JP2016190466A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet to which sufficient flame resistance is imparted by adding a flame-resistance agent to a transparent resin layer without losing transparency.SOLUTION: In a decorative sheet 1 including a raw fabric layer 2 to which a pattern printing is applied, and a transparent resin layer 4, the transparent resin layer 4 comprises a thermoplastic resin composition in which a flame-resistance agent included in a vesicle is blended with a polyolefin resin by a supercritical reverse-phase evaporation method.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet used for a building interior material, a surface of a fitting, a surface material of home appliances, and is used as a decorative sheet by being bonded to a wooden board, an inorganic board, a metal plate, or the like, for example. In particular, the present invention relates to a decorative sheet suitable for applications in which the material is required to be nonflammable.

  Conventionally, decorative sheets made of polyvinyl chloride resin have been used as the main material of decorative sheets due to their excellent processing suitability and low flammability, but there is a problem as toxic gases are generated during incineration after disposal. A decorative sheet using a polyolefin resin instead of the polyvinyl chloride resin has been proposed.

  However, the decorative sheet using the polyolefin resin is one of highly flammable resins, although the generation of toxic gas at the time of incineration is suppressed by not using the vinyl chloride resin. It was difficult to meet the technical standards of incombustible materials.

  As methods for improving the flammability of polyolefin resin and imparting incombustibility, in Patent Documents 1 to 3, layered silicate, metal hydroxide, bromine flame retardant, phosphorus flame retardant, chlorine It is disclosed that a flame retardant such as a system flame retardant, glass fiber and / or a melamine derivative is blended.

JP 2003-311901 A JP 2004-149664 A JP 2004-160818 A

  In order to impart nonflammability to a highly combustible polyolefin resin, it is necessary to add a large amount of flame retardant. However, in a decorative sheet provided with a transparent resin layer on the surface side in order to improve the surface hardness and scratch resistance of the original layer on which pattern printing has been applied, the pattern applied to the lower original layer Since it is difficult to add a flame retardant to the transparent resin layer in order to ensure the visibility of printing, most of them have added a flame retardant to the raw fabric layer.

  However, if most of the resin material of the original fabric layer is replaced with a flame retardant, the mechanical properties of the original fabric layer are significantly lowered, and the manufacturing suitability for pattern printing and lamination of the resin layer is lost. There are problems such as inability to perform easily and inferior post-processability such as V-groove bending.

  Therefore, an object of the present invention is to provide a decorative sheet imparted with sufficient incombustibility by adding a flame retardant to the transparent resin layer without losing transparency.

  In order to achieve the above object, the decorative sheet according to the first aspect of the present invention is a decorative sheet comprising at least a raw fabric layer on which pattern printing has been applied and a transparent resin layer, wherein the transparent resin layer comprises It is characterized by comprising a thermoplastic resin composition in which a flame retardant prepared by supercritical reverse phase evaporation is added to a polyolefin-based resin.

  In the decorative sheet according to the first aspect of the present invention, a transparent resin is obtained by using a crude thermoplastic resin composition in which a flame retardant vesicled by a supercritical reverse phase evaporation method is blended with a polyolefin resin. By forming the layer, it is possible to realize a decorative sheet having excellent transparency and mechanical strength appropriate for post-processing resistance and further having flame retardancy.

  The decorative sheet according to the second aspect of the present invention is characterized in that the flame retardant includes at least an inorganic flame retardant, and the inorganic flame retardant is a metal hydroxide.

  In such a decorative sheet according to the second aspect of the present invention, it is possible to provide a decorative sheet that is free from the generation of toxic gases during the incineration process and has environmental suitability.

  The decorative sheet according to the third aspect of the present invention is characterized in that the metal hydroxide is magnesium hydroxide or aluminum hydroxide.

  Such a decorative sheet according to the third aspect of the present invention has non-flammability by using magnesium hydroxide or aluminum hydroxide, which is low in cost and excellent in processability, easily and while suppressing an increase in cost. A decorative sheet can be provided.

  The decorative sheet of the fourth aspect of the present invention is characterized in that the vesicle is a liposome composed of an outer membrane of phospholipid.

  In such a decorative sheet of the fourth aspect of the present invention, the outer membrane of the vesicle is composed of phospholipid, thereby improving compatibility with the polyolefin-based resin and further improving the dispersibility of the flame retardant. It is possible to increase.

