JP2009255420A - Decorative sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet which prevents peeling from occurring between decorative sheet layers even when the sheet is used, for example, in an exterior that is an external facing application for a long period of time. <P>SOLUTION: In the decorative sheet in which a pattern layer, a thermally adhesive resin layer, and a transparent thermoplastic resin layer are formed at least in this order on a thermoplastic resin substrate, a solid ink layer is formed between the thermoplastic resin substrate and the pattern layer, and an ultraviolet absorption resin layer having an average spectral transmittance in an ultraviolet line domain 315-400 nm of 0-40% is formed between the pattern layer and the thermally adhesive resin layer. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

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 widely used more widely than a single-layer decorative sheet because it is easy to achieve high hiding 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 substrate, no adhesive force is generated, and it is necessary to place a pattern layer in order to exert the adhesive force. However, when the amount of ink in the pattern layer was extremely small, there was a problem that when the produced decorative sheet was immersed in warm water, it peeled off between the sheet layers.

As a countermeasure, we tried to apply a transparent medium pattern layer on a thermoplastic resin substrate by solid printing, but this time we irradiate ultraviolet rays to check the weather resistance performance in a short time. When the test was performed using a die plastic win tes), there was a problem of peeling between the sheet layers.
Japanese Patent No. 3853427 Japanese Patent No. 3633367

  The present invention has been made to solve the above-mentioned problems, and the object of the present invention is to provide a decorative sheet that does not cause peeling between decorative sheet layers even when used for a long time in exteriors that are exterior applications. There is to do.

  The present invention has been made to solve the above-mentioned problems, and the invention according to claim 1 is characterized in that a pattern layer, a thermoadhesive resin layer, and a transparent thermoplastic resin layer are provided on a thermoplastic resin substrate. In the decorative sheet formed in this order, a solid ink layer is provided between the thermoplastic resin substrate and the pattern layer, and between the pattern pattern layer and the thermal adhesive resin layer, in an ultraviolet ray region of 315 to 400 nm. A decorative sheet comprising an ultraviolet-absorbing resin layer having an average spectral transmittance of 0 to 40%.

  In the invention according to claim 2, the thermoplastic resin used for the thermoplastic resin substrate and the transparent thermoplastic resin layer is a mixture of one or two selected from olefin resins, acrylic resins and polyester resins. The decorative sheet according to claim 1, wherein the decorative sheet is a resin made of a copolymer.

  According to the first aspect of the present invention, the solid ink layer increases the adhesive strength between the thermoplastic resin substrate and the pattern layer, and the ultraviolet absorbing resin has an average spectral transmittance of 0% to 40% in the ultraviolet region of 315 nm to 400 nm. The layer can block the adverse effect of the ultraviolet rays on the adhesive strength between the thermoplastic resin substrate and the pattern layer, and can provide a decorative sheet that is slow to deteriorate over time even when used for an exterior or the like.

  According to the invention described in claim 2, the technique of the present invention is such that the thermoplastic resin base material and the transparent thermoplastic resin layer are composed of a thermoplastic resin selected from a polyolefin resin, an acrylic resin, and a polyester resin. In particular, a decorative sheet having a performance equal to or higher than that of a conventional polyvinyl chloride resin-based decorative sheet is obtained by the same heat laminating method as that of a conventional polyvinyl chloride resin-based decorative sheet. It has an excellent advantage that it can be easily manufactured.

Hereinafter, the decorative sheet of the present invention will be described in detail with reference to the drawings.
FIG. 1 shows a cross-sectional structure of one embodiment of the decorative sheet of the present invention. A solid ink layer 2, a pattern / pattern layer 3, an ultraviolet absorbing resin layer 4, a thermal adhesive resin layer 5, and a transparent thermoplastic resin layer 6 are provided on a thermoplastic resin substrate 1.

The kind of the thermoplastic resin constituting the thermoplastic resin substrate 1 in the present invention is not particularly limited. For example, a conventional thermoplastic resin substrate for a decorative sheet or a material used for a transparent thermoplastic resin layer is known. Any thermoplastic resin can be used. Specifically, for example, polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, polyolefin resins such as ethylene-vinyl acetate copolymer or a saponified product thereof, and ethylene- (meth) acrylic acid (ester) copolymer. Copolymer, Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, Polyarylate, Polyester resin such as polycarbonate, Acrylic resin such as polymethyl methacrylate, 6-Nylon, 6,6-Nylon, 6,10-Nylon Polyamide resin such as polystyrene resin, AS resin, ABS resin, styrene resin such as cellulose acetate, cellulose derivatives such as nitrocellulose, chlorinated resin such as polyvinyl chloride and polyvinylidene chloride, polyvinyl fluoride, poly Fluorine resins such as vinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, etc., starches such as polylactic acid resin, plant-derived material films consisting of ethanol, etc., or two or more selected from these Copolymers, mixtures, composites, laminates, and the like can be used.
However, it is a thermoplastic resin that does not contain chlorine, and in consideration of processability, interlaminar adhesion strength, weather resistance, etc., one or two types selected from olefin resins, acrylic resins, and polyester resins are mixed or co-polymerized. A resin made of a polymer is preferred.

