JP6576096B2 - Decorative sheet and method for producing the decorative sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet used for a building interior material, a building exterior member such as a front door, a flooring material, a surface of a joinery, a surface material of home appliances, and a manufacturing method of the decorative sheet. The present invention relates to a decorative sheet having a layer made of a crystalline polypropylene resin composition obtained by adding a dispersant vesicled by an inorganic filler and a method for producing the decorative sheet .

  Decorative sheets used for building interior materials, flooring materials, surfaces of joinery, etc., especially decorative sheets used for floors walking on the ground, are relatively superior in scratch resistance, ceramic-based inorganic materials, vinyl chloride It was customary to use tiles. However, ceramic inorganic materials have a problem that they are difficult to process and design is limited, and vinyl chloride tiles have been considered to generate toxic gases during combustion. In order to solve these problems and problems, Patent Document 1 proposes a decorative sheet using a polypropylene resin having a design similar to that of indoor flooring. When polypropylene resin is used, it is easy to process and not only can provide decorative sheets with various designs, but also suppresses the generation of toxic gases during combustion, but has poor scratch resistance. When applied to a decorative sheet used for the above-mentioned purposes, there have been problems such as a significant decrease in designability due to friction and scratches due to long-term walking.

JP 2013-049989 A JP 2013-122020 A

  As a method for obtaining a decorative sheet using a polypropylene resin excellent in scratch resistance, there is a method in which a part of the polypropylene resin used for the sheet material is replaced with a filler by filling the polypropylene resin with a filler. Although it has been attempted to suppress wear due to friction of the polypropylene resin by this method, sufficient adhesive strength at the interface between the polypropylene resin and the filler cannot be obtained, and the filler falls off from the polypropylene resin due to friction. There was a problem. Therefore, an attempt was made to improve the adhesive strength at the interface between the polypropylene resin and the filler by adding a dispersant. However, if a large amount of filler is added, the adhesive force between the filler and the dispersant is weakened. When trying to maintain the adhesive force between the filler and the dispersant, the filler could not be added to the extent that the scratch resistance of the decorative sheet was improved.

  In addition, when adding a filler to improve the scratch resistance of the decorative sheet, if the refractive index of the filler does not approximate the refractive index of the polypropylene resin, it becomes cloudy as the amount of filler added increases, It had the subject that property was impaired.

Here, the present inventors have, by the dispersing agent containing vesicles encasing an dispersing agent in the supercritical reverse phase evaporation method discloses Therefore vesicle in Patent Document 2, in which a filler is added to the polypropylene resin composition A polyolefin resin composition in which the filler was uniformly dispersed in the polypropylene resin material was completed.

In the present invention, by using a method of adding the above-mentioned dispersing agent encapsulating vesicle and filler obtained by encapsulating a dispersant depending on vesicle supercritical reverse phase evaporation method crystalline polypropylene resin material, abrasion resistance and designability An object of the present invention is to provide a decorative sheet and a method for producing the decorative sheet .

In order to achieve the above object, the decorative sheet according to the first aspect of the present invention is a decorative sheet comprising a plurality of resin layers, and at least one of the resin layers on the surface side is 100 wt. 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 for light having a wavelength of 550 nm and a supercritical reverse phase evaporation method to 12-hydroxy magnesium stearate, a silane coupling agent, and titanate. It is formed as a layer made of a crystalline polypropylene resin composition to which a dispersing agent-encapsulating vesicle encapsulating a dispersing agent, which is any one of a coupling agent, silicone, wax, and modified resin, is formed. wherein one layer of the back side of the first layer on the surface side, is an opaque masking layer containing a flaky metal was aluminum and flaky And said that you are.

In such a decorative sheet of the first aspect of the present invention, at least one layer on the surface side of the resin layer is formed into a vesicle by 12-hydroxymagnesium stearate, a silane coupling agent, By adding a dispersant-encapsulating vesicle that contains a titanate coupling agent, silicone, wax, or modified resin, the dispersant is uniformly dispersed in the crystalline polypropylene resin composition. In addition, the dispersion force of the dispersant can prevent the secondary aggregation of the inorganic filler and uniformly disperse it. Therefore, even if a large amount of the inorganic filler is added, sufficient at the interface between the crystalline polypropylene resin and the inorganic filler is sufficient. Since the adhesive strength can be obtained, a decorative sheet having excellent scratch resistance can be provided. Furthermore, since one layer of the resin layer on the back side from the one layer on the front side is an opaque concealing layer containing a flaky metal made of aluminum as a flake , the layer on the front side from the concealing layer Even if the layer has a transparent part, the concealing layer exerts a concealing effect due to opacity and contains a flaky metal made of aluminum as a flake , so that a normal concealing material can be used. Therefore, it is possible to provide a decorative sheet that exhibits a higher concealing property than that of the case, and has an excellent design.