  The decorative sheet according to the fifth aspect of the present invention is characterized in that the transparent resin layer has a tensile elastic modulus of 500 MPa or more and 2000 MPa or less and a tensile elongation at break of 200% or more.

  In such a decorative sheet according to the fifth aspect of the present invention, it has manufacturing suitability such as printing and lamination with other resin layers, and has excellent post-processing resistance such as V-cut bending. It is possible to provide a decorative sheet.

  The decorative sheet according to the sixth aspect of the present invention is characterized in that the polyolefin resin is a highly crystalline polypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more.

  In such a decorative sheet according to the sixth aspect of the present invention, it is possible to provide a decorative sheet having excellent scratch resistance.

  The decorative sheet according to the seventh aspect of the present invention is the building standard method construction example No. 108 2 in the exothermic test by a cone calorimeter tester based on ISO5660-1 in a state of being bonded to a nonflammable base material. It is a nonflammable material that satisfies the requirements described in No. 1 and No. 2.

  In such a decorative sheet according to the seventh aspect of the present invention, a decorative sheet excellent in incombustibility can be provided.

  ADVANTAGE OF THE INVENTION According to this invention, even when a flame retardant is mix | blended with a transparent resin layer, it becomes possible to provide the decorative sheet which maintained the outstanding transparency and was equipped with sufficient nonflammability.

  In addition, according to the decorative sheet of the present invention, since a flame retardant can be added to the resin layer other than the raw fabric layer, it is possible to maintain sufficient mechanical properties as a decorative sheet, and the A decorative sheet excellent in post-processability and excellent in nonflammability can be provided.

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

  The decorative sheet of the present invention includes at least a raw fabric layer on which pattern printing has been performed and a transparent resin layer, and the transparent resin layer is vesicled by a supercritical reverse phase evaporation method with respect to a polyolefin resin. It is important to consist of a thermoplastic resin composition containing a flame retardant.

  The flame retardant in the present invention is made of a non-flammable material that is difficult to burn, and reduces the flammability of the resin sheet by blending with the resin sheet. Specifically, phosphorus compounds, halogen compounds, alkaline earth oxides, phosphorus / nitrogen compounds, phosphorus / halogen compounds, halogen / phosphorus / nitrogen compounds, sulfur / nitrogen compounds, phosphorus / sulfur / nitrogen・ One or a mixture of two or more of halogen compounds, halogen / sulfur / nitrogen / boron compounds, complex salts produced in phosphorus / nitrogen-scattered children, halogen / polyvalent metal oxides, and other inorganic compounds In the present invention, it is important to contain at least an inorganic flame retardant.

  Inorganic compounds include zirconium compounds such as calcium carbonate, antimony trioxide, antimony soda, zircon silicide, zircon oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, borax, zinc borate, molybdenum trioxide, Complex inorganic flame retardants such as antimony molybdate and aluminum hydroxide complex, antimony trioxide and silica complex, antimony trioxide and zinc white complex, zirconium silicate, zirconium compound and antimony trioxide complex In particular, assuming application to industrial products, it is preferable to use magnesium hydroxide or aluminum hydroxide from the viewpoint of material cost because there are many grades such as particle size and surface treatment, and availability is easy. .

  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 substance that forms an outer film of a vesicle on carbon dioxide under supercritical conditions or temperature conditions above the critical point or carbon dioxide under pressure conditions above the critical point. In this method, an aqueous phase containing a flame retardant as a water-soluble or hydrophilic encapsulating substance is added to a uniformly dissolved mixture to form a capsule-like vesicle that encapsulates the encapsulating substance in a single layer. The supercritical carbon dioxide means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or more, and a temperature condition above the critical point. The lower carbon dioxide or carbon dioxide under pressure condition above the critical point means carbon dioxide under the condition that 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. Here, a vesicle refers to a vesicle having a membrane structure closed in a spherical shell shape and containing a liquid phase inside. The outer membrane containing a biological lipid such as phospholipid is called a liposome, and the outer membrane formed from other substances is called a vesicle.

  Phospholipids that form the outer membrane of vesicles include phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, etc. Glycerophospholipids, sphingomyelin, ceramide phosphorylethanolamine, sphingophospholipids such as ceramide phosphorylglycerol, and the like. Vesicles having an outer membrane made of these phospholipids are called liposomes.

