JP6629602B2 - Decorative sheet and transparent resin sheet, and method for manufacturing decorative sheet and transparent resin sheet - Google Patents

Description

The present invention relates to a decorative sheet used for a building material used for exterior and interior of a building, a surface of a fitting, a surface material of a household electrical appliance and the like, a transparent resin sheet used therefor, and a method of manufacturing the decorative sheet and the same. The present invention relates to a method for producing a transparent resin sheet, a decorative sheet having at least one layer laminated on a substrate layer, a transparent resin sheet suitable for the transparent resin layer, a method for producing the decorative sheet, and the transparent resin sheet A method for producing the same .

Conventionally, as shown in Patent Documents 1 to 5, many decorative sheets using an olefin-based resin have been proposed as decorative sheets replacing polyvinyl chloride decorative sheets.
By not using a vinyl chloride resin for these decorative sheets, generation of toxic gas and the like at the time of incineration can be suppressed. However, the decorative sheets described in Patent Literatures 1 to 5 have poor surface scratch resistance due to the use of a general polypropylene sheet or a soft polypropylene sheet, and the scratch resistance of the decorative sheet made of polyvinyl chloride is poor. It was much worse than gender.

Then, the present inventors proposed a decorative sheet excellent in surface scratch resistance and post-workability, as described in Patent Document 6, in order to solve these drawbacks.
However, as decorative sheets using decorative sheets having such performances have been increasingly used and consumers have become more and more conscious of quality, the decorative sheets are required to have surface scratch resistance and V Further improvement in post-processing resistance to groove bending and the like is required.

JP-A-2-128843 JP-A-4-083664 JP-A-6-001881 JP-A-6-198831 JP-A-9-328562 Japanese Patent No. 3777234

  The present invention has been made in view of the above points, and has an object to provide a decorative sheet having a transparent resin layer having high transparency from the viewpoint of design and excellent scratch resistance on the surface. And

  Here, the crystalline resin such as polypropylene can change the mechanical properties by controlling the degree of crystallinity, which is the ratio between the crystalline component and the amorphous component in the resin. Factors for controlling the degree of conversion include material factors due to the molecular structure of the resin itself and the addition of a nucleating agent, and process factors such as molding processing conditions for processing the crystalline resin. The present inventors, in the present invention, in particular, provided a transparent resin layer that has been intensively studied focusing on the process factors, and that has specified a range of crystallinity with excellent scratch resistance by controlling the process factors. Finished the decorative sheet.

In order to solve the problem, a decorative sheet according to one embodiment of the present invention has a transparent resin layer containing a crystalline polypropylene resin as a main component, and the transparent resin layer has a peak represented by the following formula (1). The value of the area ratio x is x ≧ 0.4.
Here, S040, S130, and Sam in the following formula (1) are peak areas determined from an X-ray diffraction spectrum obtained by measuring the transparent resin layer by X-ray diffraction. S040 represents the peak area of the polypropylene α crystal according to the Miller index (040), S130 represents the peak area of the polypropylene α crystal according to the Miller index (130), and Sam represents the amorphous peak area.
Peak area ratio x = (S040 + S130) / (Sam) Expression (1)

A transparent resin sheet according to another embodiment of the present invention contains a crystalline polypropylene resin as a main component, and has a peak area ratio x represented by the following formula (2) of 0.4 or more.
Here, S040, S130, and Sam in the following formula (2) are peak areas calculated from an X-ray diffraction spectrum obtained by X-ray diffraction of the transparent resin sheet, and S040 is a Miller index of α-crystal polypropylene ( 040), S130 represents the peak area according to the Miller index (130) of polypropylene α-crystal, and Sam represents the amorphous peak area.
Peak area ratio x = (S040 + S130) / (Sam) Equation (2)

According to the aspect of the present invention, a decorative sheet provided with a transparent resin layer having high transparency and excellent scratch resistance can be provided.
By assuring high transparency to the transparent resin layer, for example, if the transparent resin layer has a pattern layer below the transparent resin layer, the pattern of the pattern layer can have high transparency from the viewpoint of design. It becomes.

It is sectional drawing explaining the decorative sheet which concerns on 1st Embodiment based on this invention. It is sectional drawing explaining the decorative sheet which concerns on 2nd Embodiment based on this invention.

Next, an embodiment of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the plane dimension, the ratio of the thickness of each layer, and the like are different from actual ones. Further, the embodiments described below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is as follows. It is not something specific. The technical concept of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

<Transparent resin layer>
The decorative sheet of the present embodiment is a decorative sheet having a transparent resin layer containing a crystalline polypropylene resin as a main component. In the present embodiment, a case where the transparent resin layer is formed of a transparent resin sheet is exemplified. The transparent resin layer may be formed by coating.
The phrase “mainly composed of a crystalline polypropylene resin” means that, for example, 80% by mass or more and 100% by mass or less, preferably 90% by mass or more and 100% by mass or less of the resin constituting the transparent resin layer is a crystalline polypropylene resin. Refers to something.

