JP2023101532A - Decorative sheet and method for producing decorative sheet - Google Patents

Abstract

To provide a decorative sheet having a transparent resin layer excellent in high transparency and scratch resistance of a surface from a viewpoint of designability.SOLUTION: There is provided a decorative sheet comprising at least a concealing layer 2, a pattern printed layer 3, a transparent resin layer 4 and a top coat layer 5 in this order, or a decorative sheet comprising at least the concealing layer 2, the transparent resin layer 4 and the top coat layer 5 in this order, and having an embossed pattern 4a on a surface of a side of the top coat layer 5 of the transparent resin layer 4. A value of a peak intensity ratio x calculated from an absorption spectrum obtained in Fourier-type infrared spectroscopy of a transparent resin sheet as the transparent resin layer 4 by using a mathematical expression 1 is 0.65≤x≤0.85. The transparent resin sheet is formed by adding a nano-sized nucleating agent. The mathematical expression 1 is as follows.SELECTED DRAWING: Figure 1

Description

The present invention relates to a decorative sheet used for building materials used for the exterior and interior of buildings, the surface of fittings, the surface material of home appliances, and the like, and relates to a decorative sheet having a transparent resin layer and a method for producing the decorative sheet, the decorative sheet having a transparent resin layer in which the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier infrared spectroscopy is specified within a predetermined range.

In recent years, as shown in Patent Documents 1 to 5, many decorative sheets using olefin resins have been proposed as decorative sheets to replace polyvinyl chloride decorative sheets.

However, since these decorative sheets do not use vinyl chloride resin, the generation of toxic gases and the like during incineration is suppressed, but because they use general polypropylene sheets or soft polypropylene sheets, the scratch resistance of the surface is poor, and the scratch resistance is far inferior to that of conventional polyvinyl chloride decorative sheets.

In order to overcome these drawbacks, the present inventors proposed a decorative sheet having excellent surface scratch resistance and post-processability described in Patent Document 6. However, as the use of decorative sheets using such decorative sheets is expanding more and more, consumers' awareness of quality is becoming more and more sophisticated, so there is a demand for improvement in surface scratch resistance and resistance to post-processing such as V-groove bending.

In general, the mechanical properties of crystalline resins such as polypropylene can be changed by controlling the crystallinity, which is the ratio of the crystalline component to the amorphous component in the resin. Factors for controlling this crystallinity include material factors such as the molecular structure of the resin itself and the addition of a nucleating agent, and process factors such as molding conditions when processing the crystalline resin. In the present invention, the present inventors conducted intensive research focusing particularly on process factors, and by controlling the process factors, completed a decorative sheet comprising a resin sheet having a specified crystallinity range with excellent scratch resistance.

JP-A-2-128843 JP-A-4-083664 JP-A-6-001881 JP-A-6-198831 JP-A-9-328562 Japanese Patent No. 3772634

An object of the present invention is to provide a decorative sheet having a transparent resin layer with high transparency and excellent surface scratch resistance from the viewpoint of design, and a method for producing the decorative sheet.

In order to achieve the above object, the decorative sheet of the first aspect of the present invention is a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and an encapsulant on the surface of the transparent resin layer facing the topcoat layer. A decorative sheet having a boss pattern, wherein the value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65 ≤ x ≤ 0.85, and the transparent resin sheet is formed by adding a nano-sized nucleating agent. Here, in Equation 1, I997 represents the peak intensity value at wavenumber 997 cm ⁻¹ , I938 represents the peak intensity value at wavenumber 938 cm ⁻¹ , and I973 represents the peak intensity value at wavenumber 973 cm ⁻¹ .

With such a decorative sheet according to the first aspect of the present invention, it is possible to provide a decorative sheet having a transparent resin layer with high transparency and excellent scratch resistance. Further, according to the first aspect of the present invention, it is possible to provide a decorative sheet in which the masking layer can reliably maintain the masking property of the back side of the transparent layer and the degree of design freedom is increased by the transparent layer.

The decorative sheet of the second aspect of the present invention is a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and a decorative sheet comprising an embossed pattern on the surface of the transparent resin layer on the topcoat layer side. The sheet is characterized in that the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65≦x≦0.85, the transparent resin sheet is formed by adding a nucleating agent, and the nucleating agent is metal benzoate, metal pimelate, rosin metal salt, chitocridone, cyanine blue, or talc.

A decorative sheet according to a third aspect of the present invention is a decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer. In the sheet, the value of the peak intensity ratio x calculated from the absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65 ≤ x ≤ 0.85, and the transparent resin sheet is formed by adding nano-sized nucleating agent vesicles in which a nucleating agent is included in a vesicle having a single-layer outer film.