  In addition, since the outer membrane of the vesicle only needs to contain at least biological lipids such as phospholipids, the outer membrane may be formed from a mixture of biological lipids and other substances as described below.

  Other substances that form the outer membrane of the vesicle include nonionic surfactants and mixtures of this with cholesterols or triacylglycerols. Among these, nonionic surfactants include polyglycerol ether, dialkyl glycerol, 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 the present invention, it is important that the outer membrane of the vesicle is a liposome formed from phospholipid. Thereby, compatibility with the polyolefin resin can be further improved, so that the flame retardant can be dispersed extremely uniformly in the polyolefin resin.

  In the thermoplastic resin composition of the present invention, when the flame retardant is blended in a vesicle state by the supercritical reverse phase evaporation method, the vesicle and the polyolefin resin are kneaded. In addition, since the vesicles are uniformly dispersed in the polyolefin resin without agglomeration, the original transparency of the polyolefin resin is not lost. Furthermore, since the deterioration of the mechanical properties of the polyolefin resin can be suppressed by uniformly dispersing the flame retardant, a decorative sheet excellent in post-processing resistance having mechanical strength that can withstand V-groove bending is obtained. be able to. When the vesicle is kneaded into the polyolefin resin, the film forming the outer shell of the vesicle is broken and is present in the polyolefin resin in a state where the flame retardant contained therein is exposed. .

  Examples of polyolefin resins include polypropylene, polyethylene, polybutene and the like, as well as alpha olefins (eg, propylene, 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 Or the like, or ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene・ Ethylene or α-olefin was copolymerized with other monomers such as butyl methacrylate copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, etc. Things.

  In order to improve the surface strength of the decorative sheet, it is preferable to use a highly crystalline polypropylene having an isotactic pentat fraction (mmmm fraction) of 95% or more. The isotactic pentat fraction means that the resin composition constituting the transparent resin layer is obtained at a predetermined resonance frequency by a 13C-NMR measurement method (nuclear magnetic resonance measurement method) using carbon C (nuclide) having a mass of 13. It is calculated from the numerical value (electromagnetic wave absorptivity) obtained by resonating with, 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, a transparent resin layer with excellent scratch resistance is obtained. be able to.

  It is important that the decorative sheet of the present invention has a tensile modulus of 500 MPa or more and 2000 MPa or less and a tensile elongation at break of 200% or more.

The tensile elongation at break is a value representing the elongation when the sample is pulled at a predetermined speed and broken, and the length of the sample before the test (L ₀ ) is subtracted from the length of the sample at the time of break (L). The value obtained by dividing the measured value by the length of the sample (L ₀ ) before the test is expressed as a percentage. The smaller the value, the worse the elongation, the poor printability such as the occurrence of breakage during printing, and the value is The larger the size, the better the printing properties. In addition to this, for example, the larger the value, the better the post-processing resistance such as V-cut bending.

Here, in the technical standard of the non-combustible material specified in the Building Standards Act Construction Ordinance, it is necessary to satisfy the following requirements in the exothermic test by the cone calorimeter tester based on ISO5660-1 (Building Standards Act) Construction Order Article 108-2 No. 1 and No. 2). In order for the decorative sheet of the present invention to be certified as a non-combustible material, the following requirements 1 to 3 are required in a heating time of 20 minutes by heating with radiant heat of 50 kW / m ^{2 in} a state of being bonded to a non-combustible base material. It is necessary to satisfy all.
1. 1. Total calorific value is 8 MJ / m ² or less 2. The maximum heat generation rate does not exceed 200 kW / m ² continuously for 10 seconds or more. No cracks or holes penetrating to the back side, which is harmful in terms of flameproofing, are generated. The incombustible base material can be selected from a gypsum board, a fiber-mixed calcium silicate board, or a galvanized steel sheet.

  And in the exothermic test by the cone calorimeter test machine based on ISO5660-1 in the state bonded together with the said nonflammable base material, the decorative sheet of the present invention is the construction order Article 108-2 No. 1 and The non-combustible material that satisfies both requirements described in No. 2 has been realized.

  Below, the Example of a structure of the decorative sheet provided with the transparent resin layer which consists of a thermoplastic resin composition in this invention is described in detail according to figures.