An X-ray diffraction obtained by preparing the transparent resin layer as a transparent resin sheet, or preparing a transparent resin sheet having the same composition as the transparent resin layer, and measuring the X-ray diffraction of the transparent resin sheet with an X-ray diffractometer. It is important that the value of the peak area ratio x calculated from the spectrum using the following equation (3) is 0.4 or more.
In the formula (3), S040 represents the peak area of the polypropylene α crystal according to the Miller index (040), S130 represents the peak area of the polypropylene α crystal according to the Miller index (130), and Sam represents the amorphous peak area. Here, the peak of the Miller index (040) is 2θ = 16.8 ± 0.5 degrees, the peak of the Miller index (130) is 2θ = 18.5 ± 0.5 degrees, and the peak of the amorphous is 2θ = 15. Appears around ± 1.0 degrees.
Peak area ratio x = (S040 + S130) / (Sam) Equation (3)

Then, the transparent resin layer is set such that the peak area ratio x of the X-ray diffraction spectrum of the transparent resin sheet is 0.4 or more. Preferably, the transparent resin layer is set such that the peak area ratio x is in the range of 0.4 to 1.0.
When the peak area ratio x is less than 0.4, the decorative sheet having desired scratch resistance cannot be obtained due to insufficient crystallization of the transparent resin layer. On the other hand, when the peak area ratio x is set to a value larger than 1.0, the improvement in scratch resistance can be expected, but the embrittlement of the transparent resin layer becomes remarkable, and the whitening caused by stretching or bending causes the design of the decorative sheet to become poor. Is impaired.
By setting the peak area ratio x within the above range, a decorative sheet having a transparent resin layer (transparent resin sheet) which is extremely excellent in scratch resistance and at the same time whitening caused by stretching or bending does not impair the design property of the decorative sheet. Can be provided.

  In the decorative sheet of the present embodiment, the peak area ratio x of the transparent resin layer is set within the above range by controlling the film forming conditions as a process factor. At this time, the transparent resin layer is preferably formed to have a thickness of 20 μm or more and 200 μm or less. If the thickness of the transparent resin layer is less than 20 μm, there is a possibility that scratch resistance may not be ensured, and if the thickness of the transparent resin layer is greater than 200 μm, cooling in the thickness direction of the transparent resin layer is not performed uniformly, As a result, the resin may not be cured uniformly. The transparent resin layer is more preferably formed to have a thickness of 30 μm or more and 150 μm or less.

[Control of peak area ratio x]
The film forming conditions for controlling the peak area ratio x within the above range may be any as long as the crystallinity of the polypropylene resin can be adjusted. In the present embodiment, the resin temperature, the cooling temperature, the cooling The degree of crystallinity is adjusted by adjusting the time and the like. By controlling one or more of these conditions, the peak area ratio x can be adjusted within the above range.
Here, the resin temperature is the temperature at which the molten resin is discharged during film formation. The peak area ratio x increases as the resin temperature increases, that is, as the temperature increases. The cooling temperature is a temperature at which the resin immediately after being discharged is kept at a constant value equal to or lower than its melting point from a molten state for cooling. For example, in the case of crystalline polypropylene, in order to promote crystallization of the resin, the cooling temperature is desirably 50 ° C. or higher and 130 ° C. or lower at which the crystallization speed of the polypropylene resin is good. The cooling time is the time during which the resin is within the cooling temperature ± 15 ° C. Increasing the transit time increases the peak area ratio x. By combining the above conditions, crystallization and crystal size in the resin can be controlled, and the peak area ratio x can be appropriately adjusted.

[About X-ray line measurement]
The X-ray diffraction measurement will be described.
First, the X-ray diffraction measurement means that a sample is irradiated with X-rays, and the X-rays are scattered and interfered by electrons around atoms. This is a measurement method for obtaining information on the size of a crystal and strain of a crystal.
A specific measurement method of X-ray diffraction is as follows. X-rays having a wavelength (0.5 A to 3 A) approximately equal to the distance between atoms are incident on a substance, and X-rays are scattered by electrons belonging to each atom. Then, the scattered X-ray interference wave is detected. A graph obtained by plotting the diffraction angle 2θ on the horizontal axis and the detected X-ray intensity on the vertical axis by the above method is called an X-ray diffraction spectrum, and a unique pattern is recognized for each crystal form. At this time, the X-ray intensity on the vertical axis, in the case of a crystalline resin, the peak intensity at a predetermined diffraction angle and the value of the peak area change in proportion to the amount of the crystalline portion or the amorphous portion, It is also possible to perform quantitative analysis from the height and area of the peak.

