Transparent resin film, method for manufacturing a transparent resin film, decorative panel, and method for manufacturing a decorative panel.

Abstract

The present invention provides a transparent resin film which has superior design properties as a result of being textured, and which makes it possible to impart weathering resistance while suppressing yellowing and preventing a degradation of the design properties, even if irradiated with an electron beam during production. The present invention relates to a transparent resin film for protecting a pattern layer that has been layered onto one surface of a substrate. The transparent resin film is characterized by being textured on the reverse side from a side that is layered on the pattern layer and by comprising at least a transparent resin layer and a transparent surface protection layer that are layered in the given order, the transparent surface protection layer comprising an ionizing radiation–curable resin, and the transparent resin layer and / or the transparent surface protection layer containing a triazine ultraviolet absorber.

Description

[Technical Field]

[0001] The present invention relates to a transparent resin film, a method for manufacturing a transparent resin film, a decorative panel, and a method for manufacturing a decorative panel. [Background technology]

[0002] When it is desired to decorate the components used in building materials, furniture, home appliances, etc., decorative panels are commonly used.

[0003] Typically, in decorative laminates, a transparent resin film is laminated onto the base material to protect the pattern layer and provide surface performance. To improve the weather resistance of transparent resin films, weather-resistant agents may be added to the layers that make up the transparent resin film.

[0004] Patent Document 1 discloses an overlaminating film comprising a transparent polypropylene resin film with a thickness of 40 to 100 μm containing a triazine-based ultraviolet absorber and a hindered amine-based light stabilizer, with a protective layer laminated on one side and an adhesive layer laminated on the other side. Patent Document 1 also discloses the use of an ionizing radiation-curable resin as the protective layer.

[0005] In recent years, in order to add visual and tactile appeal to the design, transparent resin films are sometimes subjected to embossing or other processes to create uneven or textured surfaces. However, while Patent Document 1 discloses protecting the printed surface from light to prevent fading, it does not consider forming an uneven surface on the overlaminating film, and therefore does not possess the aesthetic appeal required in recent years.

[0006] On the other hand, in recent years, when forming protective layers using ionizing radiation-curable resins, a manufacturing method has been adopted in which the layer is cured by irradiating it with a high-energy electron beam in order to improve productivity.

[0007] When a transparent resin film has a layer to which a weather-resistant agent has been added, curing an ionizing radiation-curable resin by irradiation with an electron beam can cause the layer containing the weather-resistant agent to yellow, depending on the type of weather-resistant agent, leading to a decrease in aesthetic appeal. [Prior art documents] [Patent Documents]

[0008] [Patent Document 1] Japanese Patent Publication No. 2005-120255 [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] The present invention aims to solve the above-mentioned problems and provide a transparent resin film that has excellent design properties due to its uneven shape, and that can suppress yellowing even when irradiated with an electron beam during manufacturing, thereby preventing a decrease in design properties, while also providing weather resistance. [Means for solving the problem]

[0010] The present inventors have diligently studied to solve the above-mentioned problems and have found that, in a transparent resin film for protecting a pattern layer laminated on one side of a substrate, the film has an uneven shape on the side opposite to the side laminated to the pattern layer, and at least a transparent resin layer and a transparent surface protection layer made of an ionizing radiation-curable resin are laminated in this order, and the transparent resin layer and / or the transparent surface protection layer contains a triazine-based ultraviolet absorber, thereby having excellent design properties, providing weather resistance, suppressing yellowing caused by electron beams when curing the ionizing radiation-curable resin, and preventing a decrease in design properties, thus completing the present invention.

[0011] That is, the transparent resin film of the present invention is a transparent resin film for protecting a pattern layer laminated on one side of a base material, having a concavo-convex shape on the side opposite to the side laminated on the pattern layer, and at least a transparent resin layer and a transparent surface protection layer are laminated in this order. The transparent surface protection layer is made of an ionizing radiation-curable resin, and the transparent resin layer and / or the transparent surface protection layer contain a triazine-based ultraviolet absorber.