  FIG. 1 shows a specific configuration of the decorative sheet 1 of the present invention, which is composed of a plurality of resin layers. In the decorative sheet 1 of the present invention, from the side facing the base material B such as a wooden board, an inorganic board or a metal plate to which the decorative sheet 1 is bonded, an original fabric layer 2, a pattern pattern layer 3, an adhesive layer 7 (heat-sensitive adhesive layer, anchor coat layer, dry lamin adhesive layer), transparent resin layer 4 and top coat layer 5 are laminated. Moreover, in order to improve designability, you may provide the embossing pattern 4a suitably in the surface at the side of the topcoat layer 5 of the transparent resin layer 4. FIG.

  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.

  In addition, a sheet made of the same thermoplastic resin composition as the transparent resin layer 4 may be used for the raw fabric layer 2, and when an olefin resin is used as the raw fabric layer 2, the surface is inactive. Since it is often in a state, it is preferable to provide the primer layer 6 between the raw fabric layer 2 and the base material B. In addition, in order to improve the adhesion between the raw material layer 2 made of an olefin-based material and the base material B, corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment are performed on the front and back of the raw material layer 2. It is desirable to carry out a dichromic acid treatment.

  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.

  The pattern layer 3 is a pattern printing applied to the raw fabric layer 2 and is made of nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester or the like as a binder. It can be used by appropriately selecting from the modified products. 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. In addition to the ink application, the design can be applied by vapor deposition or sputtering of various metals.

  As the transparent resin layer 4, a thermoplastic resin composition is used in which a flame retardant prepared by the supercritical reverse phase evaporation method is mixed with the polyolefin resin as described above. In particular, the polyolefin resin can improve the scratch resistance of the surface by using a highly crystalline polypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more.

  In addition, various additives such as a heat stabilizer, 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. You can also As a heat stabilizer, phenol, sulfur, phosphorus, hydrazine, etc., as an ultraviolet absorber, benzotriazole, benzoate, benzophenone, triazine, etc., as a light stabilizer, hindered amine, etc. In general, they are added in any combination.

  The topcoat layer 5 may be a resin composition that plays a role of protecting the surface and adjusting gloss, and a thermosetting resin or a mixture of a thermosetting resin and a photocurable resin can be used. More specifically, it can be appropriately selected from polyurethane, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like. As the thermosetting resin, urethane-based resins using isocyanate are preferable 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 can be appropriately selected and used. However, in consideration of weather resistance, hexamethylene diisocyanate (HMDI) having a linear molecular structure is preferable. The form of the material is not particularly limited, such as aqueous, emulsion, solvent type. In addition to this, in order to improve the surface hardness, it is preferable to use a resin curable with active energy rays such as ultraviolet rays and electron beams. These resins can be used in combination with each other. For example, by using a hybrid type of a thermosetting resin and a photocurable resin, surface hardness can be improved, effective shrinkage can be suppressed, and a transparent resin layer can be used. 4 can be improved.

  Moreover, in order to further improve the hardness of the surface of the decorative sheet, 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 appropriately added. 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. .

  The adhesive layer 7 is desirably laminated as thin as possible in consideration of the heat quantity during the exothermic test. The adhesive is preferably one that has as little heat as possible during combustion, and is not particularly limited.

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

  The hiding layer 8 can be basically made of the same material as the pattern layer 3, but it is intended to maintain 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 the concealing property. 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 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 topcoat layer 5 is The thickness 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 250 μm. When the adhesive layer 7 is 1 μm or less, the adhesion required as a laminate cannot be obtained, and when it is 10 μm or more, there is a high possibility that the incombustible performance is inferior.

  As described above, in the decorative sheet 1 of the present invention, the thermoplastic resin composition in which the transparent resin layer 4 is blended with a flame retardant that is vesicled by a supercritical reverse phase evaporation method with respect to a polyolefin resin. Therefore, it is excellent in design without impairing the transparency of the polyolefin resin, and the proportion of the polyolefin resin is reduced by the amount filled with the flame retardant, thereby suppressing the amount of heat generated during combustion, It is possible to provide the decorative sheet 1 as the “non-combustible material” that satisfies the technical standards of the non-combustible material described in the Building Standard Law Construction Order.

  Furthermore, since the layer composed of the thermoplastic resin composition can be uniaxially stretched or biaxially stretched, the crystallinity can be improved and the mechanical strength can be further improved. A decorative sheet 1 can be provided.