  In the present embodiment, the Miller index of the α-type crystalline portion in the polypropylene transparent resin sheet in the X-ray diffraction spectrum obtained by the above-described measurement using the above-described characteristics of the X-ray diffraction spectrum ( 040) and a peak area (S040) with a diffraction angle 2θ = 16.8 ± 0.5 degrees, and a diffraction angle 2θ = 18.5 ± 0.5 corresponding to the Miller index (130) of the α-type crystalline part. Ratio of the sum of the peak area (S130) and the peak area (Sam) at the diffraction angle 2θ = 15 ± 1.0 degrees corresponding to the amorphous portion of the transparent resin sheet, that is, the degree of crystallization of polypropylene. Is calculated using the above formula (3), the relationship between the peak area ratio x and the scratch resistance of the transparent resin sheet (transparent resin layer) is clarified, and the peak area ratio within the above range is clarified. x transparent resin By providing a transparent resin layer corresponding to the sheet, a decorative sheet having excellent scratch resistance is provided. Note that the peak area of the Miller index (040) corresponding to the crystal part, the peak area of the Miller index (130), and the peak area corresponding to the amorphous part are calculated after performing background correction.

[Nucleating agent]
It is preferable that a nano-sized nucleating agent is added to the transparent resin layer. In particular, it is preferable that the nano-sized nucleating agent is added in the form of a nucleating agent vesicle in which the nucleating agent is included in a vesicle having a single-layered outer membrane.
By adding a nucleating agent vesicle to the polypropylene resin, the crystallinity of the polypropylene resin is improved, and a transparent resin sheet having extremely high transparency can be obtained.

[About the method for producing nucleating agent vesicles]
The nucleating agent vesicle can be produced by a supercritical reversed-phase evaporation method.
Supercritical reversed-phase evaporation is a method for producing nano-sized vesicles (capsules) containing a target substance using carbon dioxide in a supercritical state, at a temperature above the critical point, or at a pressure above the critical point. It is. The carbon dioxide in a supercritical state means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C.) and a critical pressure (7.3773 ± 0.0030 MPa) or higher. The term “carbon dioxide under a pressure condition equal to or higher than the critical point” means carbon dioxide under a condition where only the critical temperature or only the critical pressure exceeds the critical condition.

Specifically, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, a phospholipid, and a nucleating agent as an encapsulating substance, and the mixture is stirred to generate an emulsion of the supercritical carbon dioxide and the aqueous phase. Thereafter, when the pressure is reduced, the carbon dioxide expands and evaporates to cause phase inversion, and nanovesicles in which phospholipids cover the surface of the nucleating agent nanoparticles with a monolayer film are generated. According to this supercritical reversed-phase evaporation method, vesicles of a single-layer film can be generated, so that vesicles of an extremely small size can be obtained.
The average particle diameter of the nucleating agent vesicle containing the nano-sized nucleating agent is preferably 以下 or less of the visible light wavelength (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 where the outer membrane of the vesicle is broken and the nano-sized nucleating agent is exposed. By setting the particle size of the nucleating agent to an extremely small size within the above range, scattering of light can be reduced and a transparent resin layer having high transparency can be realized.

The nucleating agent is not particularly limited as long as it is a substance that is a starting point of crystallization when the resin is crystallized, but, for example, a phosphate metal salt, a metal benzoate, a metal pimelate, a rosin Metal salts, benzylidene sorbitol, quinacridone, cyanine blue, talc and the like. In particular, in the present embodiment, it is preferable to use a metal salt of a phosphoric acid ester, a metal salt of benzoic acid, a metal salt of pimelic acid, or a metal salt of rosin, which can be expected to be transparent.
Examples of the phospholipid include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiopine, yellow egg lecithin, hydrogenated yellow egg lecithin, soy lecithin, hydrogenated soy lecithin, sphingo, and the like. Sphingolipids such as myelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol;

The crystalline polypropylene resin is not particularly limited, but a propylene homopolymer having a pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more, that is, a highly crystalline homopolymer which is a homopolymer It is preferable to use a polypropylene resin.
The pentad fraction (mmmm fraction) refers to a resin composition constituting a transparent resin layer by ¹³ C-NMR measurement (nuclear magnetic resonance measurement) using carbon C (nuclide) having a mass number of 13. Is calculated from a numerical value (electromagnetic wave absorption rate) obtained by resonating at a predetermined resonance frequency. The pentad fraction (mmmm fraction) defines the atomic arrangement, electronic structure, and molecular fine structure in the resin composition. The pentad fraction of the polypropylene resin is a proportion of five propylene units determined by ¹³ C-NMR, and is used as a measure of crystallinity or stereoregularity. Such a pentad fraction is one of the important factors that mainly determine the scratch resistance of the surface. Basically, the higher the pentad fraction, the higher the crystallinity of the sheet becomes. Is improved.

<Structure of decorative sheet>
Hereinafter, a specific example of the configuration of the decorative sheet according to the present embodiment will be described with reference to FIGS. 1 and 2.
"Cosmetic sheet of the first embodiment"
FIG. 1 shows a first embodiment of a decorative sheet 1 of the present embodiment. The configuration of the decorative sheet 1 is as follows: a primer layer 6, a concealing layer 2 as a base layer, The pattern printing layer 3, the transparent resin layer 4, and the top coat layer 5 are sequentially laminated. In addition, examples of the base material B include wood boards (wood base material), inorganic boards (composite version), and metal plates.