[0012] In the transparent resin film of the present invention, it is preferable that the thickness of the concave portion of the concavo-convex shape is 80 μm or more. Further, the transparent resin film of the present invention has a concavo-convex shape on the side where the pattern layer is laminated, and the R defined in JIS B 0601(2001) of the concavo-convex shape on the side where the pattern layer is laminated z is preferably 80 μm or less. Moreover, it is preferable to have an adhesive primer layer on the side opposite to the transparent surface protection layer side of the transparent resin layer. Also, the transparent resin layer is preferably made of a thermoplastic resin. Moreover, the transparent resin layer preferably has at least a two-layer structure. Also, the transparent resin layer preferably contains a flame retardant. Also, the transparent surface protection layer preferably contains a flame retardant. Moreover, the layer containing the flame retardant in the transparent resin layer preferably contains a filler. Also, the flame retardant is preferably at least one selected from the group consisting of a metal phosphinate-based flame retardant, a phosphazene-based flame retardant, and a NOR type hindered amine-based flame retardant. Also, the transparent surface protection layer preferably contains at least one of an antibacterial agent, an antiviral agent, and an anti-allergen agent. Moreover, it is preferable that it is a decorative panel provided with the transparent resin film and a base material having a pattern layer. The present invention provides a method for producing a transparent resin film, comprising a preparation step of preparing a transparent resin layer containing a triazine-based ultraviolet absorber, a coating step of applying an ionizing radiation-curable resin to one surface of the transparent resin layer, and an irradiation step of irradiating the ionizing radiation-curable resin with an electron beam. The above preparation step preferably involves preparing a thermoplastic resin and laminating a thermoplastic resin containing a triazine-based ultraviolet absorber onto one of the thermoplastic resins to obtain a transparent resin layer. Furthermore, it is preferable that the above-mentioned ionizing radiation-curable resin contains a triazine-based ultraviolet absorber. The present invention relates to a method for manufacturing a decorative laminate, comprising, in this order, a substrate on which a pattern layer is laminated and a transparent resin film of the present invention, characterized by comprising the steps of: forming an adhesive layer on the side of the transparent resin film on which the pattern layer is laminated, and bonding the transparent resin film and the pattern layer via the adhesive layer. [Effects of the Invention]

[0013] This invention provides a transparent resin film that has excellent design qualities due to its uneven surface, and while providing weather resistance, it also suppresses yellowing even when irradiated with electron beams during manufacturing, thereby preventing a decrease in design quality. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 is a schematic cross-sectional view showing an example of the transparent resin film of the present invention. [Figure 2] Figure 2 is a schematic cross-sectional view showing a preferred example of the transparent resin film of the present invention. [Figure 3] Figure 3 is a schematic diagram illustrating the thickness of the recesses in the uneven shape of a transparent resin film. [Figure 4] Figure 4 is a schematic diagram illustrating the thickness of the recesses in the uneven shape of a transparent resin film. [Figure 5] Figure 5 is a schematic cross-sectional view showing an example of a decorative panel. [Figure 6] Figures 6(a) and 6(b) are schematic diagrams illustrating the method for evaluating flame retardancy. [Modes for carrying out the invention]

[0015] <Transparent resin film> The transparent resin film of the present invention will be described below. In the following description, the lower and upper limits of a numerical range represented by "~" mean "greater than or equal to" (for example, α~β means α or greater and β or less).

[0016] The transparent resin film of the present invention is a transparent resin film for protecting a pattern layer laminated on one side of a substrate, and has an uneven shape on the side opposite to the side laminated to the pattern layer, wherein at least a transparent resin layer and a transparent surface protection layer are laminated in this order, the transparent surface protection layer is made of an ionizing radiation-curable resin, and the transparent resin layer and / or the transparent surface protection layer contain a triazine-based ultraviolet absorber.

[0017] Figure 1 is a schematic cross-sectional view showing an example of the transparent resin film of the present invention. The transparent resin film 10 of the present invention comprises at least a transparent resin layer 1 and a transparent surface protection layer 2 laminated in this order, the transparent surface protection layer 2 being made of an ionizing radiation-curable resin, and the transparent resin layer 1 and / or the transparent surface protection layer 2 containing a triazine-based ultraviolet absorber.

[0018] Figure 2 is a schematic cross-sectional view showing a preferred example of the transparent resin film of the present invention. In the transparent resin film 10 of the present invention, it is preferable that the transparent resin layer 1 has a two-layer structure comprising a transparent resin layer 1a and a transparent resin layer 1b. Furthermore, it is preferable to have an adhesive primer layer 3 on the side of the transparent resin layer 1 opposite to the transparent surface protective layer 2. The following describes each component.

[0019] (Transparent resin layer) The transparent resin film 10 of the present invention has a transparent resin layer 1.

