Decorative sheet, decorative material, and method for manufacturing decorative sheet

Abstract

To provide a single-layer decorative sheet capable of ensuring concealment, a decorative material, and a method for manufacturing the decorative sheet.SOLUTION: A decorative sheet 10 comprises a transparent base film 20 formed of a single-layer film, a sealer layer 55, a printed pattern layer 50, and a coloring layer 40 laminated sequentially on one surface of the transparent base film 20, and a surface protective layer 60 laminated on the other surface of the transparent base film 20. The sealer layer 55 contains an urethane resin with an inorganic filler added. The transparent base film 20 contains a dispersant as a nano-sized additive and does not have a laminate layer composed of other films on either surface of the transparent base film 20. By providing the sealer layer 55 containing the urethane resin with the inorganic filler added, the transparent base film 20, sealer layer 55, printed pattern layer 50, and coloring layer 40 are strongly bonded to each other, thereby making it unlikely that cracking occurs in the coloring layer 40.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a cosmetic sheet, a cosmetic material, and a method for manufacturing a cosmetic sheet.

Background Art

[0002] Conventionally, cosmetic sheets used indoors are attached to the surfaces of fixtures such as indoor doors and entrance storage shelves, and also to the surfaces of architectural materials such as moldings, baseboards, skirting boards, window frames, and door frames. These are used by matching the patterns of the fixtures and architectural materials for each house or room. Among the cosmetic sheets used there, in recent years, those made of olefin-based materials are mainly used due to the problem of gases during combustion (see, for example, Patent Documents 1 to 3). Also, in order to protect the pattern from surface wear, a multi-layered cosmetic sheet is widely used, in which a pattern is printed on a colored olefin sheet and a transparent olefin sheet is laminated thereon.

[0003] In addition, since the production of a multi-layered cosmetic sheet requires a printing process and a lamination process, a single-layer cosmetic sheet using a single-layer film as the base material layer has also been proposed (see, for example, Patent Document 4).

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Summary of the Invention

Problems to be Solved by the Invention

[0005] Incidentally, concealing property is required for a cosmetic sheet. That is, the surface of the cosmetic material base material is not necessarily in conformity with a desired design, and there may be defects such as color unevenness, knots, cracks, etc. or joints, etc. Therefore, it is necessary to sufficiently conceal these so that they do not show through the pattern and are visible from the surface.

[0006] As one method for improving the concealing property of a single-layer cosmetic sheet, increasing the addition amount of an inorganic filler such as titanium oxide in the colored layer constituting the cosmetic sheet can be mentioned. In this case, while the concealing property is improved, there is a concern about cracking of the coating film after coating the colored layer. This cracking of the coating film not only impairs the appearance but also causes a decrease in barrier performance against various liquids, gases, and chemicals, leading to a problem of deterioration of physical properties.

[0007] The present invention has been made in view of the above points, and an object thereof is to provide a single-layer cosmetic sheet, a cosmetic material, and a method for manufacturing a cosmetic sheet capable of ensuring concealing property.

Means for Solving the Problem

[0008] The cosmetic sheet according to one aspect of the present invention includes a transparent base material which is a single-layer film made of a transparent olefin sheet, a sealer layer, a printed pattern layer, and a colored layer laminated in order on one surface of the transparent base material, and a surface protection layer laminated on the other surface of the transparent base material. The sealer layer contains a urethane-based resin to which an inorganic filler is added. A dispersant as a nano-sized additive is added to the transparent base material, and it is characterized in that neither surface of the transparent base material has a laminate layer made of another film.

[0009] Further, the cosmetic material according to another aspect of the present invention is characterized by including the cosmetic sheet according to the above aspect and a base material bonded to the surface of the cosmetic sheet opposite to the surface protection layer. Furthermore, a method for manufacturing a cosmetic sheet according to another aspect of the present invention includes a first step of adding a dispersant as a nano-sized additive to a transparent olefin-based thermoplastic resin and extruding the mixture to form a transparent base film made of a single-layer film, a second step of laminating a sealer layer containing a urethane-based resin to which an inorganic filler is added, a printed pattern layer, and a colored layer in this order on one surface of the transparent base film, and a third step of forming a surface protection layer on the other surface of the transparent base film after or prior to the second step, and is characterized by being manufactured inline.

Advantages of the Invention

[0010] According to one aspect of the present invention, a single-layer cosmetic sheet with excellent concealment can be obtained.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Modes for Carrying Out the Invention

[0012] Hereinafter, embodiments 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 planar dimensions, the ratio of the thickness of each layer, etc. are different from the actual ones. Further, the embodiments shown below are examples of configurations for embodying the technical idea of the present invention, and the technical idea of the present invention is not limited to the materials, shapes, structures, etc. of the components being the following. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

[0013] FIG. 1 is a cross-sectional view schematically showing a decorative sheet according to an embodiment of the present invention. In FIG. 1, reference numeral 10 denotes a decorative sheet. Although not shown, for example, it is used indoors and is pasted on the surfaces of fixtures (interior doors, entrance storage) and millwork materials (partitions, moldings, sill plates, window frames, door frames), etc., and is used by matching the patterns of fixtures and millwork materials for each house or room.