[Primer layer 6]
The material of the primer layer 6 may be appropriately selected from nitrified cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acryl, polyester, etc. alone or modified products as a binder. Can be. These may be in any form such as aqueous, solvent-based, and emulsion types. Also, the curing method can be appropriately selected and used from a one-part type that cures alone, a two-part type that uses a curing agent in combination with the main agent, and a type that cures by irradiation with ultraviolet rays or electron beams. As a general curing method, a two-pack type is used in which a urethane-based main agent is cured by combining an isocyanate-based curing agent, and this method has a workability, a price, and a cohesive force of the resin itself. It is suitable from a viewpoint. In addition to the above binders, coloring agents such as pigments and dyes, extenders, solvents, various additives, and the like are added. In particular, since the primer layer 6 is located on the rearmost surface of the decorative sheet 1, considering that the decorative sheet 1 is wound up as a continuous plastic film (web-like), the films are in close contact with each other and are not slippery. An inorganic filler such as silica, alumina, magnesia, titanium oxide, barium sulfate, etc. may be added in order to avoid the occurrence of blocking such as becoming unpeeled or to prevent peeling, and to enhance the adhesion to the adhesive. The layer thickness is preferably in the range of 0.1 μm to 3.0 μm since the purpose is to ensure adhesion to the base material B.

[Hiding layer 2]
Basically, the material used for the primer layer 6 can be used as the material of the concealing layer 2 as the base material layer. However, when concealment is important, titanium oxide, which is an opaque pigment, is used as the pigment. It is preferable to use iron or the like. In order to further improve the concealing property, it is preferable to add a metal such as gold, silver, copper, or aluminum. Generally, flake-like aluminum is often added. The concealing layer 2 can be formed using the above-mentioned materials by a comma coater, a knife coater, a lip coater, a metal deposition or a sputtering method. When the layer thickness is less than 2 μm, the concealing property is insufficient, and when it exceeds 10 μm, the cohesive force of the resin material as a main component is weakened, so that the thickness is appropriately 2 μm to 10 μm.

The same material as the primer layer 6 can be used for the material of the picture printing layer 3. 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. The pattern printing layer 3 can be formed by performing gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, ink jet printing, or the like on the transparent resin layer 4 using the above-described material. In addition to the method of forming the picture print layer 3 by applying the ink composed of the mixture of the binder and the pigment, it is also possible to apply the picture by vapor deposition or sputtering of various metals.
The transparent resin layer 4 is composed mainly of a crystalline polypropylene resin as described above. The transparent resin layer 4 may contain, if necessary, existing heat stabilizers, flame retardants, ultraviolet absorbers, light stabilizers, antiblocking agents, catalyst scavengers, coloring agents, light scattering agents, and gloss control agents. Various additives are added.

In the present embodiment, as the transparent resin layer 4, a transparent resin sheet 4 in which a resin composition having the above composition is formed into a sheet shape is used.
In particular, in the decorative sheet 1 of the present embodiment, by controlling the molding processing conditions, the peak area ratio x calculated from the infrared absorption spectrum measured by Fourier-type infrared spectroscopy based on the above equation (3). Is set to 0.4 or more. At this time, the thickness of the transparent resin sheet 4 is, for example, 20 to 200 μm. Specific examples of the molding processing conditions include a melting temperature of the resin composition, temperature conditions such as an extrusion temperature and a roll temperature related to film formation, and conveyance conditions such as a sheet winding speed, and the like. By controlling the conditions, the crystallinity of the transparent resin sheet 4 obtained by adjusting the cooling rate during film formation is adjusted, and the peak area ratio x is set to 0.4 or more.

Further, a nucleating agent vesicle is added to the resin composition constituting the transparent resin layer 4. Thereby, the crystallinity of the resin composition can be easily improved, and the transparent resin sheet 4 having extremely excellent transparency can be obtained.
Phenol, sulfur, phosphorus, hydrazine and the like can be used as the heat stabilizer. As the flame retardant, aluminum hydroxide, magnesium hydroxide, or the like can be used. Benzotriazole, benzoate, benzophenone, triazine and the like can be used as the ultraviolet absorber. As the light stabilizer, a hindered amine type or the like can be used.

[Top coat layer 5]
The material of the top coat layer 5 can be appropriately selected from polyurethane, acrylic, acrylic silicon, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd, urea, and the like. . The form of the material is not particularly limited, such as aqueous, emulsion, and solvent-based materials. The curing method can be appropriately selected and used from a one-part type that cures alone, a two-part type that uses a curing agent in combination with the main agent, and a type that cures by irradiation with ultraviolet rays or electron beams. Particularly, a mixture obtained by mixing an urethane-based main agent with an isocyanate-based curing agent and curing the mixture is preferable from the viewpoint of workability, cost, cohesive strength of the resin itself, and the like.