[0020] The transparent resin layer 1 is not particularly limited as long as the pattern layer provided on the substrate is visible, and can include colorless transparent, colored transparent, or translucent, and the material is not limited, but it is preferable that it contains a thermoplastic resin.

[0021] Examples of the above-mentioned thermoplastic resins include olefin-based thermoplastic resins such as low-density polyethylene (including linear low-density polyethylene), medium-density polyethylene, high-density polyethylene, ethylene-α-olefin copolymer, homopolypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer saponified, or mixtures thereof; thermoplastic ester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, polycarbonate, and polyarylate; acrylic-based thermoplastic resins such as polymethyl methacrylate, polyethyl methacrylate, polyethyl acrylate, and polybutyl acrylate; polyamide-based thermoplastic resins such as nylon-6 and nylon-66; or polyimide, polyurethane, polystyrene, acrylonitrile-butadiene-styrene resin, ionomer, and polyvinyl chloride. These thermoplastic resins may be used individually or in mixtures of two or more types. Among these, olefin-based thermoplastic resins are preferred because they offer excellent printability and embossing suitability for the pattern layer, and are inexpensive.

[0022] The transparent resin layer 1 may have a two-layer structure (having a transparent resin layer 1a and a transparent resin layer 1b).

[0023] If the transparent resin layer 1 consists of at least two layers, each of the transparent resin layers 1 may be laminated via a transparent adhesive layer, as described later. Furthermore, adjacent transparent resin layers 1 may be continuously laminated using a thermal lamination method. As the above-mentioned thermal lamination method, known methods such as molten co-extrusion using a T-die can be used.

[0024] The thickness of the transparent resin layer 1 is preferably 20 μm or more and 300 μm or less, more preferably 40 μm or more and 200 μm or less, and even more preferably 50 μm or more and 150 μm or less. By keeping the lower limit of the thickness of the transparent resin layer within the above range, the scratch resistance and abrasion resistance of the decorative panel using the transparent resin film 10 are further improved. Conversely, if the upper limit of the thickness of the transparent resin layer exceeds the above range, the sharpness of the decorative panel using the transparent resin film 10 (meaning the visibility of the pattern layer, as described later) may decrease.

[0025] The transparent resin layer 1 may be colored. In this case, a coloring agent can be added to the thermoplastic resin. As the coloring agent, pigments or dyes used in the pattern layer described later can be used.

[0026] In the transparent resin film 10 of the present invention, the transparent resin layer 1 and / or the transparent surface protective layer 2 contain a triazine-based ultraviolet absorber. The following describes the case where the transparent resin layer 1 contains a triazine-based ultraviolet absorber.

[0027] Examples of the above triazine-based UV absorbers include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-triazine, and 4,4',4''-(1,3,5-triazine-2,4,6-triyltriimino)tris Examples include tris(2-ethylhexyl) benzoate, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, N,N',N''-tri(m-tolyl)-1,3,5-triazine-2,4,6-triamine, 2,4,6-tris(4-butoxy-2-hydroxyphenyl)-1,3,5-triazine, and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol. It can be used individually or in combination of two or more types.

[0028] When the transparent resin layer 1 has at least two layers, it is preferable that the transparent resin layer 1 on the side having the transparent surface protective layer 2 (for example, transparent resin layer 1a in the case of a two-layer structure) contains the above-mentioned triazine-based ultraviolet absorber, from the viewpoint of providing weather resistance, preventing yellowing due to electron beam emission when forming the transparent surface protective layer 2 described later, and from the viewpoint of adhesion with the pattern layer described later.

[0029] The content of the above-mentioned triazine-based ultraviolet absorber is preferably 0.1% by mass or more and 3% by mass or less, more preferably 0.2% by mass or more and 1% by mass or less, and even more preferably 0.5% by mass or less, based on the mass of the transparent resin layer 1. If the content of the above-mentioned triazine-based ultraviolet absorber in the transparent resin layer 1 is less than 0.1% by mass, it may not be possible to impart weather resistance, and if it exceeds 3% by mass, the transparency of the film may be impaired, reducing the aesthetic appeal of the decorative panel, or sufficient adhesion with the pattern layer described later may not be obtained, resulting in reduced processability. Furthermore, even when the transparent resin layer 1 has two or more layers, it is preferable that the amount of the triazine-based ultraviolet absorber is 0.1% by mass or more and 3% by mass or less, based on the mass of the layer containing the triazine-based ultraviolet absorber. When the transparent resin layer 1 has two or more layers, from the viewpoint of suitably suppressing yellowing during manufacturing, it is preferable that each of the two or more layers contains the triazine-based ultraviolet absorber, and it is more preferable that the content in each layer is 1% by mass or less, and even more preferable that it is 0.5% by mass or less. Furthermore, when the transparent resin layer 1 has two or more layers, from the viewpoint of appropriately imparting weather resistance, it is preferable that the layer closer to the transparent surface protective layer 2 has a higher content of the triazine-based ultraviolet absorber than the layer further away from the transparent surface protective layer 2.