[0014] The decorative sheet 10 includes the following layers, and each layer is provided in order from (1). Note that the following (1) to (6) will be described later. (1) Primer layer 30 (2) Coloring layer 40 (3) Printed pattern layer 50 (4) Sealer layer 55 (5) Transparent base material 20 (6) Surface protection layer 60

[0015] Note that the layers of the decorative sheet 10 are not limited to the above (1) to (6). For example, as shown in FIG. 1, an adhesive layer 70 and a release paper 80 may be added on the side of the primer layer 30. Further, the decorative sheet 10 may form an embossed portion 90 synchronized with the pattern of the printed pattern layer 50 on the surface side of the surface protection layer 60. Although not shown, a substrate may be adhered to the surface of the decorative sheet 10 on the side opposite to the coloring layer 40 of the primer layer 30 to form a decorative board.

[0016] Also, the above “(1) Primer layer 30” may be omitted. That is, if the above “(2) Coloring layer 40” has the function of a primer layer, the primer layer 30 can be omitted. Also, a moisture-proof layer may be provided on the side of the primer layer 30. In this case, the moisture-proof layer may be provided between the coloring layer 40 and the primer layer 30. When the primer layer 30 is not provided, the moisture-proof layer may be provided on the side opposite to the printed pattern layer 50 of the coloring layer 40.

[0017] Further, a barrier layer may be provided on the side of the primer layer 30. In this case, a barrier layer may be provided between the colored layer 40 and the primer layer 30. When the primer layer 30 is not provided, a barrier layer may be provided on the side opposite to the printed pattern layer 50 of the colored layer 40. Further, a moisture-proof layer and a barrier layer may be provided together. In this case, either layer of the moisture-proof layer and the barrier layer may be provided on the outermost surface side.

[0018] (Main features of the cosmetic sheet 10) The main features of the cosmetic sheet 10 are as follows. (1) The cosmetic sheet 10 according to an embodiment of the present invention is a single-layer film made of a transparent olefin sheet. On the back side of the transparent base film 20, a sealer layer 55, a printed pattern layer 50 formed by printing a pattern, a colored layer 40, and a primer layer 30 are formed in this order from the transparent base film 20 side. On the front side of the transparent base film 20, a surface protective layer 60 is formed. The cosmetic sheet does not have a laminate layer made of another film on either the front side or the back side of the transparent base film 20. The transparent base film 20 is a single-layer film manufactured by extrusion molding using a transparent polypropylene-based thermoplastic resin, and a dispersant as a nano-sized additive is added to the transparent base film 20.

[0019] Since the cosmetic sheet 10 does not have a lamination process with other sheets during manufacturing, the number of manufacturing processes can be reduced, and the manufacturing processes from printing to applying the surface protective layer 60 can be performed in one inline process. Further, the cosmetic sheet 10 can also be synchronized with the pattern by applying a gloss / matte coat to the surface protective layer 60 as needed.

[0020] Furthermore, the cosmetic sheet 10 includes a sealer layer 55 made of a urethane-based resin added with an inorganic filler such as silica. Therefore, it is possible to make the colored layer 40 less likely to crack. As a result, even when the amount of white pigment such as titanium oxide added to the coloring layer 40 is increased to enhance concealment, cracking or the like is less likely to occur in the coloring layer 40, and it is possible to improve concealment while suppressing deterioration of appearance and physical properties.

[0021] (2) In addition, since the conventional decorative sheet is multilayered, there is a limit in film formation when thinning the sheet, and there is also a problem that the hardness of the sheet cannot be obtained. On the other hand, since the decorative sheet 10 according to an embodiment of the present invention is single-layered, it is easy to thin it, and by using an additive of nanosize, the sheet can be made hard even with a thin film. As a result, excellent moisture-proof property can be obtained.

[0022] (3) The decorative sheet 10 is formed with an embossed portion 90 synchronized with the pattern of the printed pattern layer 50. Here, when the decorative sheet is multilayered, it is difficult to achieve synchronous expression between the application of the printed pattern layer 50 and the surface protection layer 60 on the surface of the laminate film. On the other hand, the decorative sheet 10 according to an embodiment of the present invention can be easily synchronized by applying a pattern print and the embossed portion 90 in-line on the front and back surfaces of the transparent base material 20 which is a transparent olefin sheet.

[0023] (4) According to the decorative sheet 10 according to an embodiment of the present invention, first, if the frame material is made a single color, it becomes possible to respond in advance to any pattern of the door portion, so that the pattern of the door portion can be determined later, or even when the door portion is aged and the pattern is changed, it is possible to respond only by changing the door portion without breaking and replacing the frame material. Of course, the door portion itself can also be made a single color. Further, according to the decorative sheet 10, even in an apartment or the like, by unifying all rooms with a single color, it becomes easier to increase the lot and improve productivity or reduce the unit price, so there is an advantage in using a single-color sheet.

[0024] (5) Since the cosmetic sheet 10 has the adhesive layer 70 and the release paper 80 on the side of the primer layer 30, the cosmetic sheet 10 can be easily and quickly adhered to the base material. (6) Since the base material is adhered to the side of the primer layer 30 in the cosmetic material using the cosmetic sheet 10, it can be easily and quickly used as a cosmetic material. (7) By using the manufacturing method of the cosmetic sheet 10 according to an embodiment of the present invention, a highly functional cosmetic sheet 10 can be easily and quickly manufactured.

[0025] (Configuration of each layer) (Transparent base film 20) The transparent base film 20 serves as a support for the cosmetic sheet 10 and is made of a transparent olefin sheet. The transparent base film 20 is formed by adding a dispersant as a nano-sized additive to, for example, a transparent polypropylene-based thermoplastic resin. Further, it is preferable that a weather-resistant agent is blended with, for example, the transparent polypropylene resin constituting the transparent base film 20. Since the transparent base film 20 is a single layer, it is easy to make it thinner, and by using a nano-sized additive, the sheet can be made hard even if it is a thin film.