[Method of forming transparent resin sheet 4]
Here, a detailed film forming flow of the transparent resin sheet 4 will be described. First, pellets of a resin composition obtained by adding existing various additives to a crystalline polypropylene resin as a main component as described above are put into a melt extruder, and kneaded while heating to melt the pellets into a liquid state. Then, the liquid resin composition is extruded at a predetermined width from a T-die provided at the extrusion port toward a cooling roll provided on the downstream side. At this time, the liquid resin composition extruded from the T-die is quenched to a cooling temperature by contacting the cooling roll, and then is crystallized while being conveyed at a temperature near the cooling temperature. The cooling roll is rotating at a predetermined rotation speed around the center axis of the roll, and the resin composition in contact with the cooling roll becomes a sheet-shaped transparent resin sheet 4 and is conveyed downstream at a predetermined conveyance speed. And finally wound up on a take-up roll. In this embodiment, in order to keep the peak area ratio x of the obtained transparent resin sheet 4 within a predetermined range, the temperature of the resin composition extruded from the melt extruder and the temperature of the cooling roll as film forming conditions are set. And adjust the sheet conveying speed.

Subsequently, on one surface of the transparent resin sheet 4 formed by the above-described film forming flow, the above-mentioned material is formed by laminating the pattern printing layer 3, the concealing layer 2, and the primer layer 6 in this order by the above-described method. When the embossed pattern 4a is provided on the transparent resin layer 4, the embossed pattern 4a is applied to the other surface of the transparent resin sheet 4 by pressing the transparent resin sheet 4 using an embossing die roll. Further, the topcoat layer 5 is formed on the surface of the embossed pattern 4a to obtain the decorative sheet 1.
In the decorative sheet 1 of the first embodiment, the primer layer 6 is 0.1 to 3.0 μm, the concealing layer 2 is 2 to 10 μm, the picture printing layer 3 is 3 to 20 μm, and the transparent resin sheet 4 as the transparent resin layer 4. The thickness of the topcoat layer 5 is preferably 3 to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 30 to 250 μm.

"Cosmetic sheet of the second embodiment"
FIG. 2 shows a second embodiment of the decorative sheet 1 according to the present invention. The decorative sheet 1 has a configuration in which a primer layer 6, a raw material layer 7 as a base layer, The pattern printing layer 3, the adhesive layer 8, the transparent resin layer 4, and the top coat layer 5 are sequentially laminated. In addition, examples of the base material B include wood boards, inorganic boards, and metal plates.
As the primer layer 6, the pattern printing layer 3, the transparent resin layer 4, and the top coat layer 5, those having the same configuration as in the first embodiment can be used.

The raw material layer 7 as a base material layer is a sheet-shaped member, and the raw material layer 7 is paper such as thin paper, titanium paper, resin-impregnated paper, polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide. , Synthetic resins such as 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 It can be arbitrarily selected from isoprene-styrene block copolymer rubber, rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, metal foil such as aluminum, iron, gold and silver. When the raw material layer 7 is mainly composed of a polyolefin resin, the surface is inactive. Therefore, both surfaces of the raw material layer 7 are subjected to corona treatment, plasma treatment, ozone treatment, and the like. The surface is preferably activated by an electron beam treatment, an ultraviolet treatment, a dichromic acid treatment, or the like. Furthermore, a primer layer 6 may be provided between the raw material layer 7 and the pattern printing layer 3 in order to ensure sufficient adhesion. When it is desired to provide the decorative sheet 1 with a concealing property, the concealing property may be provided by providing the concealing layer 2 or adding an opaque pigment or the like to the raw material layer 7 itself.
The adhesive layer 8 can be selected from acrylic, polyester, polyurethane and the like. In general, a two-pack type material using a urethane-based polyol as a main component and an isocyanate as a curing agent is used because of high workability, cost, and high cohesion.

In the decorative sheet 1 of the present embodiment, first, the corona treatment is performed on both surfaces of the raw material layer 7 as the base material layer, and the pattern printing layer 3 and the primer layer 6 are formed on one surface of the raw material layer 7. Laminate in order. Then, the transparent resin sheet 4 as the transparent resin layer 4 formed by the above-described film forming flow, and the raw material layer 7 on which the pattern printing layer 3 and the primer layer 6 are laminated are interposed with the adhesive layer 8 interposed therebetween. Then, they are bonded and laminated using a method such as a method applying hot pressure, an extrusion laminating method or a dry laminating 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 heat pressure or a method using a cooling roll having unevenness. Is done. Finally, the topcoat layer 5 is laminated on the surface of the transparent resin layer 4 of the laminated film to obtain the decorative sheet 1.
In the decorative sheet 1 of the second embodiment, the raw material layer 7 is 100 μm to 250 μm in consideration of printing workability and cost, the adhesive layer 8 is 1 μm to 20 μm, the transparent resin layer 4 is 20 μm to 200 μm, The thickness of the layer 5 is preferably 3 μm to 20 μm, and the total thickness of the decorative sheet 1 is preferably in the range of 130 μm to 500 μm.