[0030] Furthermore, it is preferable that the transparent resin layer 1 and / or the transparent surface protective layer 2 contain a flame retardant. Flame retardants reduce flammability by preventing char formation during combustion and by capturing radicals in combustion gases. The following describes the case where the transparent resin layer 1 contains a flame retardant.

[0031] Examples of the above-mentioned flame retardants include phosphinate metal salt-based flame retardants, phosphazene-based flame retardants, NOR-type hindered amine-based flame retardants, halogen-based flame retardants, antimony-based flame retardants, metal hydroxide-based flame retardants, and phosphate ester-based flame retardants. In particular, from an environmental standpoint or because it allows for reduced additive amounts and maintains the transparency of the layer containing the flame retardant, it is preferable to use at least one selected from the group consisting of phosphinate metal salt flame retardants, phosphazene flame retardants, and NOR-type hindered amine flame retardants. It is preferable to include at least one selected from the group consisting of phosphinate metal salt flame retardants and phosphazene flame retardants in terms of its property of trapping radicals generated from organic matter during combustion and making it difficult to continue combustion, and in horizontal flammability tests, it is preferable to include at least one selected from the group consisting of phosphinate metal salt flame retardants and phosphazene flame retardants in terms of its effect of suppressing the spread of flame. Furthermore, NOR-type hindered amine flame retardants are preferred because they have the effect of reducing the amount of heat generated in the ISO 5660-1 heat generation test and can also provide weather resistance.

[0032] Examples of the above-mentioned phosphinate metal salt-based flame retardants include aluminum trisdiethylphosphinate, aluminum trismethylethylphosphinate, aluminum trisdiphenylphosphinate, zinc bisdiethylphosphinate, zinc bismethylethylphosphinate, zinc bisdiphenylphosphinate, titanyl bisdiethylphosphinate, titanium tetrakisdiethylphosphinate, titanyl bismethylethylphosphinate, titanium tetrakismethylethylphosphinate, titanyl bisdiphenylphosphinate, and titanium tetrakisdiphenylphosphinate. Examples of commercially available phosphinate metal salt-based flame retardants include those manufactured by Clariant Japan, such as "EXOLITE OP-930," "EXOLITE OP-935," "EXOLITE OP-1230," "EXOLITE OP-1240," and "EXOLITE OP-1312."

[0033] Examples of the above-mentioned phosphazene-based flame retardants include phenoxyphosphazene, (poly)tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, m-tolyloxyphosphazene, p-tolyloxyphosphazene, o,m-tolyloxyphosphazene, o,p-tolyloxyphosphazene, m,p-tolyloxyphosphazene, o,m,p-tolyloxyphosphazene, etc.), and cyclic and / or linear C(C) such as (poly)xyloxyphosphazene. 1-6 Alkyl C 6-20 aryloxyphosphazenes, (poly)phenoxytriloxyphosphazenes (e.g., phenoxy-o-tolyloxyphosphazene, phenoxy-m-tolyloxyphosphazene, phenoxy-p-tolyloxyphosphazene, phenoxy-o,m-tolyloxyphosphazene, phenoxy-o,p-tolyloxyphosphazene, phenoxy-m,p-tolyloxyphosphazene, phenoxy-o,m,p-tolyloxyphosphazene, etc.), (poly)phenoxyxylyloxyphosphazene, (poly)phenoxytriloxyxylyloxyphosphazene, and other cyclic and / or linear C12C 6-20 Aryl C 1-10 Alkyl C 6-20Examples thereof include aryloxyphosphazenes, etc., preferably cyclic and / or chain phenoxyphosphazenes, cyclic and / or chain C 1-3 alkyl C 6-20 aryloxyphosphazenes, C 6-20 aryloxy C 1-3 alkyl C 6-20 Examples thereof include aryloxyphosphazenes (e.g., cyclic and / or chain trilyloxyphosphazenes, cyclic and / or chain phenoxytolylphenoxyphosphazenes, etc.). Also included are compounds having a crosslinked structure of 4,4'-sulfonyldiphenylene (bisphenol S residue), compounds having a crosslinked structure of 2,2-(4,4'-diphenylene)isopropylidene group, compounds having a crosslinked structure of 4,4'-oxydiphenylene group, compounds having a crosslinked structure of 4,4'-thiodiphenylene group, etc., i.e., compounds having a crosslinked structure of 4,4'-diphenylene group.