The decorative sheet according to the fourth aspect of the present invention is characterized in that the transparent resin sheet is formed by adding nano-sized nucleating agent vesicles encapsulating the nucleating agent to vesicles having a single-layer outer membrane.

The method for producing a decorative sheet of the present invention comprises at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or a decorative sheet comprising the concealing layer and 90 to 10% crystalline polypropylene resin.
A method for producing a decorative sheet comprising at least a transparent resin layer containing 0% by weight as a main component and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer, wherein a nano-sized nucleating agent vesicle containing a nucleating agent is added to a vesicle having a single-layer outer film by a supercritical reverse phase evaporation method to the crystalline polypropylene resin, and the absorption spectrum obtained from Fourier-type infrared spectroscopy is obtained from the above formula (1). The transparent resin sheet as the transparent resin layer is formed so that the value of the peak intensity ratio x calculated using the formula satisfies 0.65≦x≦0.85.
The method for producing a decorative sheet of the present invention comprises at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer, in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer on the topcoat layer side. In the production method, a nucleating agent vesicle containing a nucleating agent is added to a vesicle having a single-layer outer film by a supercritical reverse phase evaporation method to the crystalline polypropylene resin, and a transparent resin sheet is formed as the transparent resin layer so that the value of the peak intensity ratio x calculated using the above formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy is 0.65 ≤ x ≤ 0.85. It is characterized by being a melate metal salt, a rosin metal salt, chitocridone, cyanine blue, or talc.

According to the present invention, it is possible to provide a decorative sheet having a transparent resin layer with high transparency and excellent surface scratch resistance from the viewpoint of design.

Further, by adding a nano-sized nucleating agent to the transparent resin sheet, more specifically, a nucleating agent vesicle in which the nucleating agent is contained in a vesicle having a single-layer outer film, a decorative sheet having extremely high transparency can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS Sectional drawing which shows 1st Embodiment of the decorative sheet of this invention. Sectional drawing which shows 2nd Embodiment of the decorative sheet of this invention.

The decorative sheet of the present invention is a decorative sheet comprising at least a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and it is important that the value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier-type infrared spectroscopic measurement of the transparent resin sheet as the transparent resin layer is x≧0.65. Here, in Equation 1, I997 represents the peak intensity value at wavenumber 997 cm ⁻¹ , I938 represents the peak intensity value at wavenumber 938 cm ⁻¹ , and I973 represents the peak intensity value at wavenumber 973 cm ⁻¹ .

Moreover, it is particularly preferable that the peak intensity ratio x of the transparent resin sheet satisfies 0.65≦x≦0.85. By setting the peak intensity ratio x within the above range, it is possible to provide a decorative sheet having a transparent resin layer with extremely excellent scratch resistance.

In the decorative sheet of the present invention, the peak intensity value x of the transparent resin sheet is set within the above range by controlling the film forming conditions as a process factor. At this time, it is important that the transparent resin sheet has a thickness of 20 to 200 μm. If the thickness is less than the above range, the scratch resistance cannot be ensured. It is particularly preferable that the transparent resin layer is formed to have a thickness of 30 to 150 μm.

The film forming conditions for making the peak intensity ratio x within the above range may be those that can adjust the crystallinity of the polypropylene resin, and in the present invention, the resin temperature, cooling temperature, cooling time, etc. are adjusted to adjust the crystallinity. By controlling one or more of these conditions, the peak intensity ratio x can be within the above range.

More specifically, the resin temperature is the temperature at which the melted resin is discharged during film formation, and the peak intensity ratio x increases as the resin temperature increases (higher temperature). The cooling temperature is the temperature at which the discharged resin is cooled, and the peak intensity ratio x increases as the cooling temperature increases (higher temperature). As for the cooling time, the peak intensity ratio x increases by lengthening the passing time around the crystallization temperature (100 to 130° C.) of the polypropylene resin. By combining the above conditions, the crystallization and crystal size in the resin can be controlled, and the peak intensity ratio x can be adjusted appropriately.