  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., for example, 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 may include, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, depending on the intended use of the decorative sheet. One or more conventionally known various additives such as 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.

  The solid ink layer 2 and the pattern layer 3 in the present invention may be transparent or colored, but are provided on the entire surface of the thermoplastic resin substrate 1. In many cases, the thermoplastic resin substrate 1 is colored and has a concealing property, and is a combination of the design and design of the design pattern layer 3, so that the solid ink layer 2 is transparent. As a constituent material and a forming method of the solid ink layer 2 and the pattern layer 3, a conventionally known method can be appropriately used. Specifically, for example, a printing ink or a coating agent dissolved or dispersed in a suitable solvent together with a suitable binder resin can be provided by solid printing. When coloring, an optional dye or pigment colorant is added.

  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, melamine resins, and fluorine resins. Various synthetic resins such as resin, silicone resin, fiber derivative, rubber resin, etc., 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 give the target decorative sheet an excellent interlayer adhesion, it is preferable to use a resin having strong adhesiveness and cohesion as the binder resin for the 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. Especially, it has moderate flexibility and softness while having a high cohesive force after crosslinking and curing, and exhibits excellent adhesiveness to inert thermoplastic resins such as polyolefin resins.
In addition, it is most desirable to use a two-component curable urethane-based resin in terms of excellent adhesiveness with an acrylic-polyester-vinyl acetate-based resin that is preferably used for the heat-adhesive resin layer 4 described later. 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.

  The formation method of the solid ink layer 2 and the pattern layer 3 is not particularly limited, and various conventionally known methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an ink jet printing method can be used. Printing methods 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, the hand-drawing method, the ink-sinking method, the photographic method, the laser beam or electron beam drawing method, the partial vapor deposition method of metal or the like, the etching method, etc., or a combination of these methods can of course be performed.

  Further, prior to the formation of the solid ink layer 2, as necessary, the surface of the thermoplastic resin substrate 1 is subjected to surface treatment such as corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment. The adhesion between the thermoplastic resin substrate 1 and the solid ink layer 2 can be improved.

  There is no particular limitation on the type of the pattern that the pattern pattern layer 3 constitutes, for example, a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, etc. that have been widely adopted in the field of conventional decorative sheets. Or, for the purpose of simple coloring or color adjustment, it may be a solid monochrome color. In short, any desired picture can be adopted according to the intended use of the decorative sheet.

  As the ultraviolet absorbing resin layer 4 in the present invention, one having an average spectral transmittance of 0 to 40% in the ultraviolet ray region 315 to 400 nm is used. There is no restriction | limiting in particular in resin to be used or layer thickness, A constituent material, a manufacturing method, application | coating thickness, etc. are adjusted suitably so that it may become a physical property within the range. Specifically, it has good bonding properties with currently used acrylic-polyester-vinyl chloride resins.

  The transparent thermoplastic resin layer 5 is made of an acrylic resin such as methyl methacrylate resin or polymethyl methacrylate.

  However, considering the adaptation to environmental problems that are becoming social problems in recent years, the use of the above-mentioned chlorine-based resins and fluorine-based resins is not very preferable, and the resin does not contain halogen elements such as chlorine and fluorine. That is, it is preferable to use a non-halogen resin. Above all, including the market price, distribution volume and ease of procurement, moderate balance of flexibility and strength as a thermoplastic resin base material for decorative sheets, processability such as bending, cutting and cutting, wear resistance It is most preferable to use a thermoplastic resin selected from a polyolefin resin, an acrylic resin, and a polyester resin from the viewpoints of various physical properties such as surface properties such as property and solvent resistance, and weather resistance.