[0034] Examples of the above NOR-type hindered amine flame retardants include: 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine; bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-6-(2-hydroxyethylamino)-s-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl) adipate; 4 An oligomeric compound formed by the condensation of 4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine, which is terminally capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine; 4,4'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine, An oligomeric compound that is a condensation product with 4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)butylamino]-s-triazine; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-piperidine-4-yl)-6-chloro]-s-triazine; reaction of peroxidized 4-butylamino-2,2,6,6-tetramethylpiperidine, 2,4,6-trichloro-s-triazine, cyclohexane, and N,N'-ethane-1,2-diylbis(1,3-propanediamine). Products include (N,N',N'''-Tris{2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)n-butylamino]-s-triazine-6-yl}-3,3'-ethylenediiminodipropylamine); bis(1-undecanoxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate; 1-undecyloxy-2,2,6,6-tetramethylpiperidine-4-one; bis(1-stearyloxy-2,2,6,6-tetramethylpiperidine-4-yl) carbonate, etc.Examples of commercially available NOR-type hindered amine flame retardants include FlamestabNOR116FF, TINUVIN NOR371, TINUVIN XT850FF, TINUVIN XT855FF, and TINUVIN PA123 from BASF, and LA-81 from ADEKA Corporation.

[0035] The above flame retardants may be used individually or in combination of two or more types.

[0036] If the transparent resin layer 1 has at least two layers, it is preferable that the layer closer to the transparent surface protective layer 2 (for example, the transparent resin layer 1a in the case of a two-layer structure) contains the above-mentioned flame retardant, from the viewpoint of improving flame retardancy.

[0037] The content of the above-mentioned flame retardant is preferably 3% by mass or more, and more preferably 4.4% by mass or more, based on the mass of the transparent resin layer 1. Furthermore, the content of the above-mentioned flame retardant is preferably 20% by mass or less, and more preferably 15% by mass or less, based on the mass of the transparent resin layer 1. By setting the lower limit of the flame retardant content within the above range, the flame retardancy of the transparent resin film 10 is further improved. Furthermore, by setting the upper limit of the flame retardant content within the above range, the transparency of the transparent resin film 10 is further maintained. Furthermore, if the transparent resin layer 1 has two or more layers, the amount of the flame retardant is preferably 3% by mass or more, more preferably 4.4% by mass or more, preferably 20% by mass or less, and more preferably 15% by mass or less, based on the mass of the layer containing the above-mentioned flame retardant.

[0038] The transparent resin layer 1 preferably contains a filler. The above-mentioned filler is not particularly limited as long as it does not impair the transparency of the transparent resin layer 1, but a filler exhibiting an average particle size less than or equal to the wavelength of visible light is preferred in that it further improves the sharpness of the decorative panel using the transparent resin film 10. Examples of the above-mentioned fillers include inorganic fillers such as silica, calcium carbonate, talc, and clay.

[0039] It is preferable that the above-mentioned filler is contained in the same layer as the layer containing the above-mentioned flame retardant. In other words, if the transparent resin layer 1 is a single layer and contains the above-mentioned flame retardant, it is preferable that the transparent resin layer 1 contains the above-mentioned filler. Also, if the transparent resin layer 1 is a two-layer structure and one of the layers contains the above-mentioned flame retardant, it is preferable that the layer containing the above-mentioned flame retardant contains the above-mentioned filler.