Here, Fourier infrared spectroscopy will be described. First, infrared spectroscopy is a measurement method that obtains information on the chemical structure and state of a substance by measuring the infrared light absorbed by the substance, based on the principle that the amount of infrared light with a wavelength of 2.5 to 25 μm absorbed by the substance changes based on the vibration and rotational motion of the substance's molecules. A specific measurement method is to irradiate a substance with infrared light from a light source, generate an interference wave by synthesizing the divided transmitted light and reflected light, and measure the infrared spectrum by calculating the light intensity of each wavenumber component from the signal intensity of the interference wave. In particular, in the present invention, the interference wave was calculated using the Fourier transform method and measured by Fourier infrared spectrometry, which is a method for measuring the infrared spectrum. A graph in which the wavenumber obtained by the above method is plotted on the horizontal axis and the measured absorbance (or transmittance) is plotted on the vertical axis is called an infrared absorption spectrum (or infrared transmission spectrum), and a unique pattern is observed for each substance. At this time, the absorbance on the vertical axis varies in proportion to the concentration and thickness of the substance, and in the case of a crystalline resin, the value of the peak intensity at a predetermined wavenumber changes in proportion to the amount of the crystalline part or amorphous part, so it is possible to perform quantitative analysis from the height and area of the peak.

本発明においては、赤外吸光スペクトルの上述のような特性を利用して、前述の測定によって得られた吸光スペクトルにおけるポリプロピレンの透明樹脂シートの結晶質部の吸光度に該当する波数９９７ｃｍ ^－１のピーク強度と、透明樹脂シートの非晶質部の吸光度に該当する波数９７３ｃｍ ^－１のピーク強度との比、すなわちポリプロピレンの結晶化度を表すピーク強度比ｘを上記の数式１を用いて算出し、当該ピーク強度比ｘと透明樹脂シートの耐傷性との関係を明らかとし、所定の範囲内のピーク強度比ｘの透明樹脂シートを透明樹脂層に採用した耐傷性に優れる化粧シートを提供するものである。 The peak intensity at wavenumber 997 cm ⁻¹ and the peak intensity at wavenumber 973 cm ⁻¹ are each subjected to background correction using the peak intensity at wavenumber 938 cm ⁻¹ .

In addition, in the decorative sheet of the present invention, it is important to form a transparent resin sheet as a transparent resin layer by adding a nano-sized nucleating agent, and in particular, it is preferable to add a nucleating agent vesicle that is encapsulated in a vesicle having a single-layer outer membrane. By adding the nucleating agent vesicle to the polypropylene resin, the degree of crystallinity of the polypropylene resin can be improved, and a transparent resin sheet having extremely high transparency can be obtained.

The nucleating agent vesicle can be produced by a supercritical reversed-phase evaporation method. The supercritical reverse phase evaporation method is a method of producing nano-sized vesicles (capsules) encapsulating a target substance using carbon dioxide in a supercritical state, under temperature conditions above the critical point, or under pressure conditions above the critical point. Carbon dioxide in a supercritical state means carbon dioxide in a supercritical state with a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and carbon dioxide under temperature conditions above the critical point or pressure conditions above the critical point means carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions.

Specifically, an emulsion of supercritical carbon dioxide and an aqueous phase is produced by injecting an aqueous phase into a mixed fluid of supercritical carbon dioxide, phospholipids, and a nucleating agent as an encapsulating substance and stirring the mixture. After that, when the pressure is reduced, the carbon dioxide expands and evaporates, causing a phase inversion and forming nanovesicles in which the phospholipid covers the surface of the nucleating agent nanoparticles with a monolayer film. According to this supercritical reversed-phase evaporation method, single-layer membrane vesicles can be produced, so vesicles of extremely small size can be obtained.

The average particle size of the nucleating agent vesicle is preferably 1/2 or less of the wavelength of visible light (400 to 750 nm), more specifically 200 nm to 375 nm or less. The nucleating agent vesicle exists in the resin composition in a state in which the outer membrane of the vesicle is broken and the nano-sized nucleating agent is exposed. By minimizing the particle size of the nucleating agent within the above range, it is possible to reduce light scattering and realize a transparent resin sheet having high transparency.

The nucleating agent is not particularly limited as long as it is a substance that serves as a starting point for crystallization when the resin crystallizes. Examples thereof include phosphate ester metal salts, benzoate metal salts, pimelate metal salts, rosin metal salts, benzylidene sorbitol, chitocridone, cyanine blue and talc. In particular, in the present invention, it is preferable to use phosphate ester metal salts, benzoate metal salts, pimelate metal salts, and rosin metal salts, which are expected to have transparency.

Phospholipids include phosphatidylcholine, phosphatidiethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, glycerophospholipids such as hydrogenated soybean lecithin, sphingophospholipids such as sphingomyelin, ceramide phosphoriethanolamine, and ceramide phosphorylglycerol.