  Various homopolymers and copolymers such as those listed above are known as polyolefin resins. Among them, the most suitable material for the thermoplastic resin base material for decorative sheets is polypropylene resin, that is, polypropylene. A single or copolymer as a component, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and a polypropylene crystal part, and a C2-C20 α- other than propylene Examples thereof include propylene-α-olefin copolymers containing 15 mol% or more of an olefin, preferably ethylene, butene-1,4-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 various thermoplastic resins obtained by singly or copolymerizing an acrylic acid derivative such as acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, acrylic ester or methacrylic ester as a main component. Can be mentioned. 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.

  In addition to the above-mentioned homopolymers such as polyethylene terephthalate and polyethylene naphthalate, polyester resins include aromatic dicarboxylic acids or dicarboxylic acid esters such as terephthalic acid and naphthalenedicarboxylic acid, ethylene glycol, and 1,4-butanediol. In a condensation polymerization reaction with an aliphatic diol such as, for example, a long-chain aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid such as sebacic acid, eicoic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, etc. Suitable for resins with improved flexibility and thermoformability by introducing and / or introducing polyether-based diols having hydroxyl groups at both ends such as polyethylene glycol and polytetramethylene glycol as diol components Can be used for Kill.

  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 which consists of the same kind or different kind of thermoplastic resin.

  When the solid ink layer 2 and the pattern pattern layer 3 are provided between the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 6, the transparent thermoplastic resin layer 6 is at least the colored solid ink layer 2 and the pattern pattern below it. The layer 3 needs to be transparent to the extent that it can be seen through, and is most preferably colorless and transparent, but it may be colored and translucent. As long as that is the case, the transparent thermoplastic resin layer 6 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 6, 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 is no particular limitation on the molding method of the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 6. For example, the thermoplastic resin substrate 1 or the transparent thermoplastic resin layer 6 can be produced by any conventionally known molding method such as an extrusion molding method, an inflation molding method, a calendar molding method, or a cast molding method. A film or sheet formed into a film can be used.

  In the case where the thermoplastic resin substrate 1 and / or the transparent thermoplastic resin layer 6 are composed of a plurality of layers, a pattern is provided between any of the layers constituting the thermoplastic resin substrate 1 and / or the transparent thermoplastic resin layer 6. 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 base material 1 and the transparent thermoplastic resin layer 6, excellent design properties with a sense of depth and three-dimensionality are provided. Can also be applied to the decorative sheet.

  There is no limitation on the constituent material and the forming method of the ultraviolet absorbing resin layer 4, and any image forming material or image forming method that has been conventionally applied to the solid ink layer and the pattern layer of the decorative sheet should be applied as appropriate. Can do. Specifically, for example, a transparent printing ink or a coating agent that is dissolved or dispersed in an appropriate solvent can be used together with an appropriate binder resin.

  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, 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.

  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 crosslinking curable resin such as a thermosetting resin or an ionizing radiation curable resin. Above all, it has moderate flexibility and flexibility while having high cohesive strength after crosslinking and curing, and also exhibits excellent adhesion to inert thermoplastic resins such as polyolefin resins. It is most preferable to use a two-component curable urethane-based resin in terms of excellent adhesiveness with an acrylic-polyester-vinyl acetate-based resin that is preferably used for the thermal adhesive resin layer 5 described later. 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 particular limitation on the method of forming the ultraviolet absorbing resin layer 4. For example, various conventionally known printing methods such as gravure printing method, offset printing method, screen printing method, flexographic printing method, electrostatic printing method, and inkjet printing method can be used. 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, the hand-drawing method, the ink-sinking method, the photographic method, the laser beam or electron beam drawing method, the partial vapor deposition method of metal or the like, the etching method, etc., or a combination of these methods can of course be performed.

  The heat-adhesive resin layer 5 is provided for the purpose of enabling adhesion by a heat laminating method between the thermoplastic resin base material 1 and a transparent thermoplastic resin layer 6 described later, and expressing adhesive strength between both layers. An acrylic resin, a polyester resin, or the like is conceivable, but a plurality of resins such as an acrylic-polyester-vinyl acetate resin may be combined. In particular, acrylic-polyester-vinyl acetate resin is a polyester resin that can be easily melted by heating and exhibits the adhesive properties, and has little decrease in cohesive force even under heating, while taking advantage of the advantages of acrylic resin and vinyl acetate resin. In view of the above characteristics, sufficient adhesion is exhibited even under relatively low temperature conditions that do not adversely affect the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 6 such as breakage, elongation, deformation, and deterioration. Thus, it can be heat laminated, and at the same time has a characteristic of maintaining sufficient peel resistance without losing adhesive strength even under high temperature use conditions such as semi-exterior applications.

