 61 and a solid pattern print on one surface of a synthetic resin transparent layer 2. The pattern printing layer 6 in which the layer 62 is formed in order is provided, the primer layer 3 is provided on the entire other surface of the synthetic resin transparent layer 2, and then the pattern printing layer 61 is synchronized with the pattern printing layer 61 on the primer layer 3. A patterned low gloss printed layer 4 is provided, a surface protective layer 5 is provided on the entire other surface of the patterned low gloss printed layer 4, and further embossed from the surface protective layer 5 side to form the patterned low gloss printed layer 4 A concave pattern 7 is formed in synchronization with the printing layer 4.

  In FIG. 1, the pattern printing layer 6 is shown in contact with the synthetic resin transparent layer 2, but the pattern printing layer 6 is not limited to this, and the synthetic resin transparent layer 2 is not limited thereto. It is only necessary that the design printing layer 6 is configured so that it can be seen from the surface protective layer 5 side through the synthetic resin transparent layer 2. FIG. 1 shows an embodiment in which the concave pattern 7 is provided in synchronization with the patterned low gloss printing layer 4. However, the concave pattern 7 does not have to be synchronized with the patterned low gloss printing layer 4. In addition, the concave pattern 7 may not be provided.

  FIG. 2 is a layer configuration diagram schematically showing one embodiment of a decorative sheet according to the present invention, wherein the decorative sheet 1 ′ is provided with a primer layer 3 ′ on at least one surface of the synthetic resin colored layer 2 ′. A solid pattern printing layer 62 and a pattern printing layer 61 are sequentially printed on the primer layer 3 'to provide a pattern printing layer 6, and further provided on the entire surface on the pattern printing layer 6 side. For example, a polyol component and A synthetic resin transparent layer 2 is bonded through an adhesive layer 8 formed of a two-component curable polyurethane adhesive composed of an isocyanate component, and a primer layer 3 is provided on the entire surface of the synthetic resin transparent layer 2, A patterned low gloss printing layer 4 is provided on the primer layer 3 in synchronism with the pattern printing layer 61, a surface protective layer 5 is provided on the entire surface of the patterned low gloss printing layer 4, and the surface protection is further provided. Embossing from layer 5 side It is obtained by forming a recessed pattern 7 is tuned to the pattern, low-gloss print layer 4. The synthetic resin colored layer 2 ′ may be a non-colored layer without being colored, and the concave pattern 7 may be the patterned low gloss printing layer as described with reference to FIG. 1. 4 may or may not be tuned.

  Next, various materials constituting the decorative sheet 1, 1 'will be described. First, the resin constituting the synthetic resin transparent layer 2 and the synthetic resin colored layer 2 ′ is excellent in processability and does not generate harmful gas during combustion. Low density polyethylene), medium density polyethylene, high density polyethylene, ethylene alpha olefin copolymer, homopolypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer Olefin-based thermoplastic resin such as polymer, ethylene-vinyl alcohol copolymer, or a mixture thereof, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, polyrelay Thermoplastic ester resins such as polymethyl methacrylate, polyethyl acrylate, polyethyl acrylate, polybutyl acrylate, and other thermoplastic thermoplastic resins such as nylon-6 and nylon-66 Alternatively, non-halogen thermoplastic resins such as polyimide, polyurethane, polystyrene, and acrylonitrile-butadiene-styrene resin can be used. These thermoplastic resins may be used singly or as a mixture of two or more. However, since the design print layer 6 and the recessed pattern 7 are provided as a design, their suitability is required. In view of the fact that no harmful gas is generated at the time of combustion, which has become a problem in recent years, or considering the cost and the like, an olefin thermoplastic resin is preferable.

  Further, the synthetic resin-made transparent layer 2 and the synthetic resin-made colored layer 2 ′ may be in an unstretched state or a uniaxial or biaxial direction, or 2 It may be in a state where more than one layer is laminated, and various configurations can be taken as appropriate, but a thickness of about 40 to 500 μm is appropriate. In addition, these layers 2 and 2 ′ can be subjected to a known easy adhesion treatment such as corona discharge treatment, plasma treatment, ozone treatment or the like on a necessary surface as necessary. Further, these layers 2 and 2 ′ may be obtained by appropriately adding known additives such as an antioxidant, a light stabilizer, and an ultraviolet ray inhibitor. The synthetic resin colored layer 2 'may be transparent or opaque, but is usually an opaque colored layer.

  The picture print layer 6 can be formed using ink by a known printing method such as a gravure printing method, an offset printing method, a silk screen printing method, or the like. The pattern print layer 61 is, for example, a pattern such as a wood pattern, a stone pattern, a cloth pattern, a skin pattern, a geometric pattern, a character, a symbol, a line drawing, various abstract patterns, and the solid pattern print layer 62. Are solid-printed with a coloring ink having a concealing property. 1 and 2, the pattern printing layer 6 is provided with both the pattern printing layer 61 and the solid pattern printing layer 62, but either one of the structures is provided. Is also good.