<Preparation of flame retardant vesicles by supercritical reverse phase evaporation>
The vesicles of the present invention were prepared by the following method by the supercritical reverse phase evaporation method. 100 parts by weight of methanol, 162 parts by weight of magnesium hydroxide or aluminum hydroxide as a flame retardant, and 5 parts by weight of phosphatidylcholine as a substance forming the outer membrane of the vesicle are placed in a high-pressure stainless steel container kept at 60 ° C. and sealed. Then, after injecting carbon dioxide into a supercritical state so that the pressure becomes 20 MPa, 100 parts by weight of ion-exchanged water is injected with vigorous stirring and mixing. After stirring for 15 minutes while maintaining the temperature and pressure inside the container, the outside is made of a phospholipid containing magnesium hydroxide or aluminum hydroxide as a flame retardant by discharging carbon dioxide and returning to atmospheric pressure. A flame retardant liposome having a membrane was obtained.

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

<Example 1>
In Example 1, a film in which 25 parts by weight of a flame retardant liposome encapsulating magnesium hydroxide is blended with polypropylene resin is used as a transparent resin layer 4, and flame retardant with magnesium hydroxide encapsulating in polyethylene resin It is set as the multilayer decorative sheet 1 which laminated | stacked the raw fabric layer 2 which mix | blended 10 weight part of agent liposome and colored.

  Specifically, a highly crystallized homopolypropylene resin having a 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, A hindered phenol-based antioxidant (Irganox 1010: manufactured by Ciba Specialty Chemicals) is 500 PPM, a benzotriazole-based ultraviolet absorber (Tinuvin 328: manufactured by Ciba Specialty Chemicals) is 2000 PPM, and a hindered amine-based light stabilizer (Kimasorb 944). : Ciba Specialty Chemicals Co., Ltd.) 100 parts by weight of a polypropylene resin containing 2000 PPM and 25 parts by weight of a flame retardant liposome encapsulated in magnesium hydroxide are extruded using a melt extruder and used as a transparent resin layer 4 80μm high crystallinity To form a film of propylene made of a transparent resin sheet 4, followed by the wetting of the film formation by the transparent resin sheet 4 on both surfaces subjected to a corona treated surface of 40 dyn / cm or more. The haze value of the crystalline polypropylene resin of the formed transparent resin sheet 4 was 6.5% by controlling the cooling conditions during extrusion film formation.

On the other hand, 10 parts by weight of a flame retardant liposome encapsulating magnesium hydroxide is added to both 100 parts of high density polyethylene (manufactured by Prime Polymer: Hi-Zex 5305E MFR = 0.8 g / 10 min (190 ° C.)) and meshed. After melt-kneading using a mold biaxial extruder, pelletization was performed by a strand cut method to obtain a pellet of a thermoplastic resin composition. A raw fabric sheet 2 as a raw fabric layer 2 having a film thickness of 70 μm was formed by a calendar molding method using pellets of this thermoplastic 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 transparent resin sheet 4 is applied to the pattern print layer 3 side formed on one surface of the original fabric sheet 2 with an adhesive for dry lamination (Takelac A540: manufactured by Mitsui Chemicals, Inc .; Bonding was performed by a 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.

<Example 2>
Example 2 is a multilayer in which a polypropylene resin is laminated with 40 parts by weight of a flame retardant liposome encapsulating magnesium hydroxide as a transparent resin layer 4, and a film made of polyethylene resin is laminated as a raw fabric layer 2. The decorative sheet 1 is used.

  Specifically, a highly crystallized homopolypropylene resin having a 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, A hindered phenol-based antioxidant (Irganox 1010: manufactured by Ciba Specialty Chemicals) is 500 PPM, a benzotriazole-based ultraviolet absorber (Tinuvin 328: manufactured by Ciba Specialty Chemicals) is 2000 PPM, and a hindered amine-based light stabilizer (Kimasorb 944). : Ciba Specialty Chemicals Co., Ltd.) 100 parts by weight of polypropylene resin containing 2000 PPM and 40 parts by weight of flame retardant liposome encapsulated in magnesium hydroxide are extruded using a melt extruder and used as a transparent resin layer 1 80μm high crystallinity To form a film of propylene made of a transparent resin sheet 4, followed by the wetting of the film formation by the transparent resin sheet 4 on both surfaces subjected to a corona treated surface of 40 dyn / cm or more. The haze value of the crystalline polypropylene resin of the formed transparent resin sheet 4 was 8.4% by controlling the cooling conditions during extrusion film formation.