The decorative sheet according to the second aspect of the present invention is a decorative sheet composed of a plurality of resin layers , and at least one layer on the surface side of the most back surface layer of the resin layers is 100 parts by weight of crystalline polypropylene resin. In contrast, 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 of light having a wavelength of 550 nm and a dispersant-encapsulating vesicle in which the dispersant is encapsulated by a supercritical reverse phase evaporation method were added. The vesicle is formed as a layer comprising a crystalline polypropylene resin composition, and the vesicle comprises a mixture of a phospholipid and a nonionic surfactant, or at least one of a phospholipid and a nonionic surfactant, cholesterols and triacylglycerol. a liposome comprising an outer film made of a mixture of the dispersant is 12-hydroxystearic acid Mug Siumu, silane coupling rig agent, titanate coupling agent, silicone, waxes, modifying resins, is any one of, the crystalline polypropylene resin is isotactic Tat fraction (mmmm fraction) high at 95% It is a crystalline homopolypropylene resin.

In such a decorative sheet of the second aspect of the present invention, at least one layer on the surface side of the most back surface side of the resin layers is encapsulated with a dispersant in the vesicle by the supercritical reverse phase evaporation method. By adding the dispersant-encapsulating vesicle, the dispersant is uniformly dispersed in the crystalline polypropylene resin composition, and the secondary agglomeration of the inorganic filler is prevented by the dispersing power of the dispersant to uniformly disperse. Therefore, even if a large amount of an inorganic filler is added, sufficient adhesive strength at the interface between the crystalline polypropylene resin and the inorganic filler can be obtained, so that a decorative sheet having excellent scratch resistance can be provided. Furthermore, the vesicle is formed into a liposome having an outer membrane composed of a mixture of a phospholipid and a nonionic surfactant or a mixture of a phospholipid and a nonionic surfactant and at least one of cholesterols and triacylglycerol. The compatibility between the crystalline polypropylene resin composition and the liposome can be improved, and as a result, the inorganic filler as an inclusion in the crystalline polypropylene resin composition can be uniformly dispersed. Furthermore, since the dispersant is any of 12-hydroxy magnesium stearate, silane coupling agent, titanate coupling agent, silicone, wax, and modified resin, the compatibility between the crystalline polypropylene resin composition and the dispersant is good. Can be reliably prevented, and as a result, sufficient adhesive strength can be exhibited at the interface between the crystalline polypropylene resin composition and the inorganic filler. Furthermore, since the crystalline polypropylene resin is a highly crystalline homopolypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more, a decorative sheet having excellent scratch resistance is provided. Can do.

The decorative sheet according to the third aspect of the present invention is a decorative sheet comprising a plurality of resin layers used by being bonded to a base material, and includes a raw fabric layer, a transparent resin layer, and a topcoat layer contained in the resin layer. Are positioned in this order, and the transparent resin layer is supercritical with 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 of light having a wavelength of 550 nm with respect to 100 parts by weight of the crystalline polypropylene resin. It is formed as a layer comprising a crystalline polypropylene resin composition in which a dispersant-encapsulating vesicle in which a vesicle is encapsulated by a reverse phase evaporation method is added, and the dispersant is 12-hydroxy magnesium stearate, silane cup rig agent, titanate coupling agent, silicone, waxes, modifying resins, is any one of, the crystalline polypropylene resin, Aisota Wherein the tic pen Tat fraction (mmmm fraction) is a highly crystalline homopolymer polypropylene with 95% or more.

In the decorative sheet according to the third aspect of the present invention, the decorative sheet is composed of a plurality of resin layers in which the raw fabric layer, the transparent resin layer, and the top coat layer are positioned in this order, Since they are used by being bonded together, they can be used by being bonded to various base materials such as wooden boards. Furthermore, by adding a dispersant-encapsulating vesicle in which the transparent resin layer in the resin layer is encapsulated in the vesicle by the supercritical reverse phase evaporation method, the dispersant is added in the crystalline polypropylene resin composition. It is possible to uniformly disperse and to prevent the secondary agglomeration of the inorganic filler by the dispersing power of the dispersant so that it can be dispersed uniformly. Therefore, even if a large amount of the inorganic filler is added, the interface between the crystalline polypropylene resin and the inorganic filler Since sufficient adhesive strength can be obtained, a decorative sheet having excellent scratch resistance can be provided. Furthermore, since the dispersant is any of 12-hydroxy magnesium stearate, silane coupling agent, titanate coupling agent, silicone, wax, and modified resin, the compatibility between the crystalline polypropylene resin composition and the dispersant is good. Can be reliably prevented, and as a result, sufficient adhesive strength can be exhibited at the interface between the crystalline polypropylene resin composition and the inorganic filler. Furthermore, since the crystalline polypropylene resin is a highly crystalline homopolypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more, a decorative sheet having excellent scratch resistance is provided. Can do.