[0026] (Primer layer 30) As shown in FIG. 1, the primer layer 30 is located on the side opposite to the printed pattern layer 50 of the colored layer 40 and is mainly provided for the purpose of improving adhesiveness. In addition to improving adhesiveness, the functions of the primer layer 30 also include surface stabilization after surface treatment, corrosion prevention of the metal surface, imparting adhesiveness, preventing deterioration of the adhesive, and the like. The primer layer 30 is formed by coating a urethane-based resin so that the solid content is 1 g / m 2 by, for example, the gravure printing method.

[0027] For the primer layer 30, for example, urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, polyester-based, etc. can be adopted. In particular, a two-component curable urethane-based primer agent or the like obtained by blending polyester polyol and polyisocyanate is preferable. Further, when inorganic powders such as silica, barium sulfate, and calcium carbonate are added to these materials to form the primer layer 30, it is effective in improving the adhesive strength due to the anchoring effect.

[0028] (Coloring layer 40) As shown in FIG. 1, the coloring layer 40 is located on the surface opposite to the transparent base material 20 of the printed pattern layer 50, and is formed by using a printing method, and is a concealing layer provided mainly for the purpose of imparting concealment. The coloring layer 40 is, for example, printed by a gravure printing method using a two-component urethane-based resin in which a white pigment of titanium oxide is mixed with a urethane resin. Note that the coloring layer 40 may be a solid layer.

[0029] (Printed pattern layer 50) As shown in FIG. 1, the printed pattern layer 50 is located on the surface opposite to the transparent base material 20 of the sealer layer 55, and is formed by using a printing method, and is provided for the purpose of imparting design to the decorative sheet 10. The printed pattern layer 50 is, for example, a pattern printed with a urethane-based resin by a gravure printing method.

[0030] As the printing method, for example, the gravure printing method is exemplified, but it is not limited thereto, and various printing methods such as offset printing method, letterpress printing method, flexographic printing method, screen printing method, inkjet printing method, and electrostatic printing method can be applied. The type of the pattern of the printed pattern layer 50 is arbitrary depending on the purpose of use, the preference of the user, etc., and for example, wood grain pattern, stone grain pattern, abstract pattern, etc. are common. The type of the pattern is not limited to the types exemplified above, and for example, solid printing over the entire surface may be used.

[0031] In addition, although urethane resins were exemplified as the printing ink, the invention is not limited thereto, and for example, coloring agents such as organic or inorganic dyes or pigments may be used, or they may be dispersed in a binder made of a synthetic resin together with appropriate additives such as fillers, tackifiers, plasticizers, stabilizers, dispersants, defoamers, leveling agents, surfactants, desiccants, etc., and solvents or diluents.

[0032] (Sealer layer 55) As shown in FIG. 1, the sealer layer 55 is located on the surface opposite to the surface protection layer 60 of the transparent base material 20 and is provided for the purpose of improving the adhesion between the transparent base material 20 and the printed pattern layer 50. The sealer layer 55 is, for example, a urethane resin to which an inorganic filler such as silica is added, printed on one surface of the transparent base material 20 by a gravure printing method. The sealer layer 55 may contain appropriate additives such as fillers, tackifiers, plasticizers, stabilizers, dispersants, defoamers, leveling agents, surfactants, desiccants, etc., and may be dispersed in a binder made of a synthetic resin together with a solvent or a diluting solvent.

[0033] Since the decorative sheet 10 has the sealer layer 55, the printability of the transparent base material 20 and the adhesion to the printed pattern layer 50 can be enhanced. In particular, by adding an inorganic filler such as silica, swelling of the sealer layer 55 when the coloring layer 40 is applied can be suppressed, or shrinkage of the sealer layer 55 after the coloring layer 40 is applied can be suppressed, making it difficult for cracks to occur in the coloring layer 40. Therefore, compared with the case where the sealer layer 55 is not provided, the addition amount of pigments such as titanium oxide added to the coloring layer 40 can be increased, that is, the concealability can be improved.

[0034] (Surface protection layer 60) The surface protection layer 60, also referred to as a top coat, is located on the surface opposite to the sealer layer 55 of the transparent base material 20 as shown in FIG. 1 and is formed using a printing method. The surface protection layer 60 is provided for the purpose of imparting surface physical properties such as abrasion resistance and water resistance. As shown in Fig. 1, the surface protection layer 60 is composed of a primer layer 61 applied to the surface of the transparent base material 20 and a topcoat layer 62 applied to the surface of the primer layer 61. The topcoat layer 62 has a lower gloss than the primer layer 61.

[0035] For example, an acrylic two-component curable resin (acrylic urethane resin manufactured by DIC Graphics Co., Ltd.) is applied to the primer layer 61 to a thickness of 6 μm. The topcoat layer 62 is coated with the same resin having a lower gloss and printed with a pattern synchronized with the printed pattern layer 50.

[0036] That is, by applying a gloss / matte coat to the surface protection layer 60, it is also possible to synchronize with the pattern. Further, an embossed portion 90 synchronized with the pattern of the printed pattern layer 50 may be formed on the surface of the topcoat layer 62.