  In laminating the thermoplastic resin substrate 1 and the transparent thermoplastic resin layer 6 via the thermal adhesive resin layer 5, the thermal adhesive resin layer 5 is previously formed on the thermoplastic resin substrate 1 side by coating. Alternatively, it may be formed on the transparent thermoplastic resin layer 6 side. Further, when the 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 6 in a sandwiched manner. You can also. However, in general, the thermoadhesive resin layer 5 tends to be excellent in adhesiveness with the surface of the coated thermoplastic resin layer, so that both the two thermoplastic resin layers to be bonded are bonded to each other. 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 6 may be provided with an emboss having a desired appropriate pattern as required, as is 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, the design can be further improved by synchronizing the embossed pattern with the pattern of the pattern layer 2, but if 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 with the laminating adhesive on the back surface of the thermoplastic resin substrate 1.

  Various primer agents such as urethane, acrylic, ethylene-vinyl acetate copolymer system, vinyl chloride-vinyl acetate copolymer system are known as the primer layer, and thermoplastic resin substrate 1 is selected from these. Select and use one that is suitable for the thermoplastic resin. 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 solid ink layer 2 is printed by a gravure printing method using a two-component curable urethane resin ink (manufactured by Toyo Ink Co., Ltd.) containing 3% by weight of an isocyanate curing agent in a polyester polyol vehicle. did.
Furthermore, the pattern pattern layer 3 was printed by the same method, and the pattern pattern layer 3 was provided.

A two-part curable urethane resin ink (manufactured by Toyo Ink Co., Ltd.) containing 3% by weight of an isocyanate curing agent in a polyester polyol vehicle on the printed surface of the pattern layer 3 and a benzotriazole ultraviolet absorber. A resin obtained by blending 1% by weight (“Tinubin PS” manufactured by Ciba Specialty Chemicals Co., Ltd.) was applied to a coating amount of 1 g / m ² after drying by a gravure coating method to form an ultraviolet absorbing resin layer 4. The average spectral transmittance in the line region 315 to 400 nm was 35%.

On this ultraviolet absorbing resin layer 4, the acrylic resin, polyester resin, and vinyl chloride resin in the acrylic-polyester-vinyl chloride resin are mixed at 40 wt% acrylic resin, 30 wt% polyester resin, and vinyl chloride vinyl chloride. 30 wt% of the resin was applied by a gravure coating method to a coating amount of 1.5 g / m ² after drying to form a heat-adhesive resin layer 5.

  A transparent acrylic resin film having a thickness of 50 μm (“HBS-006” manufactured by Mitsubishi Rayon Co., Ltd.) as a transparent thermoplastic resin layer 6 is heated on the surface of the heat-adhesive resin layer 5 at a film surface temperature of 120 ° C. Lamination was performed to obtain the decorative sheet of the present invention.

<Comparative Example 1>
In Example 1, a decorative sheet excluding the ultraviolet absorbing resin layer was produced.

<Comparative example 2>
In Example 1, a decorative sheet excluding the solid ink layer was produced.

<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). Two-part urethane resin adhesive (applied amount of about 30 μm after drying) is applied to an aluminum plate with a thickness of 70 μm on an aluminum plate with a thickness of 70 μm and laminated with a hand rubber roller with a diameter of 125 mm and a width of 200 mm for 24 hours. It was allowed to stand and cured to obtain a cosmetic material, which was used as a test piece.

<Weather resistance test>
Implementation of weather resistance test using die plastic wintes metal weather. 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.

<Peel test>
The specimen was immersed in boiling water for 15 minutes, and peeling between the sheet 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, the present invention relates to 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 side sectional explanatory drawing which shows embodiment of the decorative sheet of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Thermoplastic resin base material 2 ... Solid ink layer 3 ... Pattern pattern layer 4 ... Ultraviolet-absorbing resin layer 5 ... Thermal-adhesive resin layer 6 ... 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 provided in this order on a thermoplastic resin substrate, a solid ink layer is provided between the thermoplastic resin substrate and the pattern layer. An ultraviolet absorbing resin layer having an average spectral transmittance of 0 to 40% in an ultraviolet ray region of 315 to 400 nm is provided between the pattern layer and the thermal adhesive resin layer. Makeup sheet.   The thermoplastic resin used for the thermoplastic resin base material and the transparent thermoplastic resin layer is a resin composed of one or two kinds or a copolymer selected from an olefin resin, an acrylic resin, and a polyester resin. The decorative sheet according to claim 1.