  Examples of the ink for forming the pattern printing layer 6 include chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene as a vehicle, polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride, and vinyl chloride. -A mixture of one or more vinyl acetate copolymers, cellulose resins, polyamide resins, etc. can be used, and inks can be used by adding pigments, solvents, various auxiliary agents, etc. In consideration of the problem, a non-chlorine vehicle in which one or two or more types such as polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, cellulose resin, and polyamide resin are mixed is suitable, and more preferable. Is polyester, isocyanate and polio Polyurethane consisting Le, polyacrylic, to one without such a polyamide resin is a mixture of two or more.

  Next, the patterned low gloss print layer 4 will be described. The patterned low-gloss printing layer 4 is a region (low-gloss region) where the region provided with this layer is less glossy than the other regions. Although this mechanism has not yet been fully elucidated, when the uncured material of the surface-protective layer 5 made of the curable resin provided on the surface and the patterned low-gloss printed layer 4 is applied, It is presumed that the resin component of the patterned low-gloss printing layer 4 and the uncured product of the surface protective layer 5 exhibit some interactions such as elution, dispersion, and mixing depending on the combination of materials and application conditions. Is done. That is, the respective resin components in the uncured product of the curable resin that forms the patterned low-gloss printing layer 4 and the surface protective layer 5 are suspended without being completely compatible in a short time. It is considered that the portion present on or near the patterned low-gloss print layer 4 and in the suspended state scatters light to form a low-gloss region. Since the surface protective layer 5 is formed by crosslinking and curing while maintaining this suspended state, the region on the patterned low-gloss printing layer 4 in the surface protective layer 5 is at least a low-gloss region. By the illusion of, it is assumed that the area is recognized as if it were a recess.

  The ink that forms the patterned low-gloss printing layer 4 has a property of causing interaction with the curable resin composition (uncured curable resin) that forms the surface protective layer 5, and is curable. It is appropriately selected in relation to the resin composition (uncured curable resin). Specifically, the ink vehicle preferably contains 50% by weight or more of a urethane resin or a polyvinyl acetal resin. The urethane-based resin includes polyol components such as acrylic polyol, polyester polyol, polyether polyol and the like, and isocyanate components such as tolylene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate and other aromatic isocyanates, isophorone diisocyanate, hexamethylene diisocyanate, water. Examples include urethane resins obtained by reacting with aliphatic or alicyclic isocyanates such as tolylene diisocyanate (linearly crosslinked or network crosslinked) Can do. Moreover, a polyvinyl acetal type resin is obtained by condensation (acetalization) of polyvinyl alcohol and aldehydes. Examples of the polyvinyl acetal resin include polyvinyl formal (formal resin), polyvinyl acetoacetal, polyvinyl propional, polyvinyl butyral (butyral resin), and polyvinyl hexyl.

  If necessary, unsaturated polyester resin, acrylic resin, vinyl chloride-vinyl acetate copolymer may be used to adjust the degree of expression of the low gloss region and the contrast of the gloss difference between the low gloss region and its surroundings. A gloss adjusting resin such as the above may be used in combination. The gloss adjusting resin also has a mixing ratio in the range of 10 to 50% by weight with respect to the total amount of the vehicle. If it is within this range, a sufficient enhancement effect of low gloss area expression can be obtained. The ink for forming the patterned low gloss printing layer 4 may be uncolored or may be colored by adding a colorant such as a pigment. The pattern of the low gloss printed layer 4 includes, for example, a conduit pattern, a stone pattern, a cloth pattern, an abstract pattern, a satin pattern, a grain pattern, a hairline, a line pattern, etc. Can be mentioned.

  In the present invention, the surface protective layer 5 is provided on the patterned low-gloss printing layer 4, and the curable resin composition (the ink constituting the patterned low-gloss printing layer 4 and the surface protective layer 5 ( The region on the patterned low-gloss printing layer 4 becomes at least a low-gloss region by the interaction with the uncured product of the curable resin, and the region is recognized as if it is a concave portion by the optical illusion. Is. The thickness of the patterned low gloss printing layer 4 is suitably 0.5 μm or more and 5.0 μm or less in consideration of printability and interaction with the curable resin composition (uncured curable resin). .

