JP5298606B2 - Decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet for use in interior and exterior materials of buildings such as houses, building materials such as construction materials and fittings, furniture fixtures, vehicle interiors, surface makeup of residential equipment and home appliances, etc. In particular, the present invention relates to a decorative sheet suitable for surface decoration of a building member requiring weather resistance and heat resistance such as an exterior and an entrance door.

  Conventionally, a decorative sheet made of a polyvinyl chloride resin, which is inexpensive and excellent in processability, has been most commonly used as a decorative sheet for use in various applications as described above. This decorative sheet includes a single-layer decorative sheet obtained by printing an appropriate desired pattern such as wood grain on the front or back surface of a thermoplastic resin base material made of polyvinyl chloride resin, and a polyvinyl chloride resin. There is a multi-layered decorative sheet in which a pattern is printed on the surface of a thermoplastic resin substrate made of the above, and a transparent thermoplastic resin layer made of a transparent polyvinyl chloride resin is laminated on the printed surface. Among them, the latter multi-layered decorative sheet is protected by a polyvinyl chloride resin layer from both the front and back, and is advantageous in terms of processing and durability. It has been used more widely than single-layer decorative sheets because it can easily be highly concealed by coloring.

  In addition to the above, there was also a decorative sheet made of a combination of a polyvinyl chloride resin and another thermoplastic resin. For example, some semi-exterior applications that require weather resistance include those that use an acrylic resin with excellent weather resistance in the transparent thermoplastic resin layer, and applications that require high definition such as for steel sheets. In some cases, a polyester resin excellent in transparency and surface smoothness is used for the transparent thermoplastic resin layer. As described above, a decorative sheet constituted by a combination of polyvinyl chloride resins or a combination of a polyvinyl chloride resin and another thermoplastic resin utilizes the excellent thermal adhesiveness of the polyvinyl chloride resin, Most commonly produced by a laminating method.

  However, in recent years, it has been pointed out that polyvinyl chloride resin generates a large amount of chlorine gas, hydrogen chloride gas, etc. during combustion, which can be a direct or indirect factor in the generation of toxic substances, dioxins. From this point of view, development of a decorative sheet using a material that replaces polyvinyl chloride resin has been requested. In response to such a demand, for example, decorative sheets using thermoplastic resins not containing chlorine other than polyvinyl chloride, such as polyolefin resins, acrylic resins, and polyester resins, have already been developed and put into practical use. Substitution of vinyl chloride resin decorative sheets is gradually progressing.

  However, all of these alternative resins are inferior in thermal adhesiveness compared to polyvinyl chloride resin, and as in the case of a decorative sheet using conventional polyvinyl chloride resin, cosmetics are applied by thermal lamination. When trying to manufacture a sheet, there is a problem that it is difficult to obtain a necessary adhesive strength. In particular, when a polyolefin-based resin is used, the range of temperature conditions in which heat bonding can be performed is very narrow, and the temperature is too high, so that defective lamination such as sheet breakage, elongation, deformation, and deterioration occurs. Further, even if heat lamination is performed in a low temperature range where these disadvantages do not occur, the laminate strength is extremely low, and it is impossible to obtain a sheet that can be used practically as a decorative sheet.

  In order to address such problems, a thermoadhesive resin comprising a vinyl chloride-vinyl acetate copolymer resin (hereinafter referred to as vinyl acetate vinyl) -acrylic resin between the thermoplastic resin substrate and the transparent thermoplastic resin layer. A method of providing a layer has also been proposed (Patent Document 1). According to this method, laminating is performed by interposing a heat-adhesive resin layer that is sufficiently thermally activated and exhibits adhesiveness in a low-temperature region where no breakage, elongation, deformation, deterioration, or the like of the sheet occurs. There is an advantage that sufficient laminate strength can be achieved without causing defects.

  However, since the above-mentioned heat-adhesive resin layer consists essentially of a resin that is inferior in heat resistance, the resulting decorative sheet is inferior in heat resistance. For example, it is strong in direct sunlight in semi-exterior applications. When heated, there is a problem that the heat-adhesive resin layer is softened by the heat and the transparent thermoplastic resin layer is peeled off from the thermoplastic resin substrate. This problem will theoretically be improved if a heat-adhesive resin with a high heat softening temperature is used, but if this is done, it will inevitably require an increase in the laminating temperature. This leads to poor lamination such as breakage, elongation, deformation, and deterioration, and the intended purpose cannot be achieved.