Although the crystalline polypropylene resin is not particularly limited, it is preferable to use a highly crystalline homopolypropylene resin which is a propylene homopolymer having a pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more, that is, a homopolymer.

The pentad fraction (mmmm fraction) is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating the resin composition constituting the transparent resin layer at a predetermined resonance frequency by 13C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclide) having a mass of 13, and defines the atomic arrangement, electronic structure, and molecular fine structure in the resin composition. It is the ratio of five propylene units arranged side by side, and is used as a measure of crystallinity or stereoregularity. Such a pentad fraction is one of the important factors that mainly determines the scratch resistance of the surface. Basically, the higher the pentad fraction, the higher the crystallinity of the sheet, which improves the scratch resistance.

A specific example of the configuration of the decorative sheet of the present invention and the manufacturing method of the decorative sheet will be described below with reference to FIGS. 1 and 2. FIG.

FIG. 1 shows a first embodiment of the decorative sheet 1 of the present invention, and the configuration of the decorative sheet 1 is formed by laminating a primer layer 6, a concealing layer 2, a pattern printed layer 3, a transparent resin layer 4 and a top coat layer 5 in order from the base material B side to which the decorative sheet 1 is attached. Examples of the base material B include wooden boards, inorganic boards, and metal plates.

As the primer layer 6, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, and the like can be used as binders, either singly or modified. These may be of any form, such as aqueous, solvent-based, emulsion type, and the like. Also, the curing method can be appropriately selected from a one-liquid type that cures alone, a two-liquid type that uses a curing agent together with the main agent, and a type that cures by irradiation with ultraviolet rays, electron beams, or the like. As a general curing method, a two-liquid type in which an isocyanate curing agent is combined with a urethane base resin is used, and this method is suitable from the viewpoint of workability, cost, and cohesion of the resin itself. In addition to the above binders, coloring agents such as pigments and dyes, extender pigments, solvents, and various additives are added. In particular, since the primer layer 6 is located on the backmost surface of the decorative sheet 1, considering that the decorative sheet 1 is wound as a continuous plastic film (web-like), the films adhere to each other and become difficult to slip, and in order to avoid blocking such as peeling, and to increase adhesion to the adhesive, an inorganic filler such as silica, alumina, magnesia, titanium oxide, and barium sulfate may be added. Since the purpose of the layer thickness is to ensure adhesion to the base material B, it is preferable to set the layer thickness within the range of 0.1 to 3 μm.

The material used for the primer layer 6 can be basically used for the concealing layer 2, but when the concealing property is emphasized, it is preferable to use opaque pigments such as titanium oxide and iron oxide as the pigment. In order to further improve hiding power, it is also suitable to add metals such as gold, silver, copper and aluminum. In general, flaky aluminum is often added. The masking layer 2 can be formed using the above materials by a comma coater, knife coater, lip coater, metal vapor deposition, sputtering, or the like. If the layer thickness is less than 2 μm, the hiding property is insufficient, and if it exceeds 10 μm, the cohesive force of the resin material as the main component is weakened.

The same material as the primer layer 6 can be used for the pattern printed layer 3 as well. Highly versatile pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, pearl pigments such as mica, and the like. The pattern printed layer 3 can be formed by applying gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, or the like to the transparent resin layer 4 using the materials described above. In addition to the method of forming the pattern-printed layer 3 by applying an ink composed of a mixture of a binder and a pigment, it is also possible to apply a pattern by vapor deposition or sputtering of various metals.

As the transparent resin layer 4, it is possible to use a transparent resin sheet 4 obtained by forming a sheet of a resin composition containing 90 to 100% by weight of a crystalline polypropylene resin as a main component and optionally adding various additives such as existing heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light scattering agents, and luster modifiers. In particular, in the decorative sheet 1 of the present invention, it is important to use a transparent resin sheet 4 in which the peak intensity ratio x calculated using the above formula 1 from the infrared absorption spectrum measured by Fourier infrared spectroscopy by controlling the molding conditions is x≧0.65. At this time, the thickness of the transparent resin sheet 4 is set to 20 to 200 μm. Specific examples of molding conditions include the melting temperature of the resin composition, temperature conditions such as extrusion temperature and roll temperature related to film formation, and transport conditions such as sheet winding speed. By controlling these temperature conditions and transport conditions, the crystallinity of the transparent resin sheet 4 obtained by adjusting the cooling rate during film formation is adjusted, and the peak intensity ratio x is set to x ≥ 0.65, preferably 0.65 ≤ x ≤ 0.85.