  Moreover, it is preferable to mix | blend an extender pigment with the ink for forming the said pattern-like low gloss printing layer 4. FIG. By blending the extender, light scattering can be promoted and the low gloss effect can be further enhanced. The extender pigment is not particularly limited, and is suitably selected from, for example, silica, talc, clay, barium sulfate, barium carbonate, calcium sulfate, calcium carbonate, magnesium carbonate and the like. Among these, silica, which is a material having a high degree of freedom in material design such as oil absorption, particle size, pore volume, etc., and excellent in designability, whiteness, and coating stability as an ink, is preferable. Silica is preferred. In order to obtain the light scattering effect, the average particle diameter of silica is preferably determined from the relationship between the film thickness of the patterned low gloss printing layer 4 and the film thickness of the surface protective layer 5 and is generally 1.0 to 10.0 μm. However, from the optimum film thickness of the patterned low gloss printing layer 4 and the film thickness of the surface protective layer 5 determined in consideration of various physical properties (post-processing suitability and suitability at the time of use) required as a decorative sheet and cost. Then, 2.0-4.0 micrometers is the most preferable. Further, the amount of the extender pigment added to the ink for forming the patterned low gloss printing layer 4 is an ink composition 100 other than the extender pigment due to the effect of imparting low gloss and the thixotropy of the ink itself. 5-15 weight part is preferable with respect to a weight part.

  Next, the surface protective layer 5 will be described. This surface protective layer 5 is provided for imparting surface physical properties such as scratch resistance, abrasion resistance, stain resistance, water resistance, and weather resistance required for the decorative sheet 1, 1 ′ (see FIGS. 1 and 2). As the resin for forming the surface protective layer 5, it is appropriate to use a curable resin such as a thermosetting resin or an ionizing radiation curable resin. It is an ionizing radiation curable resin because it is hard and has excellent productivity.

As thermosetting resins, unsaturated polyester resins, polyurethane resins (including two-component curable polyurethane), epoxy resins, amino alkyd resins, phenol resins, urea resins, diallyl phthalate resins, melamine resins, guanamine resins, melamine-ureas Examples thereof include a cocondensation resin, a silicon resin, and a polysiloxane resin. If necessary, a curing agent such as a crosslinking agent or a polymerization initiator, or a polymerization accelerator is added to the resin. For example, as a curing agent, isocyanate or organic sulfonate is added to unsaturated polyester resin or polyurethane resin, organic amine is added to epoxy resin, peroxide such as methyl ethyl ketone peroxide, azoisobutyl nitrile, etc. The radical initiator is added to the unsaturated polyester resin. As a method of forming the surface protective layer with the thermosetting resin, for example, the above thermosetting resin is made into a solution, applied by a known coating method such as a roll coating method or a gravure coating method, dried and cured. Can be formed. The coating amount of the surface protective layer is suitably about 1 to ²⁰ g / m ^{2 in} terms of solid content, and in particular, the film thickness of the patterned low gloss printing layer is 0.5 μm or more and 5.0 μm or less, When the average particle size is 1.0 μm or more and 10.0 μm or less, ² to 15 g / m ² in terms of solid content is appropriate.

  Next, the ionizing radiation curable resin will be described. The ionizing radiation curable resin is a resin that undergoes a cross-linking polymerization reaction upon irradiation with ionizing radiation and changes to a three-dimensional polymer structure. 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. is there. Usually, ultraviolet rays or electron beams are used. As the ultraviolet light source, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, or a metal halide lamp can be used. As the wavelength of the ultraviolet light, a wavelength range of 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 electron beam used is 100 to 1000 keV, preferably 100 to 300 keV. The irradiation amount of the electron beam is usually about 2 to 15 Mrad.

  As the ionizing radiation curable resin, a monomer having a radically polymerizable unsaturated group such as (meth) acryloyl group or (meth) acryloyloxy group or a cationically polymerizable functional group such as epoxy group in the molecule, It consists of a polymer or polymer. These monomers, prepolymers or polymers are used alone or in combination. In this specification, (meth) acrylate is used in the meaning of acrylate or methacrylate. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and is usually an ultraviolet ray or an electron beam.

  Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth) acrylate, melamine (meth) acrylate, triazine (meth) acrylate, and polyvinylpyrrolidone. This prepolymer usually has a molecular weight of about 10,000 or less. When the molecular weight exceeds 10,000, the cured resin layer has insufficient surface properties such as scratch resistance, abrasion resistance, chemical resistance, and heat resistance. The acrylate and methacrylate can be used in common, but the acrylate is more advantageous for the purpose of curing efficiently at a high speed and in a short time because the acrylate is faster in terms of the crosslinking curing rate with ionizing radiation. .

  Examples of the prepolymer having a cationically polymerizable functional group include epoxy resins such as bisphenol type epoxy resins, novolac type epoxy resins, and alicyclic epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, urethane vinyl ethers, and ester vinyl ethers. And prepolymers such as vinyl ether resins, cyclic ether compounds, and spiro compounds.