  Therefore, a crosslinking agent such as an isocyanate compound is blended in the thermoadhesive resin, and adhesiveness is expressed by heat at the time of laminating to adhere the thermoplastic resin base material and the transparent thermoplastic resin layer at the same time. A method of improving the heat resistance after laminating by causing a crosslinking reaction inside the adhesive resin is also conceivable. However, according to such a method, after applying the heat-adhesive resin to the thermoplastic resin base material, if a time is taken until the heat laminating process, the cross-linking reaction proceeds during that time. Since it will no longer develop, it is necessary to immediately heat laminate. Therefore, the progress management of the decorative sheet manufacturing process is cumbersome, and it is not possible to make a large amount of printed thermoplastic resin base coated with a heat-adhesive resin, so it is possible to produce a variety of products in small quantities. There are problems such as being very difficult to deal with.

  In addition, there are proposals such as dry lamination and melt extrusion lamination as alternatives to thermal lamination, but these require large-scale and expensive manufacturing equipment, and can be used for high-mix low-volume production and short delivery times. In the melt-extrusion laminating method, there is a problem that the types of resins that can be used are limited, so that the thermal laminating method cannot be completely replaced.

  Furthermore, the heat-adhesive resin layer is provided for the purpose of enabling adhesion by a heat laminating method between the thermoplastic resin base material and the transparent thermoplastic resin layer, and expressing the adhesive strength between the two layers. Conventionally, a heat-adhesive resin made of acrylic-polyester-vinyl acetate resin has been employed. This heat-adhesive resin takes advantage of the advantages of the acrylic resin and vinyl acetate resin that melt easily by heating and expresses adhesiveness, while taking into account the characteristics of polyester resin with little decrease in cohesive force even under heating. It is capable of heat laminating with sufficient adhesiveness even under relatively low temperature conditions without causing adverse effects such as breakage, elongation, deformation, deterioration, etc. on the thermoplastic resin substrate and transparent thermoplastic resin layer. At the same time, there is known one having a characteristic of maintaining sufficient peel resistance without losing adhesive strength even under high temperature use conditions in a semi-exterior application or the like (Patent Document 2).

  However, when the heat-adhesive resin layer is in direct contact with the thermoplastic resin base material, no adhesive force is generated, and it is necessary to pass through the ink layer of the pattern layer in order to exert the adhesive force. However, when the ink amount of the pattern layer was extremely small, there was a problem of peeling between layers when the produced decorative sheet was immersed in warm water.

As a countermeasure, I tried to apply a transparent medium ink layer on a thermoplastic resin substrate by solid printing, but this time I tested it with a weather resistance tester that confirmed the weather resistance performance in a short time by irradiating ultraviolet rays. In such a case, there arises a problem of peeling between the layers.
Japanese Patent No. 3853427 Japanese Patent No. 3633367

  The present invention has been made in order to solve the above-mentioned problems, and the object of the present invention is to provide a decorative sheet that exhibits sufficient weather resistance and does not peel between layers even when used for an exterior or the like for exterior use. It is to provide a cosmetic material.

The present invention solves the above-mentioned problems, that is, the invention according to claim 1 is that a pattern layer, a thermoadhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order on a thermoplastic resin substrate. In the decorative sheet, the thermoplastic resin is selected from a polyolefin resin, an acrylic resin, and a polyester resin, and an ultraviolet region of 315 to 400 nm is provided between the thermoplastic resin substrate and the pattern layer. A decorative sheet characterized in that a colored solid layer having an average spectral transmittance of 40% or less is provided , and a two-component curable urethane resin is used as a binder resin for the colored solid ink layer and the pattern layer. is there.

  In the invention according to claim 2, the thermoplastic resin base material and / or the transparent thermoplastic resin layer is a plurality of layers selected from the same or different types of polyolefin resins, acrylic resins, and polyester resins. 2. The decorative sheet according to claim 1, wherein a heat-adhesive resin layer is interposed between the layers.