Furthermore, a nucleating agent vesicle is added to the resin composition constituting the transparent resin layer 4 . Thereby, the degree of crystallinity of the resin composition can be easily improved, and the transparent resin sheet 4 having extremely excellent transparency can be obtained.

Phenol-based, sulfur-based, phosphorus-based, hydrazine-based, and the like can be used as the heat stabilizer. Aluminum hydroxide, magnesium hydroxide, etc. can be used as a flame retardant. Benzotriazole-based, benzoate-based, benzophenone-based, triangine-based, and the like can be used as the ultraviolet absorber. Hindered amines and the like can be used as light stabilizers.

As the topcoat layer 5, it is possible to appropriately select and use from polyurethane, acrylic, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like. The form of the material is also not particularly limited, and may be water-based, emulsion, solvent-based, or the like. As for the curing method, it can be appropriately selected from a one-liquid type that cures alone, a two-liquid type that uses a curing agent together with a main agent, and a type that cures by irradiation with ultraviolet rays, electron beams, or the like. In particular, from the viewpoint of workability, cost, cohesion of the resin itself, etc., it is preferable to mix an isocyanate-based curing agent with a urethane-based base resin.

Here, a detailed film forming flow of the transparent resin sheet 4 will be described. First, for the crystalline polypropylene resin as the main component, pellets of the resin composition added with various existing additives as described above are put into a melt extruder, kneaded while heating to melt the pellets in a liquid state, and the liquid resin composition is extruded with a predetermined width from a T die provided at the extrusion port toward a cooling roll provided downstream. At this time, the liquid resin composition extruded from the T-die advances crystallization up to the cooling roll, and the crystallization is completed by coming into contact with the cooling roll. The cooling roll rotates at a predetermined rotation speed around the central axis of the roll, and the resin composition in contact with the cooling roll becomes a sheet-shaped transparent resin sheet 4, which is conveyed downstream at a predetermined conveying speed and finally wound up on a winding roll. In the present invention, in order to keep the peak intensity ratio x of the obtained transparent resin sheet 4 within a predetermined range, the temperature of the resin composition extruded from the melt extruder, the temperature of the cooling roll, and the conveying speed of the sheet are adjusted as film forming conditions.

The decorative sheet 1 of the present embodiment is formed by laminating the above materials in order of the pattern printed layer 3, the concealing layer 2 and the primer layer 6 by the above method on one side of the transparent resin sheet 4 formed by the above film production flow. When the embossed pattern 4a is provided on the transparent resin layer 4, the transparent resin sheet 4 is pressed using an embossing die roll to form the embossed pattern 4a on the other surface of the transparent resin sheet 4. As shown in FIG. Furthermore, the decorative sheet 1 is obtained by forming a top coat layer 5 on the surface of the embossed pattern 4a.

In the decorative sheet 1 of the first embodiment, the primer layer 6 is preferably 0.1 to 3.0 μm, the concealing layer 2 is 2 to 10 μm, the picture print layer 3 is 20 to 200 μm, the transparent resin sheet 4 as the transparent resin layer 4 is preferably 20 to 100 μm, the topcoat layer 5 is preferably 3 to 20 μm, and the total thickness of the decorative sheet 1 is preferably within the range of 130 to 500 μm.

FIG. 2 shows a second embodiment of the decorative sheet 1 of the present invention, and the configuration of the decorative sheet 1 is formed by sequentially laminating a primer layer 6, a raw fabric layer 7, a pattern printed layer 3, an adhesive layer 8, a transparent resin layer 4, and a top coat layer 5 from the base material B side to which the decorative sheet 1 is attached. In addition, as the material B, wooden boards, inorganic boards, metal plates, and the like can be used.

The primer layer 6, pattern printed layer 3, transparent resin layer 4, and top coat layer 5 may be of the same construction as in the first embodiment.

The raw fabric layer 7 includes paper such as thin paper, titanium paper, and resin-impregnated paper, synthetic resins such as polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate polymer, polyvinyl alcohol, and acrylic, or foams of these synthetic resins, ethylene-propylene polymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, polyurethane rubber, organic or inorganic nonwoven fabric, synthetic paper, It can be used by arbitrarily selecting from metal foils such as aluminum, iron, gold, and silver. When the raw fabric resin sheet 7 containing a polyolefin resin as the main component is used as the raw fabric layer 7, the surface is inert. Therefore, it is preferable to subject both surfaces of the raw fabric resin sheet 7 to surface activation treatment such as corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet treatment, and dichromic acid treatment. Further, a primer layer 6 may be provided between the original fabric resin sheet 7 and the pattern printed layer 3 to ensure sufficient adhesion. If the decorative sheet 1 is desired to have a concealing property, the concealing layer 2 may be provided, or an opaque pigment or the like may be added to the raw resin sheet 7 itself to impart the concealing property.