[0040] The above-mentioned filler more preferably contains an inorganic filler having a polar group on its surface. The flame retardancy of the transparent resin film 10 is further improved, and the sharpness of the decorative panel using the transparent resin film 10 is further improved, by including an inorganic filler having polar groups on its surface in the layer containing the above-mentioned flame retardant. This is thought to be because the polar portion of the flame retardant is attracted to the polar groups on the surface of the inorganic filler having polar groups, and the presence of the flame retardant on the surface improves its dispersibility. As the inorganic filler having polar groups on the surface mentioned above, hydrophilic inorganic fillers can be used. For example, inorganic fillers having hydroxyl groups such as silanol groups on the surface can be used, and more specifically, hydrophilic silica can be used.

[0041] The silica used as the filler may be either natural or synthetic, and may be either crystalline or amorphous. Synthetic amorphous silica may be prepared by either a wet or dry method. The method for preparing synthetic wet silica using the wet method is not particularly limited and includes methods such as sedimentation and gelation. The method for preparing synthetic dry silica using the dry method is also not particularly limited and includes methods such as combustion and arcing. The silica used as the filler described above is preferably silica with a small average particle size, more preferably fumed silica obtained by combustion, and even more preferably hydrophilic fumed silica, as this further improves the sharpness of the decorative panel using the transparent resin film 10.

[0042] The BET specific surface area of ​​the above-mentioned hydrophilic fumed silica and other fillers is 50 m². 2 Preferably 130m / g or more. 2 More preferably 200m / g or more, 2 A value of 1 / g or more is even more preferable. Because the lower limit of the BET specific surface area of ​​the filler is within the above range, the average particle size is small, and in the case of hydrophilic fumed silica, the amount of silanol increases. This further suppresses the decrease in transparency of the transparent resin layer 1 due to the addition of the filler, and further improves the dispersibility of the flame retardant. As a result, the flame retardancy of the transparent resin film 10 and the sharpness of the decorative panel using the transparent resin film 10 are further improved. In addition, because the lower limit of the BET specific surface area of ​​the filler is within the above range, the flame retardancy of the transparent resin film 10 is improved, making it possible to reduce the amount of flame retardant.

[0043] In this specification, the BET specific surface area is the BET specific surface area measured by the nitrogen adsorption method in accordance with the measurement method compliant with DIN66131.

[0044] The hydrophilic fumed silica used as the filler can be a commercially available product. Examples of such commercially available products include AEROSIL 50, AEROSIL 130, AEROSIL 200, AEROSIL 300, and AEROSIL 380, manufactured by Nippon Aerosil Co., Ltd.

[0045] If the layer containing the above-mentioned flame retardant also contains a filler, the amount of filler in the layer containing the flame retardant is preferably 50 parts by mass or more, more preferably 100 parts by mass or more, and even more preferably 200 parts by mass or more, based on the amount of the above-mentioned flame retardant in the layer containing the flame retardant within the transparent resin layer 1 being 100 parts by mass. By keeping the lower limit of the filler content in the layer containing the above-mentioned flame retardant within the above-mentioned range, the sharpness of the decorative panel using the transparent resin film 10 is further improved. Furthermore, the filler content in the layer containing the above-mentioned flame retardant is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and even more preferably 10 parts by mass or less.

[0046] The transparent resin layer 1 may contain various additives such as matting agents, foaming agents, lubricants, antistatic agents, antioxidants, light stabilizers, radical scavengers, and softening components (e.g., rubber).

[0047] The transparent resin layer 1 may be subjected to surface treatments such as saponification, glow discharge treatment, corona discharge treatment, plasma treatment, ultraviolet (UV) treatment, and flame treatment, without departing from the spirit of the present invention.

[0048] (transparent surface protective layer) The transparent resin film 10 of the present invention has a transparent surface protective layer 2. The transparent surface protection layer 2 is a layer that imparts surface properties such as scratch resistance, abrasion resistance, water resistance, and stain resistance.

[0049] The transparent surface protective layer 2 is made of an ionizing radiation-curable resin. By making the transparent surface protective layer 2 from an ionizing radiation-curable resin, high surface hardness can be imparted.

[0050] As the above-mentioned ionizing radiation-curable resin, oligomers (hereinafter including so-called prepolymers, macromonomers, etc.) having radically polymerizable unsaturated bonds or cationic polymerizable functional groups in the molecule and / or monomers having radically polymerizable unsaturated bonds or cationic polymerizable functional groups in the molecule are preferably used. Here, ionizing radiation refers to electromagnetic waves or charged particles that have the energy to polymerize or crosslink molecules, and typically refers to electron beams (EB) or ultraviolet rays (UV).