The method for producing a decorative sheet according to the first aspect of the present invention is a method for producing a decorative sheet comprising a plurality of resin layers, wherein at least one of the resin layers on the surface side is 100 parts by weight of a crystalline polypropylene resin. In contrast, 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 of light having a wavelength of 550 nm and a supercritical reverse phase evaporation method, 12-hydroxy magnesium stearate, silane coupling agent, titanate cup Formed as a layer made of a crystalline polypropylene resin composition to which a dispersing agent-encapsulating vesicle encapsulating a dispersing agent that is either a ring agent, silicone, wax, or modified resin is added, and the surface of the resin layer the hiding layer comprising a back side one layer of from 1 layer side, is formed by adding flaky metal and flaked aluminum in a resin And wherein the door.

The method for producing a decorative sheet according to the second aspect of the present invention is a method for producing a decorative sheet comprising a plurality of resin layers, wherein at least one of the resin layers is based on 100 parts by weight of the crystalline polypropylene resin. Crystalline polypropylene in which 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 of light having a wavelength of 550 nm and a dispersant-encapsulating vesicle in which a dispersant is encapsulated by a supercritical reverse phase evaporation method are added The vesicle is formed from a mixture of a phospholipid and a nonionic surfactant or a mixture of a phospholipid and a nonionic surfactant and at least one of cholesterols and triacylglycerol. comprising a liposome comprising an outer layer, the dispersing agent is magnesium 12-hydroxystearic acid , Silane coupling rig agent, titanate coupling agent, silicone, waxes, modifying resins, is any one of, the crystalline polypropylene resin is isotactic Tat fraction (mmmm fraction) High crystals is 95% or more It is a characteristic homopolypropylene resin.

According to the decorative sheet and decorative sheet production method of the present invention, a method of adding the supercritical reverse-phase evaporation method therefore and a dispersing agent containing vesicles and inorganic filler was contained a dispersant vesicles crystalline polypropylene resin material It is possible to provide a decorative sheet excellent in scratch resistance and design and a method for producing the decorative sheet .

Sectional drawing which shows embodiment of the decorative sheet of this invention

The decorative sheet of the present invention is a decorative sheet comprising a plurality of resin layers, and at least one of the resin layers has a refractive index of 1.46 at a wavelength of 550 nm with respect to 100 parts by weight of the crystalline polypropylene resin. It is formed as a layer comprising a crystalline polypropylene resin composition in which 5 to 200 parts by weight of an inorganic filler of ˜1.52 and a dispersant-encapsulating vesicle in which a vesicle is encapsulated by a supercritical reverse phase evaporation method are added . Is.

  As crystalline polypropylene resin, in addition to homopolypropylene, random polypropylene, block polypropylene, propylene and α-olefin (for example, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12 Ethyl-1-tetradecene, etc.) are copolymerized, and ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer are added to these crystalline polypropylene resins. Alloying polymers, ethylene / ethyl methacrylate copolymers, ethylene / butyl methacrylate copolymers, ethylene / methyl acrylate copolymers, ethylene / ethyl acrylate copolymers, ethylene / butyl acrylate copolymers, various rubber components, etc. Also included.

  As the inorganic filler, it is important to use a material having a refractive index of light having a wavelength of 550 nm of 1.45 to 1.52. In particular, the glass filler is relatively free by mixing silicon dioxide as a main component and appropriately mixing zirconium dioxide, boron oxide, sodium oxide, aluminum oxide, calcium oxide, zinc oxide, magnesium oxide, strontium oxide, iron and the like. This is preferable because the refractive index can be controlled.

  Examples of the dispersant include polymer surfactants, fatty acid metal salts, silane coupling agents, titanate coupling agents, silicones, waxes, modified resins, and the like. Examples of the polymeric surfactant include aliphatic polyvalent polycarboxylic acid, polycarboxylic acid alkylamine, polyacrylic acid, polymethacrylic acid, polyoxyethylene alkyl ether, and sorbitan fatty acid ester. As fatty acid metal salts, stearic acid, lauric acid, 12-hydroxystearic acid, montanic acid, behenic acid, ricinoleic acid, myristic acid, etc. and lithium, sodium, potassium, magnesium, calcium, barium, zinc, aluminum, etc. were combined. Things. As the silane coupling agent, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, Examples include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Examples of titanate coupling agents include tetrakis [2,2-bis (allyloxymethyl) butoxy] titanium (IV), di-i-poropoxytitanium diisostearate, (2-n-butoxycarbonylbenzoyloxy) tributoxy. Examples include titanium, isopropyl titanium triisostearate, di-n-butoxy bis (triethanolaminato) titanium, tetrakis (2-ethylhexyloxy) titanium, di-i-propoxy bis (acetylacetonato) titanium. As silicone, dimethyl silicone oil, methylphenyl silicone oil, methyl hydrogen silicone oil, cyclic dimethyl silicone oil, aralkyl-modified silicone oil, long-chain alkyl-modified silicone oil, higher fatty acid-modified silicone oil, and wax are polymerized olefins or And polyolefins which are thermally decomposed and further modified by oxidation or maleic acid, sulfonic acid, carboxylic acid, rosin acid and the like. Examples of the resin include those obtained by modifying polyolefin with maleic acid, sulfonic acid, carboxylic acid, rosin acid and the like.