[0037] Here, when referring to the embossed portion 90, it has an image of a certain height difference. However, the height difference between the primer layer 61 and the topcoat layer 62 synchronized with the pattern is actually only on the order of several μm. Applying a gloss / matte coat to the surface protection layer 60 has the same meaning as the expression of synchronizing with the pattern. Furthermore, the surface protection layer 60 is subjected to an antiviral treatment. As the antiviral treatment, an antiviral agent is added to the surface protection layer 60. As the antiviral agent, for example, a silver-based inorganic additive (Bioside TB-B100) manufactured by Taisho Techno Co., Ltd. carrying silver ions is used.

[0038] Here, since the surface protection layer 60 is composed of the primer layer 61 and the topcoat layer 62, the antiviral agent may be added to both the primer layer 61 and the topcoat layer 62, or may be attached only to the topcoat layer 62 located on the surface side of the surface protection layer 60.

[0039] Although an antiviral agent was added to the surface protective layer 60, the present invention is not limited thereto, and the antiviral agent may be applied to the surface side of the surface protective layer 60, at least to the surface of the topcoat layer 62.

[0040] (Resin material of the transparent base film 20) Examples of the resin material constituting the transparent base film 20 include thermoplastic resins. There is no particular limitation on the thermoplastic resin, and the same materials as those of the thermoplastic resins conventionally used as the base material layer or the like in the conventional decorative sheet 10 can be used.

[0041] Examples of the thermoplastic resin include polyolefin resins such as polyethylene, polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, ethylene-α-olefin copolymer, propylene-α-olefin copolymer; polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate, polyarylate, polycarbonate; olefin-based copolymer resins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene-(meth)acrylic acid (ester) copolymer, ethylene-unsaturated carboxylic acid copolymer metal neutralized product (ionomer); acrylic resins such as poly(meth)acrylonitrile, polymethyl (meth)acrylate, polyethyl (meth)acrylate, polybutyl (meth)acrylate, polyacrylamide; polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon; styrene resins such as polystyrene, AS resin, ABS resin; vinyl resins such as polyvinyl chloride, polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal, polyvinyl butyral; fluorine-based resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, ethylene-perfluoroalkyl vinyl ether copolymer; or mixtures, copolymers, composites, laminates, etc. of two or more of them can be used.

[0042] In particular, in view of the increasing social concern about environmental problems in recent years, it is not preferable to use a thermoplastic resin containing chlorine (halogen) such as polyvinyl chloride resin as the thermoplastic resin, and it is preferable to use a non-halogen-based thermoplastic resin.

[0043] Particularly, from the viewpoints of various physical properties, processability, versatility, economy, etc., it is most preferable to use a polyester-based resin (amorphous or biaxially oriented) or a polyolefin-based resin, particularly a polyolefin-based resin, as the non-halogen-based thermoplastic resin. For example, as the polyolefin-based resin, it is preferable to use a polypropylene resin containing 30% by mass or more and 100% by mass or less of a highly crystalline homopolypropylene resin having an isotactic pentad fraction (mmmm fraction) of 95% or more.

[0044] In the transparent base film 20, if necessary, for example, one or more selected from various additives such as a filler, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a lubricant, a flame retardant, an antibacterial agent, an antifungal agent, a friction reducing agent, a light scattering agent, and a gloss modifier may be added.

[0045] (Modification example of the transparent base film 20) The transparent base film 20 is composed of a single-layer film (transparent layer) made of a transparent olefin sheet as shown in FIG. 1. However, the transparent base film 20 may be formed of a transparent olefin sheet composed of two types of three layers laminated in the order of a transparent skin layer 21 / a transparent core layer 22 / a transparent skin layer 21 as shown in FIG. 2.

[0046] (Transparent core layer 22) In the drawing, the transparent core layer 22 and the transparent skin layer 21 are shown as forming separate layers, but in actuality, the transparent core layer 22 and the transparent skin layer 21 are continuous and there is no interface. For the transparent core layer 22, for example, a material obtained by blending a weathering agent with a transparent polypropylene resin is used. Examples of the resin material constituting the transparent core layer 22 include thermoplastic resins. The thermoplastic resin is not particularly limited, and the same resin material as that of the transparent base film 20 can be used.

[0047] (Transparent skin layer 21) The transparent skin layer 21 is formed by adding a dispersant as a nano-sized additive to a transparent polypropylene-based thermoplastic resin. Further, an inorganic filler is added to the transparent skin layer 21 in addition to the dispersant as a nano-sized additive. Transparent skin layer 21: Transparent core layer 22: Transparent skin layer 21 are co-extruded so that the thickness ratio is 0.5:9:0.5, and a transparent base film 20 with a total thickness of 50 μm is produced. There is no particular limitation on the thermoplastic resin constituting the transparent skin layer 21, and the same resin material as that of the transparent core layer 22 can be used.

[0048] (Nano-sized additives etc. (nucleating agent)) The transparent skin layer 21 contains an inorganic filler in addition to the dispersant as a nano-sized additive, and is hereinafter also referred to as a "nano-sized nucleating agent". The nano-sized nucleating agent is preferably added and used in the form of a nucleating agent vesicle, which is encapsulated in a vesicle having an outer membrane of a single-layer film, to the polypropylene resin.

[0049] Further, in the cosmetic sheet 10, part of the nucleating agent in the resin constituting the transparent skin layer 21 may be encapsulated in the vesicle in a state where a part of the nucleating agent is exposed. Since the transparent skin layer 21 contains a nucleating agent, the crystallinity can be improved, and the scratch resistance (scratch resistance) of the cosmetic sheet 10 can be improved.