[0051] Examples of the above-mentioned oligomers or monomers include compounds having radically polymerizable unsaturated groups such as (meth)acryloyl groups and (meth)acryloyloxy groups, or cationically polymerizable functional groups such as epoxy groups in their molecules. These oligomers and monomers can be used individually or in combination of multiple types. In this specification, the above-mentioned (meth)acryloyl group means either an acryloyl group or a methacryloyl group.

[0052] As oligomers having radically polymerizable unsaturated groups in the above molecules, oligomers such as urethane (meth)acrylate, polyester (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, and triazine (meth)acrylate can be preferably used, and urethane (meth)acrylate oligomers are even more preferred. Molecular weights of approximately 250 to 100,000 are usually used.

[0053] As monomers having radically polymerizable unsaturated groups in the above molecule, polyfunctional monomers are preferred, and polyfunctional (meth)acrylates are more preferred. Examples of the above-mentioned polyfunctional (meth)acrylates include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, bisphenol A ethylene oxide modified di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate {pentafunctional (meth)acrylate}, and dipentaerythritol hexa(meth)acrylate {hexafunctional (meth)acrylate}. Here, a polyfunctional monomer refers to a monomer having multiple radically polymerizable unsaturated groups.

[0054] The above-mentioned ionizing radiation-curable resin more preferably includes an ionizing radiation-curable resin composed of a urethane acrylate oligomer and a polyfunctional monomer, and it is particularly preferable that the urethane acrylate oligomer / polyfunctional monomer (mass ratio) of the ionizing radiation-curable resin is 6 / 4 to 9 / 1. Within this mass ratio range, the scratch resistance can be made even better. Furthermore, if necessary, monofunctional monomers may be used in addition to the ionizing radiation-curable resin described above, as long as they do not contradict the objectives of the present invention. Examples of the above monofunctional monomers include methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and phenoxyethyl (meth)acrylate.

[0055] The transparent surface protective layer 2 can be obtained by curing an ionizing radiation-curable resin composition made of the above-mentioned ionizing radiation-curable resin. The above-mentioned ionizing radiation-curable resin composition may contain a photopolymerization initiator. When the above-mentioned ionizing radiation-curable resin composition is a resin system having radically polymerizable unsaturated groups, acetophenones, benzophenones, thioxanthones, benzoin, and benzoin methyl ethers can be used individually or in combination as the above-mentioned photopolymerization initiator. Furthermore, if the ionizing radiation-curable resin composition is a resin system having cationic polymerizable unsaturated groups, aromatic diazonium salts, aromatic sulfonium salts, aromatic iodonium salts, metacerone compounds, benzoin sulfonic acid esters, etc., can be used as the photopolymerization initiator, either individually or in mixtures. The amount of these photopolymerization initiators added is approximately 0.1 to 10 parts by mass per 100 parts by mass of ionizing radiation-curable resin.

[0056] The transparent resin film 10 contains a triazine-based ultraviolet absorber in the transparent resin layer 1 and / or the transparent surface protective layer 2. From the viewpoint of providing weather resistance while preventing the aforementioned yellowing, it is preferable that the transparent surface protective layer 2 contains a triazine-based ultraviolet absorber, and it is more preferable that both the transparent resin layer 1 and the transparent surface protective layer 2 contain a triazine-based ultraviolet absorber. The following describes the case where the transparent surface protective layer 2 contains a triazine-based ultraviolet absorber.

[0057] As the triazine-based ultraviolet absorber mentioned above, those listed in the transparent resin layer 1 can be appropriately selected and used.

[0058] The content of the above-mentioned triazine-based ultraviolet absorber is preferably 0.1% by mass or more and 3% by mass or less, based on the mass of the transparent surface protective layer 2. If the content of the above-mentioned triazine-based ultraviolet absorber in the transparent surface protective layer 2 is less than 0.1% by mass, weather resistance may not be imparted, and if it exceeds 3% by mass, the transparency of the film may be impaired, reducing the aesthetic appeal of the decorative panel, or sufficient adhesion with the transparent resin layer 1 may not be obtained, resulting in reduced processability.

[0059] From the viewpoint of more favorably improving flame retardancy, the transparent resin layer 1 and the transparent surface protective layer 2 more preferably contain a flame retardant.

[0060] As the flame retardant mentioned above, those listed for the transparent resin layer 1 can be appropriately selected and used.