  Examples of monomers having a radically polymerizable unsaturated group include (meth) acrylate compound monofunctional monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, methoxyethyl ( (Meth) acrylate, methoxybutyl (meth) acrylate, butoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N , N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N, N-dibenzylaminoethyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, ethyl carbitol ( Me ) Acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, methoxypropylene glycol (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2 -(Meth) acryloyloxypropyl hydrogen terephthalate and the like.

  In addition, as a polyfunctional monomer having a radical polymerizable unsaturated group, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, di Propylene glycol (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, bisphenol-A-di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerin polyethylene oxide tri (meth) acrylate, tris (meth) acryloyloxy Examples thereof include ethyl phosphate.

  As the monomer having a cationic polymerizable functional group, a prepolymer monomer having the cationic polymerizable functional group can be used.

  When the above-mentioned ionizing radiation curable resin is cured by irradiating with ultraviolet rays, a photopolymerization initiator is added as a sensitizer. In the case of a resin system having a radically polymerizable unsaturated group, photoinitiators include acetophenones, benzophenones, thioxanthones, benzoin, benzoin, benzoin methyl ether, Michler benzoylbenzoate, Michler ketone, diphenyl sulfide, dibenzyl disulfide , Diethyl oxide, triphenylbiimidazole, isopropyl-N, N-dimethylaminobenzoate and the like can be used alone or in combination. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, a metallocene compound, a benzoin sulfonate ester, a freeloxyxonium diallyl iodosyl salt, etc., should be used alone or as a mixture. Can do. In addition, generally the addition amount of these photoinitiators is about 0.1-10 weight part with respect to 100 weight part of ionizing radiation curable resins. The application method and application amount of the ionizing radiation curable resin are the same as those of the thermosetting resin, and the description thereof is omitted.

  When the surface protective layer 5 is given further scratch resistance and wear resistance, for example, inorganic particles such as α-alumina, silica, kaolinite, iron oxide, diamond, silicon carbide, etc. Is mentioned. Examples of the particle shape include a spherical shape, an elliptical shape, a polyhedral shape, a scale shape, and the like. Although there is no particular limitation, a spherical shape is preferable. Examples of organic substances include synthetic resin beads such as cross-linked acrylic resin and polycarbonate resin. The particle size is usually about 3 to 200% of the film thickness. Among these, spherical α-alumina is particularly preferable because it has high hardness and a large effect on improving wear resistance, and it is relatively easy to obtain spherical particles. Moreover, the mixture ratio of the fine particles with respect to the curable resin forming the surface protective layer 5 is 1 to 80 parts by weight with respect to 100 parts by weight of the curable resin.

  The surface protective layer 5 may be made of, for example, a well-known organic ultraviolet absorber such as benzotriazole, benzophenone, or triazine, or titanium dioxide having an average particle size of about 5 to 120 nm, depending on required physical properties. Inorganic ultraviolet absorbers such as cerium oxide and zinc oxide, known light stabilizers such as hindered amines, or known additives such as antistatic agents and leveling agents can be added.

  Next, the primer layers 3, 3 'will be described. The primer layer 3 is provided for the purpose of improving the adhesive strength between the synthetic resin transparent substrate layer 2 and the patterned low-gloss printing layer 4 or the surface protective layer 5, and the primer layer 3 ' It is provided for the purpose of improving the adhesive strength between the synthetic resin colored layer 2 ′ and the picture print layer 6. In particular, when the synthetic resin-made transparent base material layer 2 and the synthetic resin-made colored layer 2 ′ are olefin-based thermoplastic resins, the patterned low-gloss printing layer 4 or the surface protective layer 5 and the pattern printing layer are used. In order to improve the adhesive strength with 6, it is desirable to provide the primer layers 3, 3 ′. Examples of the resin used for the primer layers 3 and 3 ′ include ester resins, urethane resins, acrylic resins, polycarbonate resins, vinyl chloride-vinyl acetate copolymers, polyvinyl butyral resins, nitrocellulose resins, and the like. Can be used alone or mixed to form a coating composition or ink composition, which can be formed using an appropriate coating means such as a roll coating method or a gravure printing method.

  However, the primer layer 3 is particularly preferably formed of a resin comprising (i) a copolymer of an acrylic resin and a urethane resin and (ii) an isocyanate. That is, the copolymer of (i) an acrylic resin and a urethane resin comprises an acrylic polymer component having a hydroxyl group at the terminal (component A), a polyester polyol component having a hydroxyl group at both ends (component B), and a diisocyanate component (component). C) is mixed and reacted to form a prepolymer, and a chain extender (component D) such as diamine is further added to the prepolymer to extend the chain. By this reaction, polyester urethane is formed and an acrylic polymer component is introduced into the molecule to form an acrylic-polyester urethane copolymer having a hydroxyl group at the terminal. This acrylic-polyester urethane copolymer is formed by reacting the terminal hydroxyl group with the isocyanate of (ii) and curing it.