In preparing the decorative sheet of crystalline polypropylene resin composition of the present invention, the use of a dispersing agent encapsulating vesicles encasing an dispersant Therefore vesicles supercritical reverse phase evaporation method is particularly important. A vesicle is a general term for vesicles (capsules) having a membrane structure closed in a spherical shell and containing a liquid phase inside. In particular, vesicles whose outer membrane is composed of biological lipids such as phospholipids are liposomes. Called. Such dispersing agent encapsulating vesicles vesicles of state is extremely excellent dispersibility, upon kneading the dispersing agent encapsulating vesicles, inorganic filler and the crystalline polypropylene resin, the dispersing agent in these mixtures Since the encapsulated vesicles are uniformly dispersed without agglomeration, the dispersant-encapsulated vesicles also enter between the particles of the inorganic filler to prevent the inorganic filler from aggregating, and the inorganic filler is added to the crystalline polypropylene resin. It is possible to disperse uniformly.

  Here, the supercritical reverse phase evaporation method has been proposed by the present inventors, such as Table 02/032564, JP2003-119120A, JP2005-298407A, and JP2008-063274A. It can be carried out using the supercritical reverse phase evaporation method and apparatus disclosed in the publication (hereinafter referred to as “supercritical reverse phase evaporation method publications”).

  Specifically, the supercritical reverse phase evaporation method is a mixture in which a substance that forms the outer membrane of a vesicle is uniformly dissolved in carbon dioxide under supercritical state or temperature or pressure conditions above the critical point. In this method, an aqueous phase containing a dispersant as a water-soluble or hydrophilic encapsulating substance is added to obtain a capsule-like vesicle encapsulating the dispersing agent as an encapsulating substance in a single outer membrane. The carbon dioxide in the supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher. Carbon dioxide under pressure means carbon dioxide under a condition where only the critical temperature or the critical pressure exceeds the critical condition. By this method, a single-layer lamella vesicle having a diameter of 50 to 800 nm can be obtained.

  The phospholipids that form the outer membrane include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, etc. Examples thereof include sphingophospholipids such as lipids, sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

  Other substances that form the outer membrane include nonionic surfactants and dispersants such as a mixture of this with cholesterols or triacylglycerols. Among these, nonionic surfactants include polyglycerin ether, dialkyl glycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene. -One or two of polyoxyethylene copolymer, polybutadiene-poly-2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. More than seeds can be used. As cholesterols, cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate or cholecalciferol can be used. By appropriately selecting from the above substances and using them, for example, by forming a non-water-soluble inclusion in a vesicle wrapped with a water-soluble dispersant, the inclusion that is not water-soluble in a water-soluble solvent or the like can be uniformly formed. Can be dispersed.

  In particular, in the decorative sheet of the present invention, it is important that the vesicle is a liposome having an outer membrane made of phospholipid.

  Below, the specific example of a structure of the decorative sheet provided with the layer which consists of a crystalline polypropylene resin composition in this invention is demonstrated in detail according to figures.

  FIG. 1 shows a specific embodiment of a decorative sheet 1 according to the present invention. From the side facing a base material B such as a wooden board, an inorganic board or a metal plate to which the decorative sheet 1 is bonded, a raw fabric layer 2, a pattern The pattern layer 3, the adhesive layer 7 (adhesive resin layer, heat-sensitive adhesive layer, anchor coat layer, dry laminate adhesive layer), transparent resin layer 4, and top coat layer 5 are laminated. Moreover, in order to improve designability, you may provide the embossed pattern 4a suitably in the transparent resin layer 4 surface by the side of the topcoat layer 5. FIG. In addition, if there is a problem in the adhesiveness between the raw fabric layer 2 and the base material B, the primer layer 6 may be appropriately provided between the raw fabric layer 2 and the base material B.

  As the raw fabric layer 2, paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic and other synthetic resins, Alternatively, foams of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber It can be arbitrarily selected from rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, metal foil such as aluminum, iron, gold and silver.

  As the pattern layer 3, nitrified cotton as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, or the like may be appropriately selected and used. it can. These may be water-based, solvent-based, or emulsion-type, and may be one-component type or two-component type using a curing agent. Furthermore, you may use the method of hardening ink by irradiation of an ultraviolet-ray, an electron beam, etc. Among them, the most common method is to use urethane-based ink and is a method of curing with isocyanate. In addition to these binders, colorants such as pigments and dyes contained in ordinary inks, extender pigments, solvents, various additives, and the like are added. Examples of highly versatile pigments include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and mica. Using these pigments, the design of the surface of the raw fabric layer 2 by direct metal gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, negative jet printing, and ink application and sputtering. Is given.