  According to the invention of the first aspect of the present invention, the colored solid ink layer shields ultraviolet rays more efficiently, so that the adhesion between layers can be maintained while having weather resistance. Compared with the decorative sheet and the decorative sheet on which the transparent medium ink is solidly printed, it is possible to provide a decorative sheet that has excellent weather resistance of the base material and does not deteriorate with time even when used for an exterior or the like.

  According to the invention described in claim 2, the thermoplastic resin base material and / or the transparent thermoplastic resin layer is a multi-layer laminate selected from the same or different types of polyolefin resins, acrylic resins, and polyester resins. Even in such a case, a decorative sheet having excellent heat resistance, weather resistance, and adhesive strength can be easily obtained by a thermal laminating method by interposing a thermal adhesive resin layer between the respective layers.

  The technique of the present invention is particularly useful when the thermoplastic resin substrate and the transparent thermoplastic resin layer are composed of a thermoplastic resin selected from polyolefin resins, acrylic resins, and polyester resins. A decorative sheet having a performance equal to or higher than that of a polyvinyl chloride resin-based decorative sheet can be easily produced by the same heat laminating method as that of a conventional polyvinyl chloride resin-based decorative sheet. It has excellent advantages.

  The present invention will be described in detail below. FIG. 1 shows a cross-sectional structure of one embodiment of the decorative sheet of the present invention. A colored solid ink layer 2, a pattern / pattern layer 3, a heat-adhesive resin layer 4, and a transparent thermoplastic resin layer 5 are provided on the surface of the thermoplastic resin substrate 1.

  For the thermoplastic resin substrate 1 in the present invention, a resin selected from polyolefin resins, acrylic resins, and polyester resins is used.

  Examples of the polyolefin resin include polyethylene, polypropylene, polybutene, polymethylpentene and the like. Various other homopolymers and copolymers are known. Among them, the most suitable as a material for the thermoplastic resin base material for decorative sheets is a polypropylene resin, that is, a homopolymer or a copolymer mainly composed of polypropylene. Specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and an α-olefin having 2 to 20 carbon atoms other than propylene, preferably ethylene, butene-1, Examples thereof include a propylene-α-olefin copolymer containing 15 mol% or more of a comonomer of 4-methylpentene-1, hexene-1, or octene-1. Further, modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, which are usually used for softening polypropylene resins can be added. .

  Examples of the acrylic resin include methyl methacrylate resin and polymethyl methacrylate. Specific examples include various thermoplastic resins obtained by singly or copolymerizing acrylic acid derivatives such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic acid ester or methacrylic acid ester as the main component. . Among them, a resin mainly composed of a methacrylic acid ester such as methyl methacrylate, for example, a long-chain alkyl ester of methacrylic acid such as butyl methacrylate, an acrylic acid ester such as methyl acrylate, methacrylic acid or acrylic acid, etc. Flexibility and thermoformability are improved by adding selected monomers as copolymerization components and graft copolymerization, block copolymerization or blending of rubber components such as styrene-butadiene rubber or methyl methacrylate-butadiene rubber. Thus, the resin etc. which are formed can be used conveniently.

  Examples of polyester resins include polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, and polycarbonate. Other than these homopolymers, in the condensation polymerization reaction of aromatic dicarboxylic acid or dicarboxylic acid ester such as terephthalic acid or naphthalenedicarboxylic acid and aliphatic diol such as ethylene glycol or 1,4-butanediol, dicarboxylic acid component For example, long chain aliphatic dicarboxylic acid and / or alicyclic dicarboxylic acid such as sebacic acid, eicoic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, and / or polyethylene glycol, poly A resin having improved flexibility and thermoformability by introducing a polyether diol having hydroxyl groups at both ends, such as tetramethylene glycol, can be suitably used.

  In addition, the thermoplastic resin which comprises the thermoplastic resin base material 1 and the thermoplastic resin which comprises the transparent thermoplastic resin layer 5 may be the same, and may differ. For example, the thermoplastic resin substrate 1 is made of a polyolefin resin having a relatively low cost and good processability, while the transparent thermoplastic resin layer 5 is made of an acrylic resin to provide weather resistance, or thermoplasticity. The resin base material 1 can also be comprised with the laminated body of the multiple layer chosen from the same kind or different kind of polyolefin resin, acrylic resin, and polyester resin.