[0050] (Particle size of nano-sized nucleating agent) The nano-sized nucleating agent preferably has an average particle size of 1 / 2 or less of the wavelength region of visible light. Specifically, since the wavelength region of visible light is 400 nm or more and 750 nm or less, the average particle size is preferably 375 nm or less.

[0051] Due to the extremely small particle size of the nano-sized nucleating agent, the number and surface area of the nucleating agent present per unit volume increase in inverse proportion to the cube of the particle diameter. As a result, the distance between each nucleating agent particle becomes closer. When crystal growth occurs from the surface of a single nucleating agent particle added to the resin, the end of the growing crystal immediately contacts the end of the crystal growing from the surface of another nucleating agent particle adjacent to the single nucleating agent particle, and the growth of each crystal is inhibited as the ends of the mutual crystals impede growth. Therefore, in the crystalline part of the crystalline resin, the average particle diameter of the spherulites can be reduced, for example, the spherulite size can be reduced to 1 μm or less.

[0052] As a result, a high-hardness resin film with a high degree of crystallinity can be obtained, and since the stress concentration between spherulites generated during bending processing is efficiently dispersed, a resin film that suppresses cracking and whitening during bending processing can be realized. When the nucleating agent is simply added, the nucleating agent in the resin undergoes secondary aggregation, resulting in an increase in particle size. On the other hand, when the nucleating agent vesicle is added, the dispersibility in the resin is improved, so the number of crystal nuclei with respect to the added amount of the nucleating agent increases significantly compared to the case of simply adding the nucleating agent.

[0053] For this reason, the average particle diameter of the spherulites in the crystalline part of the resin becomes smaller, and the occurrence of cracking and whitening during bending processing can be suppressed. Therefore, by adding the nucleating agent vesicle, the degree of crystallinity can be further increased, making it possible to better balance the improvement of the elastic modulus and processability. The transparent skin layer 21 is formed of, for example, a resin material in which a nucleating agent is added in the range of preferably 0.05 parts by mass or more and 0.5 parts by mass or less, more preferably 0.1 parts by mass or more and 0.3 parts by mass or less, based on 100 parts by mass of a polypropylene resin as the main component.

[0054] When using the nucleating agent vesicle, the addition amount of the nucleating agent to the resin material is the addition amount converted to the nucleating agent in the nucleating agent vesicle. When the addition amount of the nucleating agent is less than 0.05 parts by mass, the crystallinity of polypropylene may not be sufficiently improved, and the scratch resistance of the transparent skin layer 21 may not be sufficiently improved.

[0055] Also, when the addition amount of the nucleating agent exceeds 0.5 parts by mass, since there are too many crystal nuclei, the spherulite growth of polypropylene is inhibited conversely, and as a result, the crystallinity of polypropylene may not be sufficiently improved, and the scratch resistance of the transparent skin layer 21 may not be sufficiently improved. Here, the "main component" refers to a resin material that occupies 50% by mass or more of the resin material constituting the transparent skin layer 21.

[0056] (Method for nano-sizing the nucleating agent) Also, as a method for nano-sizing the nucleating agent, for example, a solid-phase method in which mechanical pulverization is mainly performed on the nucleating agent to obtain nano-sized particles, a liquid-phase method in which synthesis or crystallization of nano-sized particles is performed in a solution in which the nucleating agent or the nucleating agent is dissolved, a gas-phase method in which synthesis or crystallization of nano-sized particles is performed from a gas or vapor composed of the nucleating agent or the nucleating agent, etc. can be appropriately used. Examples of the solid-phase method include a ball mill, a bead mill, a rod mill, a colloid mill, a conical mill, a disk mill, a hammer mill, a jet mill, etc.

[0057] Also, examples of the liquid-phase method include a crystallization method, a coprecipitation method, a sol-gel method, a liquid-phase reduction method, a hydrothermal synthesis method, etc. Further, examples of the gas-phase method include an electric furnace method, a chemical flame method, a laser method, a thermal plasma method, etc.

[0058] (Supercritical reverse phase evaporation method) As a method for nano-sizing the nucleating agent, the supercritical reverse phase evaporation method is preferable. The supercritical reverse phase evaporation method is a method for producing a capsule (nano-sized vesicle) encapsulating a target substance using carbon dioxide under supercritical state or temperature conditions or pressure conditions above the critical point.

[0059] Supercritical carbon dioxide means carbon dioxide in a supercritical state at a critical temperature (30.98 °C) and a critical pressure (7.3773 ± 0.0030 MPa) or higher, and carbon dioxide under temperature conditions or pressure conditions above the critical point means carbon dioxide under conditions where only the temperature or only the pressure exceeds the critical conditions.

[0060] Further, as a specific nanosizing treatment by the supercritical reverse phase evaporation method, first, an aqueous phase is injected into a mixed fluid of supercritical carbon dioxide, a phospholipid as an outer membrane forming substance, and a nucleating agent as an encapsulated substance, and stirred to generate an emulsion of supercritical carbon dioxide and the aqueous phase.

[0061] Next, by reducing the pressure, carbon dioxide expands and evaporates, causing a phase inversion, and generating nanocapsules (nanovesicles) in which the phospholipid covers the surface of the nucleating agent particles with a monolayer membrane. By using this supercritical reverse phase evaporation method, unlike the conventional encapsulation method in which the outer membrane becomes a multi-layer membrane on the surface of the nucleating agent particles, capsules with a monolayer membrane can be easily generated, so that smaller diameter capsules can be prepared.