On the other hand, using a high-density polyethylene (manufactured by Prime Polymer: Hi-Zex 5305E MFR = 0.8 g / 10 min (190 ° C.)), an original fabric sheet 2 as an original fabric layer 2 having a thickness of 70 μm was formed by a calendar molding method. 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 transparent resin sheet 4 is applied to the pattern print layer 3 side of the original fabric sheet 2 with an adhesive for dry lamination (Takelac A540: manufactured by Mitsui Chemicals, applied amount: 2 g / m ² ). Bonding was carried out by the dry laminating method through the adhesive layer 7. 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>
Comparative Example 1 is a multilayer decorative sheet in which a polypropylene resin is laminated with 40 parts by weight of magnesium hydroxide that has not been vesicled as a transparent resin layer 4, and a film made of polyethylene resin is laminated as a raw fabric layer 2. Set to 1.

  Specifically, in Example 2, high crystallization with a 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. Homopolypropylene resin, hindered phenolic antioxidant (Irganox 1010: Ciba Specialty Chemicals) 500PPM, benzotriazole UV absorber (Tinuvin 328: Ciba Specialty Chemicals) 2000PPM, hindered amine light 100 parts by weight of a polypropylene resin containing 2000 PPM of a stabilizer (Kimasorb 944: manufactured by Ciba Specialty Chemicals) and 40 parts by weight of magnesium hydroxide that has not been vesicle-treated are extruded using a melt extruder, and a transparent resin layer Thickness used as 1 To form a film of high crystallinity polypropylene transparent resin sheet 4 0 .mu.m, followed by the wetting of the film formation by the transparent resin sheet 4 on both surfaces subjected to a corona treated surface of 40 dyn / cm or more. The haze value of the crystalline polypropylene resin of the formed transparent resin sheet 4 was 23.4%. With respect to the subsequent steps, the decorative sheet 1 was obtained by performing the same processing as in Example 2.

<Comparative example 2>
In Comparative Example 2, a film in which 40 parts by weight of magnesium hydroxide subjected to nano-treatment by a solid phase method is blended with a polypropylene resin as a transparent resin layer 4, and a film made of polyethylene resin as a raw fabric layer 2 is laminated. A multilayer decorative sheet 1 is obtained.

  Specifically, in Example 2, high crystallization with a 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. Homopolypropylene resin, hindered phenolic antioxidant (Irganox 1010: Ciba Specialty Chemicals) 500PPM, benzotriazole UV absorber (Tinuvin 328: Ciba Specialty Chemicals) 2000PPM, hindered amine light A stabilizer (Kimasorb 944: manufactured by Ciba Specialty Chemicals) 100 parts by weight of a polypropylene resin containing 2000 PPM and a mixture of isopropyl alcohol and magnesium hydroxide for 60 minutes using a 30 μm stabilized zirconia bead, 40 parts of magnesium hydroxide subjected to nano-treatment by the phase method are extruded using a melt extruder to form a transparent resin sheet 4 made of a highly crystalline polypropylene having a thickness of 80 μm and used as the transparent resin layer 1. Subsequently, both surfaces of the formed transparent resin sheet 4 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 17.3%. With respect to the subsequent steps, the decorative sheet 1 was obtained by performing the same processing as in Example 2.

<Comparative Example 3>
In Comparative Example 3, a film made of a polypropylene resin is used as a transparent resin layer 4, and a film in which 80 parts by weight of magnesium hydroxide that has been nanonized by a solid phase method is blended with a polyethylene resin is laminated as an original fabric layer 2. A multilayer decorative sheet 1 is obtained.

  Specifically, a highly crystallized homopolypropylene resin having a 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, A hindered phenolic antioxidant (Irganox 1010: manufactured by Ciba Specialty Chemicals) is 500 PPM, a benzotriazole ultraviolet absorber (Tinuvin 328: manufactured by Ciba Specialty Chemicals) is 2000 PPM, and a hindered amine light stabilizer (Kimasorb 944). : Ciba Specialty Chemicals Co., Ltd.) is used to extrude a polypropylene resin blended with 2000 PPM using a melt extruder to form a transparent resin sheet 4 made of a highly crystalline polypropylene having a thickness of 80 μm to be used as the transparent resin layer 4. A transparent resin sheet 4 of wetting of the surface subjected to a corona treatment on both sides was 40 dyn / cm or more. The haze value of the crystalline polypropylene resin of the formed transparent resin sheet 4 was 1.9% by controlling the cooling conditions during extrusion film formation.