  As the component A, a linear acrylate polymer having a hydroxyl group at the terminal is used. Specifically, linear polymethyl methacrylate (PMMA) having a hydroxyl group at the terminal is preferable because it is excellent in weather resistance (particularly the property against photodegradation) and can be easily copolymerized with urethane. . The component A is an acrylic resin component in the copolymer, and those having a molecular weight of 5000 to 7000 (weight average molecular weight) are preferably used because of particularly good weather resistance and adhesiveness. In addition, the component A may be used only having a hydroxyl group at both ends, but a mixture having a conjugated double bond at one end is mixed with the above-mentioned one having a hydroxyl group at both ends. Is also good. By mixing the acrylic polymer in which the conjugated double bond remains, the conjugated double bond of the layer contacting the primer layer, for example, the ionizing radiation curable resin of the surface protective layer 21 and the acrylic polymer reacts. In addition, the adhesion between the ionizing radiation curable resin can be improved.

  Component B reacts with diisocyanate to form polyester urethane and constitutes a urethane resin component in the copolymer. The component B is a polyester diol having hydroxyl groups at both ends. Examples of the polyester diol include an addition reaction product of a diol compound having an aromatic or spiro ring skeleton and a lactone compound or a derivative thereof, or an epoxy compound, a condensation product of a dibasic acid and a diol, and a cyclic ester compound. Examples thereof include a derived polyester compound. Examples of the diol include short-chain diols such as ethylene glycol, propylene glycol, diethylene glycol, butanediol, hexanediol, and methylpentenediol, and alicyclic short-chain diols such as 1,4-cyclohexanedimethanol. Examples of the dibasic acid include adipic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. Preferred as the polyester polyol is adipate-based polyester using adipic acid or a mixture of adipic acid and terephthalic acid as the acid component, particularly preferably adipic acid, and 3-methylpentanediol and 1,4-cyclohexanedimethanol as the diol component. is there.

  In the primer layer 3, the urethane resin component formed by the reaction between the component B and the component C gives the primer layer 3 flexibility, and is made of the synthetic resin transparent substrate layer 2 or the synthetic resin. This contributes to adhesion with the colored layer 2 ′. Further, the acrylic resin component made of an acrylic polymer contributes to weather resistance and blocking resistance in the primer layer 3. In the urethane resin, the molecular weight of the component B may be within a range in which a urethane resin capable of sufficiently exhibiting flexibility in the primer layer is obtained. Adipic acid or a mixture of adipic acid and terephthalic acid, and 3-methylpentanediol In the case of a polyester diol composed of 1,4-cyclohexanedimethanol, 500 to 5000 (weight average molecular weight) is preferable.

  As the component C, an aliphatic or alicyclic diisocyanate compound having two isocyanate groups in one molecule is used. Examples of the diisocyanate include tetramethylene diisocyanate, 2,2,4 (2,4,4) -1,6-hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and 1,4′-cyclohexyl. A diisocyanate etc. can be mentioned. As the diisocyanate component, isophorone diisocyanate is preferable in terms of excellent physical properties and cost. When the above-mentioned components A to C are reacted, the equivalent ratio of the total hydroxyl group (may be an amino group) of the acrylic polymer, polyester polyol and chain extender described below and the isocyanate group is such that the isocyanate group becomes excessive. To.

  When the above three components A, B and C are reacted at 60 to 120 ° C. for about 2 to 10 hours, the isocyanate group of the diisocyanate reacts with the hydroxyl group at the end of the polyester polyol to form a polyester urethane resin component and an acrylic polymer. A compound in which a diisocyanate is added to a terminal hydroxyl group is also mixed, and a prepolymer is formed in a state where excess isocyanate groups and hydroxyl groups remain. As a chain extender, for example, a diamine such as isophorone diamine or hexamethylene diamine is added to this prepolymer, the isocyanate group is reacted with the chain extender, and the chain is extended so that the acrylic polymer component is contained in the polyester urethane molecule. The (i) acrylic-polyester urethane copolymer introduced and having a hydroxyl group at the terminal can be obtained.