<Effect of this embodiment>
In the decorative sheet 1 of the present embodiment, the transparent resin sheet 4 as the transparent resin layer 4 contains a crystalline polypropylene resin as a main component, and further obtains the expression (3) from the X-ray diffraction spectrum obtained in the X-ray diffraction measurement. The value of the peak area ratio x calculated using the value is in the range of x ≧ 0.4, more preferably x ≧ 0.5.
According to this configuration, it is possible to provide a decorative sheet 1 having more excellent scratch resistance than a conventional decorative sheet.

In addition, the decorative sheet 1 of the present embodiment has a nano-sized nucleating agent added to the resin composition constituting the transparent resin sheet 4.
Since the nucleating agent is nano-sized, transparency is ensured even when the nucleating agent is added.
Further, a nano-sized nucleating agent is added in the form of a nucleating agent vesicle encapsulated in a vesicle having a single-layered outer membrane.
According to this configuration, a high dispersibility of the nucleating agent is realized in the resin composition, and the crystallinity of the resin composition is improved by the nucleating agent, thereby forming the transparent resin sheet 4 having high transparency. The provided decorative sheet 1 can be provided.

Hereinafter, specific examples of the decorative sheet 1 of the present invention will be described.
<Examples 1 to 6, Comparative Examples 1 and 2>
In Examples 1 to 6 and Comparative Examples 1 and 2 based on the present invention, a hindered phenol-based antioxidant (Irganox 1010, manufactured by BASF) was used for a highly crystalline homopolypropylene resin. 500 PPM, a benzotriazole-based UV absorber (Tinuvin 328, manufactured by BASF), 2000 PPM, a hindered amine-based light stabilizer (Chimassorb 944, manufactured by BASF) 2000 PPM, and a phosphate ester metal salt-based nucleating agent (ADEKA STAB NA-) 21, a transparent resin sheet 4 having a thickness of 100 μm was formed as a transparent resin layer 4 by performing the above-described film forming flow using a melt extruder on the resin composition to which 1000 PPM was added. .

At this time, each of Examples 1 to 6 and Comparative Examples 1 and 2 was manufactured by individually controlling the peak area ratio x. Table 1 shows the peak area ratio x of the produced transparent resin sheets of Examples 1 to 6 and Comparative Examples 1 and 2.
The X-ray diffraction spectrum was measured by a parallel method using an X-ray diffractometer RINT TTRIII (manufactured by Rigaku Corporation). Cu was used as an X-ray source, and scattered X-rays were measured with a scintillation counter.

<Examples 7 to 11>
In Examples 7 to 11 according to the present invention, a hindered phenol-based antioxidant (Irganox 1010, manufactured by BASF) and a benzotriazole-based ultraviolet absorber (Tinuvin 328) were used for the highly crystalline homopolypropylene resin. By using a melt extruder, a resin to which 2000 PPM (manufactured by BASF Corporation), 2000 PPM of a hindered amine light stabilizer (Chimasorb 944, manufactured by BASF Corporation) and 1000 PPM of a nucleating agent are subjected to the above film forming flow using a melt extruder. A 100 μm thick transparent resin sheet 4 used as the transparent resin layer 4 is formed. Table 1 shows the peak area ratio x of each of the obtained transparent resin sheets 4.

  The nucleating agent vesicle added was 100 parts by mass of methanol, 82 parts by mass of a phosphate ester metal salt-based nucleating agent (ADEKA STAB NA-21, manufactured by ADEKA), and 5 parts by mass of phosphatidylcholine. After sealing in a stainless steel container and injecting carbon dioxide to a supercritical state so that the pressure becomes 20 MPa, 100 parts by mass of ion-exchanged water is injected with vigorous stirring and mixing. After stirring for 15 minutes while maintaining the temperature and pressure in the vessel, the phosphate ester nucleating agent is encapsulated in the vesicle having a single-layer outer membrane by discharging carbon dioxide and returning to atmospheric pressure. Nucleating agent vesicles are obtained. The particle size of the nucleating agent vesicle obtained was in the range of 0.05 to 0.8 μm.

Subsequently, both surfaces of each of the transparent resin sheets 4 of Examples 1 to 11 and Comparative Examples 1 and 2 obtained by the above method were subjected to corona treatment to make the surface wet tension 40 dyn / cm or more. 4 is printed with a two-component curable urethane ink (V180, manufactured by Toyo Ink Mfg. Co., Ltd.) to form a pattern printing layer 3, and has a concealing property by overlapping the pattern printing layer 3. two-component curing type urethane ink (V180, manufactured by Toyo ink Mfg. Co., Ltd.) to form a hiding layer 2 by coating the at coating amount 6 g / ^{m 2.} Further, a two-component curable urethane ink (PET-E, Regiser, manufactured by Dainichi Seika Co., Ltd.) was applied on the concealing layer 2 at a coating amount of 1 g / m ² to form the primer layer 6. Thereafter, the other surface of the transparent resin sheet 4 is pressed by using an embossing mold roll to apply an embossed pattern 4a, and a two-component curable urethane top coat (W184, DIC) is formed on the surface of the embossed pattern 4a. (Graphics) was applied at an application amount of 3 g / m ² to obtain a decorative sheet 1 having a layer thickness of 110 μm shown in FIG.