[0062] The nucleating agent vesicles are prepared, for example, by the Bangham method, the extrusion method, the hydration method, the surfactant dialysis method, the reverse phase evaporation method, the freeze-thaw method, the supercritical reverse phase evaporation method, etc. Among them, the nucleating agent vesicles are preferably prepared using the supercritical reverse phase evaporation method in particular.

[0063] (Outer membrane constituting the nucleating agent vesicle) The outer membrane constituting the nucleating agent vesicle is composed of, for example, a monolayer membrane. Further, the outer membrane is composed of a substance containing a biological lipid such as a phospholipid, for example.

[0064] In this specification, a nucleating agent vesicle whose outer membrane is composed of a substance containing a biological lipid such as a phospholipid is referred to as a nucleating agent liposome. Examples of the phospholipid constituting the outer membrane include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soybean lecithin, hydrogenated soybean lecithin, and sphingomyelins such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0065] (Other substances serving as the outer membrane) Examples of other substances serving as the outer membrane of the vesicles include nonionic surfactants and dispersants such as mixtures of these with cholesterol or triacylglycerol.

[0066] Among these, examples of nonionic surfactants include one or more of polyglycerol ether, dialkyl glycerol, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly(2-vinylpyridine), polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethyl ethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc. Examples of cholesterol include cholesterol, α-cholestanol, β-cholestanol, cholestane, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, or colecalciferol, etc., which can be used.

[0067] Also, the outer membrane of the liposome may be formed from a mixture of phospholipid and a dispersant. In the cosmetic sheet 10, it is preferable that the nucleating agent vesicle be a radical scavenging liposome having an outer membrane made of phospholipid. By configuring the outer membrane from phospholipid, the compatibility between the resin material, which is the main component of the cosmetic sheet 10, and the vesicle can be made good.

[0068] The nucleating agent is not particularly limited as long as it is a substance that serves as a crystallization starting point when the resin crystallizes. Examples of the nucleating agent include metal phosphate esters, metal benzoates, metal pimelates, metal rosins, benzylidene sorbitol, quinacridone, cyanine blue, and talc. In particular, in order to maximize the effect of the nano-sizing treatment, it is preferable to use metal phosphate esters, metal benzoates, metal pimelates, and metal rosins, which are non-melting types and can be expected to have good transparency. However, when the material itself can be made transparent by the nano-sizing treatment, colored quinacridone, cyanine blue, talc, etc. can also be used. Further, a melting type of benzylidene sorbitol may be appropriately mixed with the non-melting type of nucleating agent and used.

[0069] (Features of the transparent skin layer 21) As described above, the cosmetic sheet 10 is characterized in that the transparent skin layer 21 contains a resin material and a nucleating agent.

[0070] Further, the cosmetic sheet 10 is characterized in that when forming the transparent skin layer 21, a nucleating agent encapsulated in vesicles is added to the resin material to crystallize the resin material. By adding the nucleating agent encapsulated in vesicles to the resin composition, the effect of dramatically improving the dispersibility of the nucleating agent in the resin material, that is, in the transparent skin layer 21, is achieved. On the other hand, it can be considered difficult and unrealistic to directly identify the nucleating agent encapsulated in vesicles based on the structure and properties of the object in the state of the completed cosmetic sheet 10 depending on the situation. The reason is as follows.

[0071] The nucleating agent added in the state of vesicles is in a dispersed state with high dispersibility and is highly dispersed in the transparent skin layer 21 even in the state of the laminate which is a precursor of the produced cosmetic sheet 10. However, in the manufacturing process of the cosmetic sheet 10, usually, various treatments such as compression treatment and curing treatment are performed on the laminate, and in such treatments, the outer membrane of the vesicles encapsulating the nucleating agent may be crushed or a chemical reaction may occur.

[0072] Therefore, due to the processing steps of the cosmetic sheet 10, there is a high possibility that the outer membrane of the nucleating agent in the completed cosmetic sheet 10 is crushed, the occurrence state of the chemical reaction varies, and the nucleating agent may not be enclosed (encased) by the outer membrane. And when the nucleating agent is not enclosed by the outer membrane, it is difficult to specify the physical properties of the nucleating agent itself within a numerical range. Also, it is assumed that there may be cases where it is difficult to determine whether the constituent material of the crushed outer membrane is the outer membrane of the vesicle or a material added separately from the nucleating agent.

[0073] Thus, although the present disclosure differs from the prior art in that the nucleating agent is blended with high dispersion in the cosmetic sheet 10, it is also assumed that in the state of the cosmetic sheet 10, it is impractical to specify within a numerical range obtained by analyzing its structure and properties based on measurement whether it is because the nucleating agent was added in the state of being enclosed in a vesicle.

[0074] (Barrier layer) The barrier layer is mainly provided for the purpose of suppressing gas permeation. For example, it can be provided by applying or printing a two-component curable acrylic resin by means of a bar coater, a gravure printing method, or the like.

[0075] Here, the cosmetic sheet is attached to, for example, a wood-based substrate to become a decorative material. When the cosmetic sheet is attached to a wood-based substrate, there is a concern about discoloration of the base material for pale printing due to β-caryophyllene, which is a kind of terpene, a volatile organic compound released from the heat-treated compressed wood that becomes the wood-based substrate. By providing the barrier layer, discoloration due to volatile organic compounds diffused from the substrate can be prevented.