  Addition of isocyanate of (ii) to acrylic-polyester urethane copolymer of (i), coating method, coating solution adjusted to necessary viscosity in consideration of coating amount after drying, gravure coating method, roll The primer layer 3 may be formed by coating by a known coating method such as a coating method. The isocyanate of (ii) may be any isocyanate that can be crosslinked and cured by reacting with the hydroxyl group of the acrylic-polyester urethane copolymer of (i). An aliphatic isocyanate can be used, and an aliphatic isocyanate is particularly desirable from the viewpoint of thermal discoloration prevention and weather resistance. Specifically, a monomer such as tolylene diisocyanate, xylylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate, or a multimer such as a dimer or trimer thereof, or And polyisocyanates such as derivatives (adducts) obtained by adding these isocyanates to polyols. In addition, although the thing of the structure which provided the primer layers 3 and 3 'was shown in the decorative sheet | seat 1 and 1' of FIG. 1, FIG. 2, this is a decorative sheet specification corresponding to a high level request | requirement, request | requirement When the level is low, these primer layers 3, 3 ′ are not necessarily provided.

As the coating amount after drying of the primer layer 3,3 'is from 1 to 20 g / m ^2, preferably from 1 to 5 g / m ^2. The primer layers 3 and 3 ′ may be layers to which additives such as silica powder, additives such as a light stabilizer and a colorant are added as necessary.

  Further, although not shown, a primer layer is provided on the back surface of the synthetic resin colored layer 2 ′ shown in FIG. 2 (the surface opposite to the surface on which the pattern printing layer 6 is provided), and the decorative sheet 1 ′ is used for a decorative board. You may comprise so that the adhesive force at the time of sticking to a base material (not shown) through an adhesive bond layer and making it a decorative board may improve. The primer layer provided on the back surface of the synthetic resin colored layer 2 ′ (the surface opposite to the surface provided with the pattern printing layer 6) may be appropriately provided as necessary when the adhesive force is insufficient. Is. Note that the resin described in the primer layers 3 and 3 ′ may be appropriately selected and used for the primer layer in this case. Moreover, as an adhesive agent used for the adhesive bond layer which sticks decorative sheet 1 'and the base material for decorative boards, any type, such as a thermoplastic resin type | system | group, a thermosetting resin type | system | group, rubber | gum (elastomer) type | system | group, is mentioned, for example. It may be an adhesive. These may be known ones or commercially available products. Thermoplastic resin adhesives include polyvinyl acetate resin, polyvinyl alcohol, polyvinyl acetal (polyvinyl formal, polyvinyl butyral, etc.), cyanoacrylate, polyvinyl alkyl ether, polyvinyl chloride, polyamide, polymethyl methacrylate, nitrocellulose, acetic acid Cellulose, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and the like can be mentioned. Examples of thermosetting resin adhesives include urea resins, melamine resins, phenol resins, Resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide resin, polyamideimide, polybenzimidazole, polybenzothiazole, and the like can be given. Rubber-based adhesives include natural rubber, recycled rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber, butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber, Examples include block copolymer rubber (SBS, SIS, SEBS, etc.).

  The decorative board substrate (not shown) may be a medium-density fiber board (MDF), a high-density fiber board (HDF), a wood-based substrate such as particle board or plywood, a cement board, or silicic acid. Inorganic base materials, such as a calcium plate, a metal plate, etc. can be mentioned. As the thickness of the base material for decorative plate, a thickness of 0.5 mm or more is appropriate for a metal plate, and 1.0 mm or more is suitable for practical use in other cases.

  In addition, the concave pattern 7 can be formed by heating press or hairline processing, and as the pattern, for example, a conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a sand texture, a hairline, a multiline groove, Mirror surface etc.

  Next, the present invention will be described in further detail with reference to examples.

  A patterned print layer of wood grain pattern and the pattern print on one side of a transparent polypropylene film (synthetic resin transparent layer referred to in the present application) having a thickness of 80 μm subjected to double-sided corona discharge treatment with a two-component curable urethane printing ink After forming a pattern printing layer consisting of a 3μm thick solid pattern printing layer with a two-part curable acrylic printing ink on the layer, an acrylic / urethane block copolymer is the main agent on the other side in-line, and a curing agent As a transparent primer layer having a thickness of 2 μm is formed by applying a two-component curable urethane resin to which isocyanate is added, and then the number average molecular weight is 3,000 and the glass transition temperature (Tg) is − on the transparent primer layer surface. Printing ink set in which 10 parts by weight of silica particles having an average particle size of 4.0 μm are blended with 100 parts by weight of polyester urethane printing ink at 62.8 ° C. After forming a 2.0 μm-thick conduit pattern layer (patterned low-gloss printed layer in this application) in synchronism with the pattern print layer by using a gravure printing method, the conduit pattern layer An ionizing radiation curable resin composition (100 parts by weight of urethane acrylate ionizing radiation curable resin blended with 16 parts by weight of silica whose surface is coated with silicone oil) is applied to the entire surface on which an electron beam is formed. [Acceleration voltage: 175 KeV, irradiation amount: 5 Mrad] was irradiated to form a transparent surface protective layer having a thickness of 5 μm. Thereafter, the decorative sheet according to the present invention shown in FIG. 1 was formed off-line by embossing from the transparent surface protective layer side to synchronize with the conduit pattern layer to form a concave pattern composed of conduit grooves. The embossing plate used for embossing was made by copying a conduit pattern (conduit groove) from the surface of a wood plate by electroforming, and the pitch of the conduit pattern (conduit groove) was changed to the conduit pattern. The conduit pattern layer and the embossed plate are used by setting the layer (patterned low-gloss printing layer in the present application) to be 0 to 0.5% larger than the pitch and the width to be 0 to 0.2% smaller. The register mark provided on the sensor was detected by a sensor, and the tension increase / decrease amount was controlled in accordance with the amount of registration deviation, and the conduit pattern layer and the conduit groove were synchronized to perform embossing.