  In general, the decorative sheet as in the present invention often requires a concealing property against the color and defects of the surface of the adherend substrate. Therefore, in order to impart sufficient concealability to the target decorative sheet, the thermoplastic resin substrate 1 is concealed by adding a concealing pigment to the thermoplastic resin constituting the thermoplastic resin substrate 1. You can also.

  As the concealing pigment, it is desirable to use an inorganic pigment having a high refractive index and excellent concealing property. Specifically, for example, yellow lead, yellow iron oxide, cadmium yellow, titanium yellow, barium yellow, quinacridone, aureolin, molybdate orange, cadmium red, petal, red lead, cinnabar, mars violet, manganese violet, cobalt violet, Colored pigments such as cobalt blue, cerulean blue, ultramarine, bitumen, emerald green, chrome vermilion, chromium oxide, viridian, iron black, carbon black, etc., such as titanium oxide (titanium white, titanium white), zinc oxide (zinc white) White pigments such as basic lead carbonate (lead white), basic lead sulfate, zinc sulfide, lithopone, and titanox can be used.

  Above all, it is excellent in concealability and light resistance, and is suitable for decorative sheets in terms of design and color tone. Colored pigments are petals, iron oxide pigments such as yellow iron oxide and iron black, and white pigments are oxidized. It is most desirable to use a titanium pigment. Of course, other concealing or non-concealing inorganic pigments or organic pigments can be used together for the purpose of adjusting the color tone, in which case organic pigments such as cobalt blue and carbon black can be used. In the case of a pigment, it is preferable to use a pigment having excellent weather resistance such as a phthalocyanine pigment such as phthalocyanine blue. In addition, extender pigments such as silica, calcium carbonate, and barium sulfate can be used in combination as necessary.

  In addition, the thermoplastic resin constituting the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 5 may include, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, depending on the intended use of the decorative sheet. One or more conventionally known various additives such as a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, and a filler may be added.

  Examples of antioxidants include phenols, sulfurs, phosphoruss, etc., ultraviolet absorbers such as benzophenones, benzotriazoles, salicylates, cyanoacrylates, formamidines, oxanilides, etc. Hindered amines, nickel complexes, etc., heat stabilizers such as hindered phenols, sulfurs, hydrazines, etc., plasticizers depending on the type of resin, but phthalates, phosphates, fatty acids, etc. Type, aliphatic dibasic acid ester type, oxybenzoic acid ester type, epoxy type, polyester type, etc., as the lubricant, for example, fatty acid ester type, fatty acid type, metal soap type, fatty acid amide type, higher alcohol type, paraffin type, etc. Antistatic agents include, for example, cationic, anionic, and nonio Examples of flame retardants such as bromine, phosphorus, chlorine, nitrogen, aluminum, antimony, magnesium, boron, and zirconium, and fillers such as calcium carbonate and barium sulfate. , Talc, wax, kaolin and the like.

  When the colored solid ink layer 2 and the pattern layer 3 described later are provided between the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 5, the transparent thermoplastic resin layer 5 is at least the colored solid ink layer 2 below it. The pattern layer 3 should be transparent enough to be seen through, and is most preferably colorless and transparent, but it may be colored or translucent. As long as that is the case, the transparent thermoplastic resin layer 5 may contain a colorant and a filler.

  There is no restriction | limiting in particular in the thickness of the thermoplastic resin base material 1 or the transparent thermoplastic resin layer 5, For example, it can be set as the same thickness as those in the conventional general decorative sheet. Specifically, although it depends on the use of the decorative sheet and the type of resin, generally, the thickness of the thermoplastic resin substrate 1 is about 20 to 300 μm, more preferably about 50 to 200 μm, and the transparent thermoplastic resin layer. The thickness of 5 is about 10 to 200 μm, more preferably about 10 to 100 μm.

  There are no particular limitations on the molding method of the thermoplastic resin substrate 1 or the transparent thermoplastic resin layer 5, and it can be produced by any conventionally known molding method such as an extrusion molding method, an inflation molding method, a calendar molding method, a cast molding method, or the like. A film or sheet formed into a film can be used.