[0076] (Manufacturing method of the cosmetic sheet 10) The cosmetic sheet 10 has the above-described configuration, and its manufacturing method has the following first to third steps and is manufactured inline.

[0077] Here, "inline" means that since there is no laminating process for laminating films, printing, which usually involves multiple processes, can be processed in one line, that is, on one production line. That is, the manufacturing process from printing to applying the surface protection layer 60 can be carried out in one inline process.

[0078] (1) First step The first step is a process of manufacturing a transparent base material 20 by adding a dispersant as a nano-sized additive to a transparent polypropylene-based thermoplastic resin and performing extrusion molding.

[0079] (2) Second step The second step is a process of sequentially forming a sealer layer 55, a printed pattern layer 50, a colored layer 40, and a primer layer 30 on one side (the back side) of the transparent base material 20 manufactured in the first step.

[0080] (3) Third step The third step is a process of forming a surface protection layer 60 on the other side (the front side) of the transparent base material 20 manufactured in the first step after or prior to the second step.

[0081] The order of the above steps is two ways: the order of the first step, the second step, and the third step, and the order of the first step, the third step, and the second step.

[0082] (Decorative material) Although not shown in the figure, the decorative material is formed by using an adhesive or the like on the side of the primer layer 30 of the decorative sheet 10 having the above-described configuration and adhering a base material. Also, the decorative material can be configured by peeling off the release paper 80 in FIG. 1 and directly adhering the base material to the adhesive layer 70. Here, the base material may be made of any type such as wood, steel, resin, etc. For example, it may be composed of a non-combustible steel plate or a non-combustible material defined in Notification No. 1400 of the Ministry of Construction. A substrate may be used as the base material, and a decorative sheet may be adhered to the substrate to form a decorative board. At this time, a moisture-proof film may be adhered to the surface of the substrate opposite to the surface to which the decorative sheet is adhered.

[0083] (Another embodiment of the layer structure on the back side of the transparent base film 20) Although not shown, the layer structure on the back side of the transparent base film 20 may be as follows. (a) Only the printed pattern layer 50 and the colored layer 40 may be formed in this order on the back side of the transparent base film 20. (b) Only the printed pattern layer 50, the colored layer 40, and the primer layer 30 may be formed in this order on the back side of the transparent base film 20.

Example

[0084] In order to confirm the effect of the cosmetic sheet 10 according to the present invention, a cosmetic sheet according to Example 1 was produced as a cosmetic sheet for evaluation.

[0085] (Example 1) The cosmetic sheet according to Example 1 is a single-layer sheet and was produced using the following materials and the following procedure. First, a transparent base film was produced. Specifically, a sheet-shaped transparent base film with a thickness of 70 μm was produced by extrusion molding using a resin obtained by adding a light-resistant agent, a dispersant as a nano-sized additive, etc. to a transparent polypropylene resin.

[0086] Second, on one surface (back surface) of the transparent base film, a sealer layer made of a urethane-based resin to which silica was added was formed by a bar coater, and further, a colored layer made of a two-component urethane-based resin to which an inorganic filler was added was formed. Thereby, the cosmetic sheet of Example 1 composed of a colored layer, a sealer layer, and a transparent base film was produced.

[0087] (Comparative Example 1) The cosmetic sheet according to Comparative Example 1 is the same as the cosmetic sheet of Example 1 except that in the second step, a sealer layer was formed using a urethane-based resin in which silica was not added (the content of the inorganic filler is about 1% or less).

[0088] 〔Evaluation method〕 〔Presence or absence of cracks〕 For each cosmetic sheet, visually check whether there are cracks in the coating film. Those with visible cracks were marked as "×", and those without cracks were marked as "○". 〔Concealment (color difference measurement)〕 For each cosmetic sheet, it was placed on a BYK color chart (black and white base paper), and the color difference was measured using a color chroma meter CR-400 (D65 light source) manufactured by Konica Minolta Inc. 〔Evaluation results〕 For each cosmetic sheet, the measurement results are shown in Table 1.

[0089]

Table 1

[0090] In both Example 1 and Comparative Example 1, the color differences were comparable and it was confirmed that concealment was obtained. However, in Comparative Example 1 where no inorganic filler was added to the sealer layer, cracks were confirmed. In Example 1 where an inorganic filler was added to the sealer layer, no cracks were confirmed.