  A solid print layer 3 μm thick with a two-part curable acrylic printing ink on one side of a 60 μm thick colored polypropylene film (synthetic resin colored layer as referred to in this application) subjected to double-sided corona discharge treatment; After forming a pattern printing layer composed of a woodgrain pattern printing layer with urethane printing ink on the solid pattern printing layer by a gravure printing method, a urethane / nitrified cotton primer layer is formed on the other surface by a gravure printing method. After that, an adhesive layer having a thickness of 2 μm made of a two-component curable urethane resin is formed on the pattern print layer surface, and an ethylene / propylene / butene copolymer as a main component is formed on the adhesive layer surface. A polypropylene thermoplastic elastomer to which a UV absorber and a hindered amine radical scavenger are added is melt-extruded by heating with a T-die extruder and has a thickness of 80 μm. Akira resin layer an intermediate sheet in which the form (synthetic resin transparent layer as referred herein) were prepared.

  On the transparent resin layer surface of the intermediate sheet, a two-component curable urethane resin having an acrylic / urethane block copolymer as a main agent and an isocyanate added as a curing agent is applied to form a transparent primer layer having a thickness of 2 μm. 10 weight parts of silica particles having an average particle diameter of 4.0 μm with respect to 100 parts by weight of a polyester urethane printing ink having a number average molecular weight of 3,000 and a glass transition temperature (Tg) of −62.8 ° C. Using a printing ink composition containing a part, a 2.0 μm-thick conduit pattern layer (pattern-like low-gloss printing layer in this application) is formed in synchronization with the above-mentioned pattern print layer by gravure printing. After that, the ionizing radiation curable resin composition [silica is added to 100 parts by weight of the urethane acrylate ionizing radiation curable resin over the entire surface on which the conduit pattern layer is formed. Electron beam with applying a silica 16 obtained by compounding parts by weight] obtained by coating the surface with N'oiru [accelerating voltage: 175KeV, dose: 5 Mrad] to form a transparent surface protective layer of 5μm thick by irradiating. Thereafter, the decorative sheet according to the present invention shown in FIG. 2 was formed off-line, which was embossed from the transparent surface protective layer side to synchronize with the conduit pattern layer to form a concave pattern composed of conduit grooves. The pattern print layer and the conduit pattern layer are detected by detecting a register mark provided on the pattern print layer with a sensor and controlling the peripheral speed of the printing plate provided with the conduit pattern layer. Combined. In addition, the registration between the conduit pattern layer and the embossed plate has been described in the first embodiment, and is therefore omitted.

  In the acrylic / urethane block copolymer, the isocyanate component of the urethane portion is isophorone diisocyanate and hydrogenated MDI (methylene diisocyanate), and the curing agent is a hexamethylene diisocyanate curing agent. Silica used for the transparent surface protective layer is added to make the transparent surface protective layer matte. Use silica with an average particle diameter of 5 μm and coat with silicone oil. Thus, the alkali resistance treatment was performed.

[Comparative Example 1]
Using a two-component curable urethane printing ink containing 10% by weight of acrylic resin beads on the surface of the transparent resin layer of the intermediate sheet prepared in Example 2, a solid pattern printing layer (gloss adjusting layer) and the solid are printed by gravure printing. A pipe pattern layer (matte printing layer) is coated with acrylic matte printing ink (black acrylic matting printing ink containing 45% by weight of acrylic resin beads and carbon black as a pigment) on the pattern printing layer surface. A decorative sheet (a decorative sheet having a concavo-convex pattern due to a difference in gloss on the surface) was prepared as a comparative example.

[Comparative Example 2]
A decorative sheet as a comparative example was produced in the same manner as in Example 2 except that the conduit pattern layer and the recessed pattern were not synchronized with the pattern print layer.