The adhesive layer 8 can be selected from acrylic, polyester, polyurethane and the like. In general, a two-liquid type material is used in which urethane-based polyol is used as the main agent and isocyanate is used as the curing agent because of its high workability, price, and cohesion.

In the decorative sheet 1 of the present embodiment, first, both surfaces of the raw resin sheet 7 as the raw fabric layer 7 are subjected to corona treatment, and the pattern printed layer 3 and the primer layer 6 are laminated in order on one surface of the raw fabric resin sheet 7. Then, the transparent resin sheet 4 as the transparent resin layer 4 formed by the above-described film-forming flow and the raw resin sheet 7 in which the pattern printed layer 3 and the primer layer 6 are laminated are bonded and laminated with the adhesive layer 8 interposed therebetween using a method such as a method applying heat pressure, an extrusion lamination method, or a dry lamination method to form a laminated film. At this time, when the embossed pattern 4a is provided on the surface of the transparent resin layer 4, the embossed pattern 4a is formed on the laminated film by a method using hot pressing or a method using a cooling roll having unevenness. Finally, the decorative sheet 1 is obtained by laminating the topcoat layer 5 on the surface of the transparent resin layer 4 of the laminated film.

In the decorative sheet 1 of the second embodiment, the raw fabric layer 7 is preferably 100 μm to 250 μm, the adhesive layer 8 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, the topcoat layer 5 is preferably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably within the range of 130 μm to 500 μm.

In the decorative sheet 1 of the present invention, the transparent resin sheet 4 as the transparent resin layer 4 as in the above-described embodiment has a peak intensity ratio x calculated using Equation 1 from the absorption spectrum obtained by Fourier infrared spectroscopy, x≧0.65, more preferably 0.65≦x≦0.85.

Further, in the decorative sheet 1 of the present invention, a nano-sized nucleating agent, more specifically, a nucleating agent vesicle containing a nucleating agent in a vesicle having a single-layer outer film is added to the resin composition constituting the transparent resin sheet 4. Therefore, the nucleating agent can be highly dispersed in the resin composition, and the nucleating agent can improve the crystallinity of the resin composition, thereby providing the decorative sheet 1 having the transparent resin sheet 4 with high transparency. I can.

Specific examples of the decorative sheet 1 and the method for manufacturing the decorative sheet 1 of the present invention are described below.

<Examples 1 to 6, Comparative Examples 1 and 2>
In Examples 1 to 6 and Comparative Examples 1 and 2 of the present invention, 500 PPM of a hindered phenolic antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals), 2000 PPM of a benzotriazole-based UV absorber (Tinuvin 328, manufactured by Ciba Specialty Chemicals), and 2 hindered amine light stabilizers (Chimasorb 944, manufactured by Ciba Specialty Chemicals) were added to the highly crystalline homopolypropylene resin. 000 PPM and 1000 PPM of a phosphate ester metal salt-based nucleating agent (ADEKA STAB NA-21, manufactured by ADEKA) are added to the resin composition and subjected to the above film-forming flow using a melt extruder to form a transparent resin sheet 4 having a thickness of 100 μm to be used as the transparent resin layer 4. Table 1 shows the peak intensity ratio x of each transparent resin sheet 4 obtained.

<Examples 7 to 10>
In Examples 7 to 10 of the present invention, a hindered phenol antioxidant (Irganox 1010, manufactured by Ciba Specialty Chemicals) at 500 PPM, a benzotriazole ultraviolet absorber (Tinuvin 328, manufactured by Ciba Specialty Chemicals) at 2000 PPM, and a hindered amine light stabilizer (Chimasorb 944, manufactured by Ciba Specialty Chemicals) at 2000 PPM for the highly crystalline homopolypropylene resin. , and a nucleating agent vesicle of 1000 PPM are added to the above film-forming flow using a melt extruder to form a transparent resin sheet 4 having a thickness of 100 μm to be used as the transparent resin layer 4 . Table 1 shows the peak intensity ratio x of each transparent resin sheet 4 obtained.