As the transparent resin layer 4, it is preferable to use a highly crystalline homopolypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more. In the decorative sheet 1 of the present invention, 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 and a supercritical reverse phase evaporation with respect to the highly crystalline homopolypropylene resin. It is important that a dispersant-encapsulating vesicle in which a dispersant is encapsulated in a vesicle is added by the method. Here, the isotactic pentat fraction means that the resin composition constituting the transparent resin layer is predetermined by a 13C-NMR measurement method (nuclear magnetic resonance measurement method) using carbon C (nuclide) having a mass of 13. It is calculated from a numerical value (electromagnetic wave absorptivity) obtained by resonating at the resonance frequency, and defines the atomic arrangement, electronic structure, and molecular microstructure in the resin composition. The pentat fraction of the polypropylene resin is the ratio of five propylene units determined by 13C-NMR, and is used as a measure of crystallinity or stereoregularity. This is one of the important factors that mainly determine the scratch resistance of the surface. Basically, the higher the pentat fraction, the higher the crystallinity of the sheet. Therefore, the transparent resin layer 4 having excellent scratch resistance and can do.

  In addition, various additives such as a heat stabilizer, a flame retardant, an ultraviolet absorber, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjusting agent are added to the transparent resin layer 4 as necessary. An agent can also be added. Phenol, sulfur, phosphorus, hydrazine, etc. as heat stabilizers, aluminum hydroxide, magnesium hydroxide, etc. as flame retardants, benzotriazole, benzoate, benzophenone, triazine as UV absorbers As a light stabilizer such as a system, a hindered amine system is generally added in any combination.

  The transparent resin layer 4 may be provided with an embossed pattern 4a. The embossed pattern 4a is an embossed plate having a concavo-convex pattern by applying heat and pressure to the transparent resin sheet 4 formed as a film. It can be formed using a method of applying an embossed pattern by using a method or a method of applying an embossed pattern simultaneously with cooling using a cooling roll having a concavo-convex pattern when forming a film using an extruder. Further, the embossed pattern 4a can be further improved in design by embedding ink or the like.

  The top coat layer 5 is not particularly defined, but is suitably selected from polyurethane, acrylic, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like. You can choose. The form may be any of aqueous, emulsion, and solvent systems, and the curing may be a one-component type or a two-component type using a curing agent. Of these, a urethane-based topcoat utilizing an isocyanate reaction is desirable from the viewpoints of workability, cost, cohesion of the resin itself, and the like. Isocyanates include tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), hexamethylene diisocyanate (HMDI), metadiisocyanate (MDI), lysine diisocyanate (LDI), isophorodiisocyanate (IPDI), methylhexane diisocyanate (HTDI). , Methylcyclohexanone diisocyanate (HXDI), trimethylhexamethylene diisocyanate (TMDI) and the like.

  In order to further improve the hardness of the surface of the decorative sheet 1, it is possible to use a resin that is cured by irradiation with ultraviolet rays or electron beams as the top coat layer 5. In order to further improve the weather resistance, an ultraviolet absorber and a light stabilizer may be added as appropriate. And in order to provide various functions, addition of functional additives, such as an antibacterial material and a mold prevention material, can also be performed arbitrarily. Furthermore, in order to improve the design of the surface, alumina, silica, silicon nitride, silicon carbide, glass beads, etc. can be added for adjusting the gloss or further imparting wear resistance. .

  As the primer layer 6, basically, the same material as that of the pattern layer 3 can be used. However, in consideration of performing winding in a web shape because it is applied to the back surface of the decorative sheet 1, blocking is avoided. In order to enhance the adhesion with the adhesive, an inorganic filler such as silica, alumina, magnesia, titanium oxide, barium sulfate, or the like may be added.

  Examples of the adhesive layer 7 include acrylics, polyesters, and polyurethanes. In general, it is preferable to use a two-component effect type urethane system that reacts with a polyol using an isocyanate. Lamination can be performed by heat lamination, extrusion lamination, dry lamination, or the like.

  Further, when it is desired to provide concealment to the decorative sheet 1, concealment is provided by using the original fabric layer 2 as a colored sheet, or the original fabric layer 2 remains a transparent sheet and is separately provided with an opaque concealment layer. By providing 8, concealability can be imparted.

  The hiding layer 8 can be basically composed of the same material as the picture pattern layer 3, but is intended to have hiding properties, so that the pigment is an opaque pigment, titanium oxide, iron oxide, etc. Is preferably used. It is also possible to add metals such as gold, silver, copper, and aluminum in order to improve concealment. In general, flaky aluminum is often added.

  In forming the decorative sheet 1 of the present invention, the laminating method is not particularly limited, and it is appropriately selected from generally used methods such as a method using hot pressure, an extrusion laminating method and a dry laminating method. be able to. In the case of forming the embossed pattern 4a, the embossed pattern 4a can be formed simultaneously with the extrusion laminating method by providing the embossed pattern 4a by heat pressure after laminating by the laminating method, or by providing an uneven pattern on the cooling roll. .