  For the decorative sheets of Examples 1 and 2 and Comparative Examples 1 and 2 prepared above, the evaluation of design properties, stain resistance, weather adhesion, and abrasion resistance were evaluated by the following evaluation methods, and the results were evaluated. These are summarized in Table 1.

〔Evaluation method〕
-Design property: The design property of the appearance was visually evaluated by the following evaluation.
〔Evaluation criteria〕
A: The design expression is rich in three-dimensionality and deep.
○: The design expression is three-dimensional and deep.
Δ: The design expression is three-dimensional, but there is no sense of depth.
X: The design expression is monotonous and there is no sense of depth.
・ Contamination resistance:
Contaminants were applied to the surface of the decorative sheet in accordance with JIS K-6902, and the remaining condition of the contaminants after wiping was visually evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◎: There is no change compared to before the contamination application ○: There is a slight change compared to before the contamination application △: There is a change compared to before the contamination application ×: There is a significant change compared to before the contamination application Yes, weather-resistant adhesion:
After exposing the decorative sheet for 100 hours using an i-super UV tester [Iwasaki Electric Co., Ltd .: SUV-W231 (trade name)], a 25 mm wide cellophane tape [Nichiban Co., Ltd .: Cellotape (registered trademark)] ] Was affixed to the surface of the decorative sheet, peeled off rapidly in the 45 ° direction, and the peeled surface of the decorative sheet was visually evaluated according to the following evaluation criteria.
〔Evaluation criteria〕
◎: Peeling of the pattern is not recognized at all ○: Peeling of the pattern is recognized, but it is minor and there is no practical problem △: Peeling of the pattern is clearly recognized ×: Peeling of the pattern is remarkably recognized / Abrasion resistance sex:
Steel wool (# 1000) is attached to a weight adjusted to a load of 29.4 kPa (300 g / cm ² ), the surface of the decorative sheet is rubbed 50 times, and the surface change is visually evaluated according to the following evaluation criteria. did.
〔Evaluation criteria〕
◎: No surface change is observed. ○: Surface change is recognized, but it is minor and there is no practical problem. △: Surface change is clearly recognized. ×: Surface change is significantly recognized.

  As is apparent from Table 1, the decorative sheet of the present invention has a texture and depth (depth) that is visually recognized as a recess by synchronizing the pattern-like low gloss print layer with the pattern print layer of the pattern print layer. )) And an excellent design property having a three-dimensional effect by synchronizing the concave pattern. In addition, a decorative sheet excellent in resistance at the time of use such as stain resistance, weather resistance adhesion and abrasion resistance could be obtained.

It is a layer block diagram which shows the basic form of the decorative sheet concerning this invention schematically. It is a layer block diagram which shows one Example of the decorative sheet concerning this invention schematically.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 1 'decorative sheet 2 Synthetic resin transparent layer 2' Synthetic resin colored layer 3, 3 'Primer layer 4 Pattern-like low gloss printing layer 5 Surface protective layer 6 Picture printing layer 7 Recessed pattern 8 Adhesive layer 61 Pattern Printing layer 62 Solid pattern printing layer

Claims (7)

A pattern printing layer in which a pattern printing layer and a solid pattern printing layer are sequentially formed is provided on one surface side of the synthetic resin transparent layer, and the other surface of the synthetic resin transparent layer is formed of printing ink containing fine particles. A decorative sheet provided with a surface protective layer on the entire other surface after providing a patterned low gloss printed layer, wherein the surface protective layer is made of a curable resin and the patterned low gloss printed layer is the pattern The pattern-like low gloss printing layer forms the pattern-like low gloss printing layer when viewed from the surface protection layer side, and forms the resin component and the surface protection layer in the ink . the further interaction with the resin component is recognized as a visual recess by the effect of promoting the scattering of light particles were formulated into ink forming the pattern low glossy printed layer in the uncured product of curable resin Decorative sheet which is characterized. 2. The decorative sheet according to claim 1, wherein a synthetic resin colored layer is provided on one surface side of the synthetic resin transparent layer so as to sandwich the pattern print layer. The decorative sheet according to claim 1, wherein a concave pattern is provided on the surface protective layer side. 4. The decorative sheet according to claim 3, wherein the concave pattern is provided in synchronism with the patterned low gloss printing layer. The decorative sheet according to claim 1, wherein the curable resin is an ionizing radiation curable resin. 5. The pattern print layer according to claim 3, wherein the pattern print layer is a wood grain pattern print layer, the patterned low gloss print layer is a conduit pattern print layer, and the recessed pattern is a conduit groove pattern. The decorative sheet described in 1. A decorative board, wherein the decorative sheet according to any one of claims 1 to 6 is attached to a base for a decorative board via an adhesive layer.

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