The nucleating agent vesicle is prepared by placing 100 parts by weight of methanol, 82 parts by weight of a phosphate ester metal salt-based nucleating agent (ADEKA STAB NA-21, manufactured by ADEKA), and 5 parts by weight of phosphatidylcholine in a high-pressure stainless steel container kept at 60° C., sealing the container, injecting carbon dioxide so that the pressure becomes 20 MPa to make it a supercritical state, and then injecting 100 parts by weight of ion-exchanged water while vigorously stirring and mixing. After stirring for 15 minutes while maintaining the temperature and pressure in the container, carbon dioxide is discharged and the pressure is returned to atmospheric pressure to obtain nucleating agent vesicles in which the phosphate ester metal salt-based nucleating agent is encapsulated in vesicles having a single-layer outer membrane. The particle size of the obtained nucleating agent vesicle was 0.05 to 0.8 μm.

続いて、上記の方法によって得られた実施例１～１０および比較例１，２の各透明樹脂シート４の両面にコロナ処理を施して表面の濡れを４０ｄｙｎ／ｃｍ以上とし、当該透明樹脂シート４の一方の表面に２液硬化型ウレタンインキ（Ｖ１８０、東洋インキ製造株式会社製）にて絵柄印刷を施して絵柄印刷層３を形成するとともに、当該絵柄印刷層３に重ねて隠蔽性のある２液効果型ウレタンインキ（Ｖ１８０、東洋インキ製造株式会社製）を塗布量６ｇ／ｍ ^２にて塗布して隠蔽層２を形成した。 Further, a primer layer 6 was formed by applying a two-liquid curable urethane ink (PET-E, Resiuser, manufactured by Dainichiseika Co., Ltd.) over the masking layer 2 at a coating amount of 1 g/m ² . Thereafter, the other surface of the transparent resin sheet 4 was pressed using an embossing die roll to form an embossed pattern 4a, and a two-liquid curing urethane topcoat (W184, manufactured by Dainippon Ink Co., Ltd.) was applied to the surface of the embossed pattern 4a at a coating amount of 3 g/m2 to obtain a decorative sheet ¹ having a layer thickness of 110 µm shown in FIG.

The decorative sheets 1 of Examples 1 to 10 and Comparative Examples 1 and 2 obtained by the above method were subjected to a coin scratch evaluation test for evaluating scratch resistance and a haze value measurement test for evaluating transparency.

Detailed methods of the coin scratch evaluation test and the haze value measurement test are described below.

<Coin scratch evaluation test>
First, in the coin scratch evaluation test, a coin is held in contact with the surface of each decorative sheet 1 obtained by the above method and fixed using a jig. A load of 1, 2, 3, or 4 kg is applied to the jig and the coin is slid at a constant speed. In this evaluation test, it was judged that the decorative sheet 1 that did not get scratched under a load of 2 kg or more was acceptable because it may be used in a place where a load such as a floor is significantly applied.

<Haze value measurement test>
Here, the haze value is a value obtained by dividing the value (diffuse transmittance) obtained by subtracting the integrated value (linear transmittance) of only the linear component of the light beams emitted from the other surface from the integrated value (total light transmittance) of all the light rays emitted from one surface of an object when the light emitted from one surface of the object is emitted to the other surface, by the total light transmittance. The smaller the value, the higher the transparency. This haze value is determined by the internal haze determined by the internal state of the object such as the degree of crystallinity and spherulite size in the crystal part, and the external haze determined by the surface state of the object such as the presence or absence of irregularities on the entrance surface and the exit surface. In the present invention, simply referring to a haze value means a value determined by internal haze and external haze. In this example, the haze value measurement test was performed on each transparent resin sheet using a haze value measurement tester (manufactured by Nippon Denshoku Co., Ltd.; NDH2000). A blank measurement is performed in advance with nothing attached to the sample holder. In the measurement of each transparent resin sheet, the sample was attached to the sample holder and the sample transmission measurement was performed under the same conditions as the blank measurement, and the ratio between the sample transmission measurement and the blank measurement was expressed as a percentage and calculated as the haze value. In the present invention, samples with a haze value of less than 15% were judged to pass the test.

Table 1 shows the above coin scratch evaluation test results and haze value measurement test results.

As shown in Table 1, the evaluation test results of each decorative sheet 1 revealed that each of the decorative sheets 1 of Examples 1 to 10, in which the peak intensity ratio x of the transparent resin sheet 4 was x≧0.65, was not scratched even in a coin scratch test in which a load of 2 kg or more was applied, and had extremely excellent scratch resistance and transparency with a haze value of 14% or less. Incidentally, the transparent resin sheet 4 with x>0.85 could not be formed into a film. Further, the decorative sheets 1 of Comparative Examples 1 and 2, in which the peak intensity ratio x of the transparent resin sheet 4 is set to x<0.65, were found to have noticeable scratches in a coin scratch test with a load of 1 kg or less, and had a haze value of 15.1 or more, indicating poor scratch resistance and transparency.