<Evaluation>
For the decorative sheets 1 of Examples 1 to 11 and Comparative Examples 1 and 2 obtained by the above method, a coin scratch evaluation test for evaluating scratch resistance, a haze value measurement test for evaluating transparency, and post-processing A bending whitening test was performed to evaluate the properties.

The detailed method of each test is described below.
<Coin scratch evaluation test>
First, in the coin scratch evaluation test, a coin was fixed to a surface of each decorative sheet 1 obtained by the above method using a jig in a state in which the coin was in contact with the surface, and 1, 2, 3, or 4 kg of the jig was fixed to the jig. The coin was slid at a constant speed while applying a load, and it was examined whether or not the surface of the decorative sheet 1 was scratched, and the scratch resistance was evaluated.
In addition, in this evaluation test, the decorative sheet 1 which was not scratched under a load of 2 kg or more was judged to be acceptable because it may be used for a place such as a floor where a load is significantly applied.

<Haze value measurement test>
Here, the haze value is defined as a value obtained by calculating the integrated value (total light transmittance) of the light beams emitted from the other surface when the light incident from one surface of the object is emitted to the other surface. This is a value obtained by dividing the value (diffuse transmittance) obtained by deriving the integral value (linear transmittance) of only the linear component of the emitted light rays by the total light transmittance, and is expressed as a percentage. It indicates that the property is high. This haze value is determined by the internal haze determined by the internal state of the object such as crystallinity and spherulite size in the crystal part, and the external haze determined by the state of the surface of the object such as the presence or absence of irregularities on the entrance and exit surfaces. Determined. In the present invention, when simply referred to as a haze value, it means a value determined by an internal haze and an 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; 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, 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 expressed as a percentage was calculated as a haze value. In the present invention, those having a haze value of less than 15% were judged to be acceptable.

<Bending whitening test>
In the bending whitening test, the decorative sheet was attached to a wooden building material such as MDF using an appropriate adhesive, and the wooden building material was attached to the back of the decorative sheet-attached surface so as to reach about 5 μm immediately below the decorative sheet. A straight groove is cut from the end face of the sheet to the opposite end face, and the decorative sheet is bent along the groove at 90 ° together with the wooden building material to determine the presence or absence of whitening to such an extent that the design of the decorative sheet is impaired. did. The evaluation of bending whitening was performed by visual sensory evaluation, and the results are shown in Table 1.

<Sign of appearance change>
：: No whitening or slight whitening ×: Whitening or cracking Table 1 shows the results of the coin scratch evaluation test, the haze value measurement test result, and the bending whitening evaluation result of each of Examples and Comparative Examples.

  As can be seen from Table 1, each of the decorative sheets 1 of Examples 1 to 11 in which the peak area ratio x of the transparent resin sheet 4 is set to x ≧ 0.4 was also used in the coin scratch test in which a load of 2 kg or more was applied. No flaws were found, and the haze value was found to be 14% or less, exhibiting extremely excellent scratch resistance and transparency. On the other hand, in the decorative sheets 1 of Comparative Examples 1 and 2 in which the peak area ratio x of the transparent resin sheet 4 was set to x <0.4, remarkable scratches were recognized in a coin scratch test with a load of 1 kg. The haze value was 15.1 or more, which was poor in scratch resistance and transparency.

Further, in Examples 7 to 11 in which the nucleating agent vesicles were added, the haze value was extremely low at 8.4% or less even when compared with the other Examples and Comparative Examples, and it had excellent transparency. You can see that there is.
In the transparent resin layer of Example 11 where x> 1.0, although the coin scratch evaluation and the haze value passed, whitening occurred in the bending whitening test.
From the above results, the peak area ratio x of the transparent resin sheet 4 as the transparent resin layer 4 is 0.4 or more, preferably 0.4 ≦ x ≦ 1.0, so that the scratch resistance and the transparency are excellent. At the same time, it was revealed that a decorative sheet 1 in which whitening caused by stretching or bending does not impair the design of the decorative sheet can be obtained.

In addition, by adding a nucleating agent vesicle to the transparent resin sheet 4, the dispersibility of the nucleating agent in the transparent resin sheet 4 is improved, and the decorative sheet 1 having extremely high transparency and excellent design is provided. It has become clear that can be obtained.
The decorative sheet 1 of the present invention is not limited to the above embodiments and examples, and various changes can be made without departing from the characteristics of the present invention.