  In the decorative sheet 1 of this embodiment, the raw fabric layer 2 is 20 μm to 150 μm in consideration of printing workability, cost, etc., the adhesive layer 7 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, and the top coat layer 5. Is preferably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 45 μm to 450 μm.

As described above, in the decorative sheet 1 of the present invention, the refractive index of light having a wavelength of 550 nm is 1 with respect to 100 parts by weight of the crystalline polypropylene resin with respect to the transparent resin layer 4 as a layer made of the crystalline polypropylene resin composition. .46～1.52 of an inorganic filler relative to crystalline polypropylene resin composition filled in a high proportion of 5 to 200 parts by weight, more supercritical reverse phase evaporation method thus dispersing agent obtained by enclosing a dispersant vesicles Since the inclusion vesicles are added, in the crystalline polypropylene resin, due to the high dispersibility of the dispersant inclusion vesicles , the dispersant and the inorganic filler are uniformly dispersed and mixed, resulting in the aggregation of the inorganic filler. The whitening of crystalline polypropylene resin is suppressed and the design is excellent, and the addition of hard inorganic filler makes it scratch resistant. The can be a decorative sheet 1.

Further, in the crystalline polypropylene resin, the dispersant- containing vesicle and the inorganic filler are uniformly dispersed and mixed due to the high dispersibility of the dispersant-containing vesicle , so that at the interface between the crystalline polypropylene resin and the inorganic filler. Since excellent adhesive strength is realized and the falling off of the inorganic filler can be suppressed even in a use situation involving friction, it is possible to prevent the occurrence of abrasive wear caused by the dropped inorganic filler particles. As a result, it is possible to provide the decorative sheet 1 with less design deterioration due to wear and scratches even during long-term use.

  Below, the specific Example of the decorative sheet 1 of this invention is described.

  First, a specific procedure for preparing a vesicle will be described. The vesicle was prepared by sealing 100 parts by weight of methanol, 70 parts by weight of a dispersant and 5 parts by weight of phosphatidylcholine as a phospholipid in a high-pressure stainless steel container maintained at 60 ° C., and the pressure in the container was 20 MPa. Inject carbon dioxide into a supercritical state, inject 100 parts by weight of ion-exchanged water with vigorous stirring and mixing, stir and mix for 15 minutes while maintaining temperature and pressure, and discharge carbon dioxide to atmospheric pressure. The dispersion liposome having an outer membrane made of phospholipid was obtained by the supercritical reverse phase evaporation method.

<Example>
In Example 1, a highly crystalline homopolypropylene resin having an isotactic pentat fraction of 97.8% as a crystalline polypropylene resin, a dispersant liposome vesicled with 12-hydroxy magnesium stearate as a dispersant, and an inorganic filler A decorative sheet 1 having a transparent resin layer 4 to which 50 parts by weight of glass beads having a refractive index of 1.49 was added was obtained.

  Specifically, a highly crystallized homopolymer having an isotactic pentad fraction of 97.8%, an MFR (melt flow rate) of 15 g / 10 min (230 ° C.), and a molecular weight distribution MWD (Mw / Mn) of 2.3. To 100 parts by weight of polypropylene resin, 0.05 part by weight of hindered phenol antioxidant (Irganox 1010: manufactured by BASF) and 0.2 weight of benzotriazole UV absorber (Tinuvin 328: manufactured by BASF) 0.2 parts by weight of a hindered amine light stabilizer (Kimasorb 944: manufactured by BASF), 0.1 part by weight of the above-described dispersant liposome, and 50 parts by weight of glass beads having a particle size of 5 μm and a refractive index of 1.49 A transparent resin sheet 4 made of a highly crystalline polypropylene having a thickness of 80 μm and used as a transparent resin layer 4 is extruded using a melt extruder. Was formed. Subsequently, both surfaces of the formed transparent resin sheet were subjected to corona treatment so that the surface wettability was 40 dyn / cm or more. In addition, the haze value of the crystalline polypropylene resin of the formed transparent resin sheet 4 was 7.0%.

On the other hand, 15 parts by weight of iron oxide pigment was added to 100 parts by weight of high-density polyethylene (manufactured by Prime Polymer: Hi-Zex 5305E MFR = 0.8 g / 10 min (190 ° C.)), and melt-kneaded using a mesh type twin-screw extruder. Thereafter, pelletization was performed by a strand cutting method to obtain pellets of a crystalline polypropylene resin composition. A raw fabric sheet 2 as a raw fabric layer 2 having a film thickness of 70 μm having a concealing property was formed by a calender molding method using pellets of the crystalline polypropylene resin composition. A pattern printing layer 3 is formed on one surface of the original fabric sheet 2 using a two-component curable urethane ink (V180: manufactured by Toyo Ink Manufacturing Co., Ltd.). Primer layer 6 was formed by applying a primer coat to the other surface. Thereafter, the transparent resin layer 4 made of the above-mentioned transparent resin sheet 4 is applied to one side of the original sheet 2 on which the pattern printing layer 3 is formed, as an adhesive for dry lamination (Takelac A540: manufactured by Mitsui Chemicals, Inc.). And bonded together by the dry laminating method through the adhesive layer 7 with a coating amount of 2 g / m 2). Next, the embossed pattern 4a is applied to the upper surface of the transparent resin layer 4 of the laminated sheet by using an embossing die roll, and then a two-component curable urethane topcoat (on the surface of the embossed pattern 4a). W184 (manufactured by DIC Graphics Co., Ltd.) was applied at a coating amount of 3 g / m 2 to form the topcoat layer 5 to obtain a decorative sheet 1 having a total thickness of 154 μm shown in FIG .