  The colored solid ink layer 2 in the present invention has an average spectral transmittance of 40% or less in the ultraviolet region of 315 to 400 nm. Specifically, it is appropriately selected from conventionally known colored inks and additives, but the type and amount of the pigment differ depending on the design required for the decorative sheet, but are added as appropriate within the range appropriate for the coating thickness and other cost effectiveness. The average spectral transmittance is adjusted to fall within the above range with an additive or the like.

  The pattern pattern layer 3 is provided for the purpose of imparting a desired decorative design to the target decorative sheet. Therefore, the surface coloring and color adjustment can be sufficiently achieved by coloring the thermoplastic resin substrate 1 and forming the colored solid ink layer 2 as in the case of a plain decorative sheet intended only for surface coloring and color adjustment. In some cases, the pattern layer 3 is not particularly provided. However, generally, the pattern layer 3 having an appropriate pattern is often provided on the front surface of the thermoplastic resin substrate 1 or the back surface of the transparent thermoplastic resin layer 5 by means such as a printing method.

  When the thermoplastic resin substrate 1 and / or the transparent thermoplastic resin layer 5 is composed of a plurality of layers, a pattern is formed between any layers of the thermoplastic resin substrate 1 and / or the transparent thermoplastic resin layer 5. The pattern layer 3 can also be provided (provided that all the resin layers on the surface side from the portion have transparency). Moreover, by providing the pattern layer 3 at a plurality of locations selected from these layers and between the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 5, an excellent design with a sense of depth and a three-dimensional effect is provided. Can also be applied to the decorative sheet.

  There are no restrictions on the constituent materials and forming methods of the colored solid ink layer 2 and the pattern layer 3, and any image forming material or image forming method that has been conventionally applied to the pattern layer of the decorative sheet is appropriately applied. be able to. Specifically, for example, a printing ink or a coating agent in which a colorant such as a dye or a pigment is dissolved or dispersed in an appropriate solvent together with an appropriate binder resin can be used.

  Examples of the colorant include inorganic pigments such as carbon black, titanium white, zinc white, dial, bitumen, cadmium red, azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazines. Organic pigments such as pigments, metal powder pigments such as gold powder, silver powder, copper powder, aluminum powder, and bronze powder, pearl luster pigments such as fish scale powder, basic lead carbonate, bismuth oxide chloride, and titanium oxide-coated mica, fluorescent pigments, night light A pigment or the like, or a mixture of two or more selected from these can be used.

  Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, polyvinyl resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, and melamine resins. , Various synthetic resins such as fluorine-based resins, silicone-based resins, fiber derivatives, and rubber-based resins, or a mixture or copolymer of two or more thereof can be used.

  Examples of the solvent include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane, ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate. Ester organic solvent, alcoholic organic solvent such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, ketone organic solvent such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, Ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran, and chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene It can be used various kinds and organic solvents such as solvents, inorganic solvents such as water, or two or more mixed solvents thereof.

  In addition, various additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion assistants, desiccants, stabilizers, curing agents, curing accelerators, or curing retarders as necessary. Can also be added as appropriate.

  In order to provide the target decorative sheet with excellent interlayer adhesion, it is preferable to use a resin having strong adhesiveness and cohesion as the binder resin for the colored solid ink layer 2 and the pattern layer 3. It is preferable to use a cross-linking curable resin such as a thermosetting resin or an ionizing radiation curable resin. Among them, it has moderate flexibility and flexibility while having high cohesive strength after crosslinking and curing, and exhibits excellent adhesiveness to inert thermoplastic resins such as polyolefin resins. In the present invention, it is most desirable to use a two-component curable urethane resin because it is excellent in adhesiveness with the acrylic-polyester-vinyl acetate resin used for the heat-adhesive resin layer 4. Specifically, after printing a printing ink composition in which 3 to 10 parts by weight of an isocyanate compound such as xylene diisocyanate or hexamethylene diisocyanate is added to 100 parts by weight of the main component having a polyester polyol-based resin as a main component, Most preferably, the colored solid ink layer 2 and the pattern layer 3 are formed by crosslinking and curing under heating.