Moreover, in Examples 7 to 10 in which the nucleating agent vesicle was added, the haze values were extremely low at 8.4%, 8.1%, 7.2% and 6.8%, indicating excellent transparency.

From the above results, it was clarified that the decorative sheet 1 having excellent scratch resistance and transparency can be obtained by setting the peak intensity ratio x of the transparent resin sheet 4 as the transparent resin layer 4 to x≧0.65, preferably 0.65≦x≦0.85.

Further, it was found that by adding nucleating agent vesicles to the transparent resin sheet 4, the dispersibility of the nucleating agent in the transparent resin sheet 4 can be improved, and the decorative sheet 1 having extremely high transparency and excellent design can be obtained.

The decorative sheet 1 and the manufacturing method of the decorative sheet 1 of the present invention are not limited to the above embodiments and examples, and various modifications are possible without impairing the characteristics of the invention.

1 decorative sheet 2 concealing layer 3 pattern printed layer 4 transparent resin layer, transparent resin sheet 4a embossed pattern 5 top coat layer 6 primer layer 7 raw fabric layer, raw fabric resin sheet 8 adhesive layer

Claims (6)

A decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer on the topcoat layer side,
The value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65 ≤ x ≤ 0.85,
A decorative sheet, characterized in that the transparent resin sheet is formed by adding a nano-sized nucleating agent.
Here, in Equation 1, I997 represents the peak intensity value at wavenumber 997 cm ⁻¹ , I938 represents the peak intensity value at wavenumber 938 cm ⁻¹ , and I973 represents the peak intensity value at wavenumber 973 cm ⁻¹ .

A decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer on the topcoat layer side,
The value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65 ≤ x ≤ 0.85,
forming the transparent resin sheet by adding a nucleating agent;
The decorative sheet, wherein the nucleating agent is metal benzoate, metal pimelate, metal rosin, chitocridone, cyanine blue, or talc.
Here, in Equation 1, I997 represents the peak intensity value at wavenumber 997 cm ⁻¹ , I938 represents the peak intensity value at wavenumber 938 cm ⁻¹ , and I973 represents the peak intensity value at wavenumber 973 cm ⁻¹ .

A decorative sheet comprising at least a concealing layer, a pattern printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer on the topcoat layer side,
The value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy of the transparent resin sheet as the transparent resin layer is 0.65 ≤ x ≤ 0.85,
A decorative sheet, wherein the transparent resin sheet is formed by adding nano-sized nucleating agent vesicles containing a nucleating agent to vesicles having a single-layer outer membrane.
Here, in Equation 1, I997 represents the peak intensity value at wavenumber 997 cm ⁻¹ , I938 represents the peak intensity value at wavenumber 938 cm ⁻¹ , and I973 represents the peak intensity value at wavenumber 973 cm ⁻¹ .

3. The decorative sheet according to claim 1, wherein the transparent resin sheet is formed by adding nano-sized nucleating agent vesicles containing the nucleating agent to vesicles having a single-layer outer membrane. A decorative sheet comprising at least a concealing layer, a pattern-printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer,
Nano-sized nucleating agent vesicles containing a nucleating agent are added to vesicles having a single-layer outer film by a supercritical reverse phase evaporation method to the crystalline polypropylene resin, and a transparent resin sheet is formed as the transparent resin layer so that the value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy is 0.65 ≤ x ≤ 0.85.

A decorative sheet comprising at least a concealing layer, a pattern-printed layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, or a decorative sheet comprising at least a concealing layer, a transparent resin layer containing 90 to 100% by weight of a crystalline polypropylene resin as a main component, and a topcoat layer in this order, and having an embossed pattern on the surface of the transparent resin layer facing the topcoat layer,
A nucleating agent vesicle containing a nucleating agent is added to a vesicle having a single-layer outer film by a supercritical reverse phase evaporation method to the crystalline polypropylene resin, and a transparent resin sheet as the transparent resin layer is formed so that the value of the peak intensity ratio x calculated using the following formula 1 from the absorption spectrum obtained by Fourier infrared spectroscopy is 0.65 ≤ x ≤ 0.85.
A method for producing a decorative sheet, wherein the nucleating agent is metal benzoate, metal pimelate, metal rosin, chitocridone, cyanine blue, or talc.

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