<Comparative Example 1>
In the comparative example 1, it was set as the decorative sheet 1 which added 50 weight part of glass beads of refractive index 1.60 as an inorganic filler. About another structure, it is the same as that of an Example. In addition, the haze value of the crystalline polypropylene resin of the formed transparent resin sheet 4 was 18.3%.

<Comparative example 2>
In the comparative example 2, it was set as the decorative sheet 1 which added 250 weight part of glass beads of refractive index 1.49 as an inorganic filler. About another structure, it is the same as that of an Example.

<Comparative Example 3>
In Comparative Example 3, a decorative sheet 1 to which 12-hydroxy magnesium stearate as a non-vesicle dispersant was added was used. About another structure, it is the same as that of an Example.

<Comparative example 4>
In Comparative Example 4, the decorative sheet 1 was prepared by adding 50 parts by weight of calcium carbonate having a particle size of 5 μm and a refractive index of 1.58 as an inorganic filler. About another structure, it is the same as that of an Example.

<Comparative Example 5>
In Comparative Example 5, the decorative sheet 1 was prepared by adding a dispersant liposome obtained by vesicleizing sodium dodecyl sulfate as a dispersant. About another structure, it is the same as that of an Example.

<Comparative Example 6>
In Comparative Example 6, the decorative sheet 1 was formed using a homopolypropylene resin having an isotactic pentat fraction of 90% as the crystalline polypropylene resin. About another structure, it is the same as that of an Example.

  After each decorative sheet obtained in the above Examples and Comparative Examples 1 to 6 is bonded to a wooden base material using a urethane-based adhesive, the pencil hardness test specifies scratch resistance and JAS special plywood. An evaluation test was performed in which wear resistance and visual design were judged by the wear A test (Taber abrasion). Each test method is briefly described below. The obtained results are shown in Table 1.

<Pencil hardness test>
Using pencils of 2B, B, HB, F, H, 2H, 3H, fix the pencil angle to the decorative sheet at 45 ± 1 °, and slide the pencil with a load of 1 kg. It is determined whether or not a flaw is formed on the decorative sheet (based on the old JIS standard JISK5400).

<Abrasion A test>
A decorative sheet is attached to a rotating horizontal disk, and a load of 0.5 kg is applied to each of the pair of friction wheels to which the abrasive paper of S-42 is attached. Judgment is made as to whether or not the rotation speed of the horizontal disk can withstand without being worn.

<Designability test>
The transparency of the transparent layer composed of the top coat layer 5 and the transparent resin layer 4 is visually confirmed to determine whether whitening is observed.

  As a result of carrying out each evaluation test, as shown in Table 1, in the examples, all evaluation items of scratch resistance, wear resistance, and designability were very excellent. On the other hand, in Comparative Example 1, white turbidity was observed in the transparent resin sheet 4. This is presumably because the refractive index of the added glass beads and crystalline polypropylene was poorly compatible, and light was scattered by the glass beads. In Comparative Example 2, although scratch resistance and design properties were slightly inferior, the abrasion resistance was particularly inferior. This is presumably because the glass beads were dropped off due to an excessive amount of glass beads added and abrasive wear occurred. In Comparative Example 3, although it was excellent in scratch resistance and design properties, it was inferior in wear resistance. This is presumably because the dispersion was not vesicled and secondary aggregation occurred in the dispersant and the glass beads, causing the glass beads to fall off and causing abrasive wear. In Comparative Example 4, a general decrease in physical properties was observed. This is a decrease in scratch resistance and wear resistance due to the low Mohs hardness of calcium carbonate. It is considered that the deterioration of the design property due to the difference in the refractive index between crystalline polypropylene and calcium carbonate is the cause. In Comparative Example 5, although the scratch resistance and the design property were very excellent, the wear resistance was inferior. This is probably because the compatibility between the resin and the dispersant was poor, and sufficient wear strength was not obtained at the interface between the crystalline polypropylene and the glass beads, causing the glass beads to fall off and causing abrasive wear. It is done. In Comparative Example 6, although the wear resistance and the design properties were very excellent, the scratch resistance was poor. This is thought to be because the hardness of the crystalline polypropylene resin was low and inferior to scratches.