On the other hand, 80 parts by weight of magnesium hydroxide nano-treated by the solid phase method used in Comparative Example 2 was added to 100 weights of high-density polyethylene (manufactured by Prime Polymer: Hi-Zex 5305E MFR = 0.8 g / 10 min (190 ° C.)). It added to both parts and the original fabric sheet 2 as the original fabric layer 2 with a film thickness of 70 μm was formed by a calender molding method. 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 transparent resin sheet 4 is applied to the pattern print layer 3 side formed on one surface of the original fabric sheet 2 with an adhesive for dry lamination (Takelac A540: manufactured by Mitsui Chemicals, Inc .; Bonding was performed by a 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.

  Table 1 shows the results of the exothermic test and the tensile test performed on the decorative sheets obtained in Examples 1 and 2 and Comparative Examples 1 to 3 using a cone calorimeter tester.

  From the results of each test, as shown in Table 1, makeup in Examples 1 and 2 employing a transparent resin layer 4 to which a flame retardant vesicles added by the supercritical reverse phase evaporation method of the present invention was added. It is clear that the sheet 1 is an “incombustible material” that has excellent transparency and good visibility of the pattern printed layer 3 and meets the technical standards of the incombustible material stipulated in the Building Ordinance of the Building Standards Act. It was. About the comparative example 1 which added the flame retardant which has not performed the nano-ized process, and the comparative example 2 which performed the nano-ized process by the solid-phase method, it is inferior to the transparency of the transparent resin layer 4, and is calculated | required as the decorative sheet 1. Designability cannot be obtained, and technical standards for incombustible materials are not met. On the other hand, Comparative Example 3 in which the flame retardant is excessively added to the raw fabric layer 2 satisfies the technology of non-combustible material, but is a result of high elastic modulus in tensile test and low elongation at break. However, it can be said that there is a problem in the post-processing resistance as the decorative sheet 1.

  On the other hand, the decorative sheet 1 in Examples 1 and 2 has a tensile elastic modulus of 500 MPa or more and 2000 MPa or less and a tensile breaking elongation of 200% or more in any decorative sheet 1, and is a machine required for a decorative sheet. It was revealed that the decorative sheet 1 was excellent in post-processing resistance and provided with sufficient strength.

  From the above results, the decorative sheet 1 in Examples 1 and 2 is a “non-combustible material” that meets the technical standards for non-combustible materials specified in the Building Ordinance of the Building Standards Act, and has transparency and resistance required for the decorative sheet. It can be said that it is the decorative sheet 1 excellent in post-processability.

  The decorative sheet 1 of the present invention is not limited to the above-described embodiments and examples, and various modifications can be made without departing from the characteristics of the invention.

DESCRIPTION OF SYMBOLS 1 Decorative 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 Concealing layer B Base material 8 Concealing layer B Base material

Claims (7)

A decorative sheet comprising at least a raw fabric layer and a transparent resin layer on which pattern printing has been performed,
A decorative sheet, wherein the transparent resin layer is made of a thermoplastic resin composition containing a flame retardant vesicled by a supercritical reverse phase evaporation method with respect to a polyolefin resin. The flame retardant includes at least an inorganic flame retardant,
The decorative sheet according to claim 1, wherein the inorganic flame retardant is a metal hydroxide.   The decorative sheet according to claim 1 or 2, wherein the metal hydroxide is magnesium hydroxide or aluminum hydroxide.   The decorative sheet according to any one of claims 1 to 3, wherein the vesicle is a liposome composed of a phospholipid outer membrane.   The makeup according to any one of claims 1 to 4, wherein the transparent resin layer has a tensile elastic modulus of 500 MPa or more and 2000 MPa or less, and a tensile elongation at break of 200% or more. Sheet.   The makeup according to any one of claims 1 to 5, wherein the polyolefin resin is a highly crystalline polypropylene resin having an isotactic pentat fraction (mmmm fraction) of 95% or more. Sheet.   In the exothermicity test by the cone calorimeter tester based on ISO5660-1 in a state of being bonded to a non-combustible base material, the requirements described in Building Standard Act Construction Example No. 108 No. 2 No. 1 and No. 2 are satisfied. The decorative sheet according to any one of claims 1 to 6, wherein the decorative sheet is a non-combustible material to be filled.

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