REFERENCE SIGNS LIST 1 decorative sheet 2 concealing layer 3 picture printing layer 4 transparent resin layer
4a Embossed pattern 5 Top coat layer 6 Primer layer 7 Raw material layer 8 Adhesive layer

Claims (10)

Having a transparent resin layer containing a crystalline polypropylene resin as a main component,
The transparent resin layer state, and are values of 0.4 or more of the peak area ratio x represented by the following formula (1),
The transparent resin layer contains a nano-sized nucleating agent,
A decorative sheet , wherein the nucleating agent is at least one of a metal salt of a phosphoric acid ester, a metal salt of benzoic acid, a metal salt of pimelic acid, and cyanine blue .
Here, S040, S130, and Sam in the following formula (1) are peak areas calculated from an X-ray diffraction spectrum obtained by X-ray diffraction of the transparent resin layer, and S040 is a Miller index of α-crystal polypropylene. The peak area according to (040), S130 represents the peak area according to the Miller index (130) of polypropylene α crystal, and Sam represents the amorphous peak area.
Peak area ratio x = (S040 + S130) / (Sam) Expression (1) Further having a concealing layer formed on one side of the transparent resin layer,
The decorative sheet according to claim 1, wherein the concealing layer contains flake-like aluminum. Decorative sheet of the peak area ratio x of the transparent resin layer according to claim 1 or claim 2, characterized in that a 0.4 ≦ x ≦ 1.0. 4. The transparent resin layer according to claim 1, wherein the nano-sized nucleating agent is contained in the transparent resin layer in a state where the nucleating agent is included in a vesicle having an outer membrane of a single-layer film . The decorative sheet according to any one of the preceding claims. The decorative sheet according to claim 4, wherein the vesicle containing the nano-sized nucleating agent has an average particle size in a range of 200 nm to 375 nm. The crystalline polypropylene resin as a main component, the following (2) Ri der value 0.4 or more of the peak area ratio x represented by the formula,
The crystalline polypropylene resin contains a nano-sized nucleating agent,
The transparent resin sheet , wherein the nucleating agent is at least one of a metal salt of a phosphoric acid ester, a metal salt of benzoic acid, a metal salt of pimelic acid, and cyanine blue .
Here, S040, S130, and Sam in the following formula (2) are peak areas calculated from an X-ray diffraction spectrum obtained by X-ray diffraction of the transparent resin sheet, and S040 is a Miller index of α-crystal polypropylene. The peak area according to (040), S130 represents the peak area according to the Miller index (130) of polypropylene α crystal, and Sam represents the amorphous peak area.
Peak area ratio x = (S040 + S130) / (Sam) Equation (2) Containing nucleating agent nanosized, nucleating agents of the nano-sized claim 6, characterized in that the state in which nucleating agent is contained in vesicles comprising outer membrane of the single-layer film transparent resin sheet. The transparent resin sheet according to claim 7, wherein the average particle size of the vesicle containing the nano-sized nucleating agent is in a range of 200 nm or more and 375 nm or less. Having a transparent resin layer containing a crystalline polypropylene resin as a main component,
In the transparent resin layer, the resin temperature of the crystalline polypropylene resin, the cooling temperature of the crystalline polypropylene resin, and the temperature of the crystalline polypropylene resin are set such that the value of the peak area ratio x represented by the following formula (3) becomes 0.4 or more. Adjusting at least one of the cooling times of the crystalline polypropylene resin,
The transparent resin layer contains a nano-sized nucleating agent,
The method for producing a decorative sheet, wherein the nucleating agent is at least one of a metal salt of a phosphoric acid ester, a metal salt of benzoic acid, a metal salt of pimelic acid, and cyanine blue.
Here, S040, S130, and Sam in the following formula (3) are peak areas calculated from an X-ray diffraction spectrum obtained by X-ray diffraction of the transparent resin layer, and S040 is a Miller index of α-crystal polypropylene. The peak area according to (040), S130 represents the peak area according to the Miller index (130) of polypropylene α crystal, and Sam represents the amorphous peak area.
Peak area ratio x = (S040 + S130) / (Sam) Equation (3) The resin temperature of the crystalline polypropylene resin and the cooling temperature of the crystalline polypropylene resin so that the crystalline polypropylene resin is a main component and the peak area ratio x represented by the following formula (4) is 0.4 or more. And adjusting at least one of the cooling times of the crystalline polypropylene resin,
The crystalline polypropylene resin contains a nano-sized nucleating agent,
The method for producing a transparent resin sheet, wherein the nucleating agent is at least one of a metal salt of a phosphoric acid ester, a metal salt of benzoic acid, a metal salt of pimelic acid, and cyanine blue.
Here, S040, S130 and Sam in the following formula (4) are peak areas calculated from an X-ray diffraction spectrum obtained by X-ray diffraction of the transparent resin sheet, and S040 is a Miller index of α-crystal polypropylene. The peak area according to (040), S130 represents the peak area according to the Miller index (130) of polypropylene α crystal, and Sam represents the amorphous peak area.
Peak area ratio x = (S040 + S130) / (Sam) Equation (4)

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