  From the above results, the decorative sheet 1 of the present invention in Examples is a decorative sheet having superior scratch resistance, abrasion resistance, and design compared to the decorative sheets 1 of Comparative Examples 1-6. It became clear.

The decorative sheet 1 and the manufacturing method of the decorative sheet 1 of the present invention are not limited to the above-described embodiments and examples, and various modifications are possible within a range that does not impair the features of the invention.

DESCRIPTION OF SYMBOLS 1 Makeup sheet 2 Original fabric layer 3 Picture pattern layer 4 Transparent resin layer 4a Embossed pattern 5 Top coat layer 6 Primer layer 7 Adhesive layer 8 Concealment layer B Base material

Claims (5)

A decorative sheet comprising a plurality of resin layers,
Among the resin layers, at least one layer on the surface side is supercritically reversed with 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 of light having a wavelength of 550 nm with respect to 100 parts by weight of the crystalline polypropylene resin. A crystal in which a vesicle is added with a dispersant-encapsulating vesicle containing 12-hydroxymagnesium stearate, a silane coupling agent, a titanate coupling agent, a silicone, wax, or a modified resin encapsulated by a phase evaporation method. Formed as a layer made of a conductive polypropylene resin composition,
One of the resin layers on the back side from the one on the front side is an opaque concealing layer containing a flaky metal made of aluminum as a flaky shape . A decorative sheet comprising a plurality of resin layers,
Among the resin layers, at least one layer on the front side than the layer on the backmost side is an inorganic filler 5 to 200 having a refractive index of 1.46 to 1.52 for light having a wavelength of 550 nm with respect to 100 parts by weight of the crystalline polypropylene resin. It is formed as a layer composed of a crystalline polypropylene resin composition in which a dispersant and a dispersant-encapsulating vesicle in which a dispersant is encapsulated by a supercritical reverse phase evaporation method is added,
The vesicle is a liposome having an outer membrane composed of a mixture of a phospholipid and a nonionic surfactant or a mixture of a phospholipid and a nonionic surfactant and at least one of cholesterols and triacylglycerol,
The dispersant is any one of 12-hydroxy magnesium stearate, silane coupling agent, titanate coupling agent, silicone, wax, and modified resin .
The crystalline polypropylene resin is a highly crystalline homopolypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more. A decorative sheet comprising a plurality of resin layers used by being bonded to a base material,
The raw fabric layer, the transparent resin layer, and the topcoat layer contained in the resin layer are positioned in this order, and the transparent resin layer has a refractive index of 1 at a wavelength of 550 nm with respect to 100 parts by weight of the crystalline polypropylene resin. It is formed as a layer comprising a crystalline polypropylene resin composition in which 5 to 200 parts by weight of an inorganic filler of 46 to 1.52 and a dispersant-encapsulating vesicle in which a vesicle is encapsulated by a supercritical reverse phase evaporation method are added. And
The dispersant is any one of 12-hydroxy magnesium stearate, silane coupling agent, titanate coupling agent, silicone, wax, and modified resin .
A decorative sheet, wherein the crystalline polypropylene resin is a highly crystalline homopolypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more. A method for producing a decorative sheet comprising a plurality of resin layers,
Among the resin layers, at least one layer on the surface side is supercritically reversed with 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 for light having a wavelength of 550 nm with respect to 100 parts by weight of the crystalline polypropylene resin. A crystal in which a vesicle is added with a dispersant-encapsulating vesicle containing 12-hydroxymagnesium stearate, a silane coupling agent, a titanate coupling agent, a silicone, wax, or a modified resin encapsulated by a phase evaporation method. Formed as a layer composed of a conductive polypropylene resin composition,
A concealing layer that is one layer on the back side from one layer on the front side of the resin layer is formed by adding a flake-like metal in which aluminum is flake-like into the resin. A method for producing a decorative sheet. A method for producing a decorative sheet comprising a plurality of resin layers,
At least one of the resin layers is composed of 5 to 200 parts by weight of an inorganic filler having a refractive index of 1.46 to 1.52 of light having a wavelength of 550 nm with respect to 100 parts by weight of the crystalline polypropylene resin, and a supercritical reverse phase evaporation method. Formed as a layer composed of a crystalline polypropylene resin composition in which a dispersant-encapsulating vesicle in which a dispersant is encapsulated is added, and the vesicle is a mixture of a phospholipid and a nonionic surfactant or a phospholipid and a nonion A liposome having an outer membrane comprising a mixture of a surfactant and at least one of cholesterols and triacylglycerol, wherein the dispersant is 12-hydroxy magnesium stearate, silane coupling agent, titanate coupling agent, silicone , waxes, modifying resins, is any one of, Serial crystalline polypropylene resin, the decorative sheet manufacturing method of which is a highly crystalline homopolymer polypropylene with isotactic pen Tat fraction (mmmm fraction) of 95% or more.