  There is no restriction | limiting in particular in the formation method of the coloring solid ink layer 2 and the pattern layer 3, For example, various conventionally well-known various methods, such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, an inkjet printing method, etc. The printing method can be used. In addition, for example, in the case of a solid surface, in addition to the above-described various printing methods, for example, 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 Various coating methods such as a dip coating method can also be used. In addition, for example, a hand-drawn method, ink-sink method, photographic method, laser beam or electron beam drawing method, partial vapor deposition method or etching method of metal or the like, or a combination of these methods can of course be performed.

  Further, prior to the formation of the colored solid ink layer 2, the surface of the thermoplastic resin substrate 1 may be subjected to, for example, a corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromate treatment, anchor or primer treatment. By performing the treatment, the adhesion between the thermoplastic resin substrate 1 and the colored solid ink layer 2 can be improved.

  There is no particular limitation on the type of the pattern that the above-described pattern pattern layer 3 constitutes. For example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, or a geometric pattern that has been widely used in the field of the conventional decorative sheet. For the purpose of simple coloring or color adjustment, it may be a solid monochrome color. In short, any desired picture can be adopted depending on the intended use of the decorative sheet.

  The heat-adhesive resin layer 4 is provided for the purpose of enabling adhesion by a heat laminating method between the thermoplastic resin base material 1 and the transparent thermoplastic resin layer 5 and expressing adhesive strength between both layers. Yes, a plurality of resins such as acrylic resin and polyester resin may be combined.

  In laminating the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 5 via the thermal adhesive resin layer 4, the thermal adhesive resin layer 4 is previously formed on the thermoplastic resin substrate 1 side by coating. It may be formed on the transparent thermoplastic resin layer 5 side. When a film-like heat-adhesive resin layer 4 is available, heat lamination is performed by overlapping the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 5 in a sandwiched manner. You can also. However, in general, the thermoadhesive resin layer 4 tends to be excellent in adhesiveness with the surface of the coated thermoplastic resin layer, and therefore, on both bonded surfaces of the two thermoplastic resin layers to be bonded together. When the heat-adhesive resin layer 4 is previously formed by coating, the most excellent adhesive strength by the heat laminating method can be obtained.

  The surface of the transparent thermoplastic resin layer 5 may be provided with an emboss having a desired appropriate pattern as required, as conventionally known. The type of embossed pattern is not particularly limited, and may be various patterns such as, for example, wood grain (especially a conduit pattern), stone texture, fabric texture, Japanese paper texture, geometric pattern, or the like. It may be a simple matte shape, a grain shape, a hairline shape, a suede tone or the like. Further, by synchronizing these embossed patterns with the pattern of the pattern layer 3, it is possible to further improve the design, but if it is not necessary, the pattern may be non-synchronized. It is also possible to provide embossing of a pattern that includes both a pattern that is synchronized with the pattern and a pattern that is not synchronized.

  The embossing method is not particularly limited, but a mechanical embossing method using a metal embossing plate is the most common. There is no particular limitation on the emboss formation time, and any time can be selected from before, simultaneously with or after lamination of the transparent thermoplastic resin layer 5 with the thermoplastic resin substrate 1. Embossing of the same or different pattern can be performed a plurality of times at a plurality of times selected from the above times. In particular, according to the method of embossing at the same time as the lamination of the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 5 by the thermal laminating method, the lamination and the embossing can be performed in one step. From the standpoint of thermal energy efficiency.

  The decorative sheet of the present invention is used by adhering (laminating) to the surface of various base materials such as a wooden base material and an inorganic base material, as in the case of a conventional decorative sheet. For example, an appropriate adhesive such as urethane or vinyl acetate is used for application, but depending on the type of the adhesive, the adhesive with the thermoplastic resin constituting the thermoplastic resin substrate 1 is insufficient. Can be. In preparation for such a case, it is preferable to provide a primer layer (not shown) made of a resin excellent in adhesiveness to the laminating adhesive on the back surface of the thermoplastic resin substrate 1.

  Various primer agents such as urethane-based, acrylic-based, ethylene-vinyl acetate copolymer and the like are known as the primer layer, and those suitable for the thermoplastic resin constituting the thermoplastic resin substrate 1 are selected from these. Select and use. In addition, when powder such as silica, alumina, calcium carbonate, barium sulfate is added to the primer layer, the surface of the primer layer can be roughened to prevent blocking during winding and storage of the decorative sheet, It is also possible to improve the adhesiveness with the laminating adhesive due to the anchoring effect.