[0091] Incidentally, the present invention can be configured as follows, for example. (1) A transparent base material which is a single-layer film composed of a transparent olefin sheet, A sealer layer, a printed pattern layer, and a colored layer laminated in sequence on one surface of the transparent base material, A surface protection layer laminated on the other surface of the transparent base material, having The sealer layer contains a urethane-based resin to which an inorganic filler is added, A dispersant as a nano-sized additive is added to the transparent base material, A cosmetic sheet characterized in that neither surface of the transparent base material has a laminate layer made of another film. (2) The transparent base material is composed of a core layer and two skin layers arranged with the core layer sandwiched therebetween, and the cosmetic sheet according to (1) above. (3) The cosmetic sheet according to (2) above, wherein an inorganic filler is added to each of the two skin layers. (4) The cosmetic sheet according to any one of (1) to (3) above, wherein the colored layer contains titanium oxide. (5) The cosmetic sheet according to any one of (1) to (4) above, wherein an embossed portion that synchronizes with the pattern of the printed pattern layer is formed on the surface of the surface protection layer opposite to the transparent base material. (6) The cosmetic sheet according to any one of (1) to (5) above, wherein a primer layer is formed on the surface opposite to the surface protection layer. (7) The cosmetic sheet according to any one of (1) to (5) above, wherein a moisture-proof layer is formed on the surface opposite to the surface protection layer. (8) The cosmetic sheet according to any one of (1) to (5) above, wherein a moisture-proof layer and a primer layer are formed in this order on the surface opposite to the surface protection layer. (9) The cosmetic sheet according to any one of (1) to (8) above, wherein an adhesive layer and a release paper are formed in this order on the surface opposite to the surface protection layer. (10) The cosmetic sheet according to any one of (1) to (9) above, wherein a barrier layer is provided on the surface opposite to the surface protection layer. (11) The cosmetic sheet according to any one of (1) to (9) above, wherein a barrier layer and a primer layer are provided in this order on the surface opposite to the surface protection layer. (12) A cosmetic sheet according to any one of (1) to (11) above, and a base material bonded to the surface of the cosmetic sheet opposite to the surface protection layer, characterized by comprising a cosmetic material. (13) The cosmetic material according to the above (12), characterized in that a moisture-proof film is adhered to the side of the base material opposite to the cosmetic sheet. (14) A first step of adding a dispersant as a nano-sized additive to a transparent olefin-based thermoplastic resin and extrusion-molding to form a transparent base web made of a single-layer film; A second step of laminating, in this order, a sealer layer containing a urethane-based resin to which an inorganic filler is added, a printed pattern layer, and a colored layer on one surface of the transparent base web; A third step of forming a surface protection layer on the other surface of the transparent base web after or prior to the second step, the method for manufacturing a cosmetic sheet, characterized by being manufactured inline. The method for manufacturing a cosmetic sheet, characterized by being manufactured inline. (15) The first step is a step of forming a transparent base web, which is a single-layer film obtained by extrusion-molding a transparent core layer using a polypropylene-based transparent thermoplastic resin and transparent skin layers located on the front and back surfaces of the transparent core layer, respectively, and adding a dispersant as a nano-sized additive to the transparent thermoplastic resin, the method for manufacturing a cosmetic sheet according to the above (14).

Explanation of reference numerals

[0092] 10 Cosmetic sheet 20 Transparent base web 21 Transparent skin layer 22 Transparent core layer 30 Primer layer 40 Colored layer 50 Printed pattern layer 55 Sealer layer 60 Surface protection layer 61 Undercoat layer 62 Topcoat layer 70 Adhesive layer 80 Release paper 90 Embossed portion

Claims

1. A transparent base fabric which is a single-layer film composed of a transparent olefin sheet, A sealer layer, a printed pattern layer, and a colored layer sequentially laminated on one surface of the transparent base fabric, A surface protection layer laminated on the other surface of the transparent base fabric, and The sealer layer contains a urethane resin to which an inorganic filler is added, A dispersant as a nano-sized additive is added to the transparent base fabric, The decorative sheet is characterized in that neither surface of the transparent base fabric has a laminate layer made of another film.

2. The decorative sheet according to claim 1, wherein the transparent base fabric is composed of a core layer and two skin layers disposed sandwiching the core layer.

3. The decorative sheet according to claim 2, wherein an inorganic filler is added to each of the two skin layers.

4. The decorative sheet according to claim 1, wherein the colored layer contains titanium oxide.

5. The decorative sheet according to claim 1, wherein an embossed portion synchronized with the pattern of the printed pattern layer is formed on the surface of the surface protection layer opposite to the transparent base fabric.

6. The decorative sheet according to claim 1, wherein a primer layer is formed on the surface opposite to the surface protection layer.

7. The decorative sheet according to claim 1, wherein a moisture-proof layer is formed on the surface opposite to the surface protection layer.

8. The decorative sheet according to claim 1, wherein a moisture-proof layer and a primer layer are formed in this order on the surface opposite to the surface protection layer.

9. The decorative sheet according to claim 1, wherein an adhesive layer and a release paper are formed in this order on the surface opposite to the surface protective layer.

10. The decorative sheet according to claim 1, wherein a barrier layer is provided on the surface opposite to the surface protective layer.

11. The decorative sheet according to claim 1, wherein a barrier layer and a primer layer are provided in this order on the surface opposite to the surface protective layer.

12. The decorative sheet according to any one of claims 1 to 11, and a base material bonded to the surface opposite to the surface protective layer of the decorative sheet, characterized in that it comprises a decorative material.

13. The decorative material according to claim 12, wherein a moisture-proof film is adhered to the surface of the base material on the side opposite to the decorative sheet.

14. A first step of adding a dispersant as a nano-sized additive to a transparent olefin-based thermoplastic resin and extrusion-molding to form a transparent base film made of a single-layer film, A second step of laminating a sealer layer, a printed pattern layer, and a colored layer containing a urethane-based resin to which an inorganic filler is added in this order on one surface of the transparent base film, A third step of forming a surface protective layer on the other surface of the transparent base film after the second step or prior to the second step, and A method for manufacturing a decorative sheet, characterized in that it is manufactured inline.

15. The method for manufacturing a decorative sheet according to claim 14, wherein the first step is a step of forming a transparent base film, which is a single-layer film obtained by extrusion-molding a transparent core layer made of a polypropylene-based transparent thermoplastic resin and transparent skin layers located on the front and back surfaces of the transparent core layer, respectively, and having a dispersant added as a nano-sized additive to the transparent thermoplastic resin.

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