  As the thermoplastic resin substrate 1, a colored polyethylene resin film having a thickness of 90 μm (“TECLEAR E” manufactured by Bando Chemical Co., Ltd.) was used. On this surface, a colored solid ink layer 2 is formed by a gravure printing method using a two-component curable urethane resin ink (manufactured by Toyo Ink Manufacturing Co., Ltd.) formed by blending 3% by weight of an isocyanate curing agent with a polyester polyol vehicle. Printed. The average spectral transmittance in this ultraviolet region 315 to 400 nm was 20%. Furthermore, the picture pattern layer 3 was printed on it by the same method.

An acrylic-polyester copolymer resin (acrylic resin 60% by weight, polyester resin 40% by weight) is applied on the pattern layer 3 by applying a gravure coating method to a coating amount of 5 g / m ² after drying, The thermoadhesive resin layer 4 was molded. Further, a transparent acrylic resin film having a thickness of 50 μm (“HBS-006” manufactured by Mitsubishi Rayon Co., Ltd.) is used as the transparent thermoplastic resin layer 5 on the surface of the heat-adhesive resin layer 4, and the film surface temperature is 120 ° C. A decorative sheet was obtained by heat lamination under the following conditions.

<Comparative Example 1>
A decorative sheet was obtained in the same manner as in Example 1 except that the colored solid ink layer 2 was removed.

<Comparative example 2>
Instead of the colored solid ink layer 2, Example 1 and a decorative sheet were obtained except that the transparent medium ink was solid-printed (average spectral transmittance in the ultraviolet region of 315 to 400 nm was 70%).

<Performance comparison>
The decorative sheets of Example 1 and Comparative Examples 1 and 2 produced as described above were tested at room temperature between 21 ° C. and 26 ° C. (JIS K7100-1999). Apply a two-component urethane resin adhesive (applying amount of about 30 μm after drying) to an aluminum plate with a thickness of 70 μm on an aluminum plate with a thickness of 70 μm and laminate it with a hand rubber roller with a diameter of 125 mm and a width of 200 mm for 24 hours. It was left indoors and cured to obtain a cosmetic material, which was used as a test piece.

<Performance test 1>
A weather resistance test was conducted using a metal weather manufactured by Daipura Wintes. Test conditions are as follows: illumination 65 mW / cm ² , black panel temperature 53 ° C., LIGHT irradiation condition (53 ° C./70% RH / 20 hours), DEW condensation conditions (30 ° C./98% RH / 4 hours), LIGHT One cycle of 30 seconds shower is 24 hours.

<Performance test 2>
The test piece was immersed in boiling water for 4 hours, and peeling between layers was observed. The results are shown in Table 1.

The present invention relates to a decorative sheet for use in interior and exterior materials of buildings such as houses, building materials such as construction materials and fittings, furniture fixtures, vehicle interiors, housing equipment, home appliances, etc. In particular, it can be used as a decorative sheet suitable for surface decoration of building members that require weather resistance and heat resistance such as exteriors and entrance doors.

It is explanatory drawing which shows the shape of the cross section of one implementation of the decorative sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Thermoplastic resin base material 2 ... Colored solid ink layer 3 ... Picture pattern layer 4 ... Thermal-adhesive resin layer 5 ... Transparent thermoplastic resin layer

Claims (2)

In a decorative sheet in which a pattern layer, a thermoadhesive resin layer, and a transparent thermoplastic resin layer are laminated at least in this order on a thermoplastic resin substrate, the thermoplastic resin is a polyolefin resin, an acrylic resin, or a polyester resin. A colored solid layer having an average spectral transmittance of 40% or less in an ultraviolet region of 315 to 400 nm is provided between the thermoplastic resin base material and the pattern layer, and the colored solid ink layer; A decorative sheet comprising a two-component curable urethane-based resin as a binder resin for the design pattern layer .   The thermoplastic resin substrate and / or the transparent thermoplastic resin layer is a plurality of layers selected from the same or different types of polyolefin resins, acrylic resins, and polyester resins, and a thermoadhesive resin layer is interposed between the layers. The decorative sheet according to claim 1.