[0061] The content of the flame retardant in the transparent surface protective layer 2 is preferably 3% by mass and more preferably 4.4% by mass, with the total mass of the transparent surface protective layer 2 being 100% by mass. The upper limit of the flame retardant content is preferably 20% by mass and more preferably 15% by mass.

[0062] The transparent surface protective layer 2 may contain the aforementioned flame retardant. The transparent surface protective layer 2 contains a flame retardant, which reduces flammability by causing char formation and radical scavenging ability in the combustion gas in response to heat applied from the surface during combustion. The content of the flame retardant in the transparent surface protective layer 2 is preferably 3% by mass and more preferably 4.4% by mass, with the total mass of the transparent surface protective layer 2 being 100% by mass. The upper limit of the flame retardant content is preferably 20% by mass and more preferably 15% by mass.

[0063] From the viewpoint of improving flame retardancy while maintaining the sharpness of the decorative panel using the transparent resin film 10, the transparent surface protective layer 2 preferably contains the above-mentioned flame retardant and filler. As the filler mentioned above, any of those described in the transparent resin layer 1 can be appropriately selected and used, and silica is preferred, fumed silica is more preferred considering the dispersibility of the flame retardant, and hydrophilic fumed silica is even more preferred among fumed silicas.

[0064] The amount of the above-mentioned filler to be added is approximately 1 to 80 parts by mass per 100 parts by mass of the ionizing radiation-curable resin.

[0065] The transparent surface protective layer 2 may contain additives other than the fillers mentioned above. Examples of these additives include antioxidants, lubricants, foaming agents, ultraviolet absorbers, light stabilizers, deodorizers, antibacterial agents, antiviral agents, antiallergens, antifungal agents, and the like. In particular, the transparent surface protective layer 2 preferably contains at least one of an antibacterial agent, an antiviral agent, and an anti-allergen agent, if necessary.

[0066] The transparent surface protective layer 2 can impart antibacterial and antiviral properties to the transparent resin film 10 by containing antibacterial and antiviral agents. Furthermore, the transparent surface protective layer 2 can impart anti-allergen properties to the transparent resin film 10 by containing anti-allergen agents.

[0067] The above-mentioned antibacterial and antiviral agents can generally be broadly classified into organic and inorganic types. Organic antibacterial and antiviral agents include quaternary ammonium salts, quaternary phosphonium salts, pyridines, pyrithiones, benzimidazoles, organic iodines, isothiazolins, anions, and ethers. Examples of inorganic antibacterial and antiviral agents include those in which metal ions such as silver, copper, and zinc are supported on zeolites, apatite, zirconia, glass, molybdenum oxide, etc. Furthermore, the above-mentioned antibacterial and antiviral agents may be used individually or in combination of two or more.

[0068] Among the above-mentioned organic antibacterial and antiviral agents, antibacterial and antiviral agents of the benzimidazole type or anionic type that maintain their particle shape are particularly preferred. The phrase "maintaining particle shape" means that the particles remain in a granular state without dissolving within the composition that becomes the curable resin of the transparent surface protective layer 2 (the curable resin composition before curing). Therefore, during the process of forming the transparent surface protective layer 2, the benzimidazole compound particles or anionic compound particles tend to float to the surface, making it easier to concentrate the benzimidazole compound particles or anionic compound particles on the outermost surface of the transparent surface protective layer 2. Furthermore, by unevenly distributing benzimidazole-based compound particles or anionic compound particles on the outermost surface of the transparent surface protective layer 2, the amount of antibacterial or antiviral agent required to obtain the desired antibacterial and antiviral properties can be suppressed, thereby making it easier to prevent a decrease in the scratch resistance of the transparent surface protective layer 2.

[0069] The above-mentioned anionic antibacterial and antiviral agents preferably include, for example, styrene resins, styrene polymer derivative compounds, and unsaturated carboxylic acid derivative compounds. Furthermore, the above-mentioned styrene polymer derivative compound and unsaturated carboxylic acid derivative compound preferably contain at least one structure from among styrene, sodium sulfonate, acrylic acid, maleic acid, and fumaric acid, and more preferably contain all of these structures. This is because viruses exist in two types, with and without envelopes, and the structures of antibacterial and antiviral agents that can effectively inhibit the activity of each type are thought to be different. Therefore, for example, workman If the goal is to target only the influenza virus, which is an epinephrotic virus, then it is sufficient to include only styrene polymer derivative compounds, and in some cases, even just styrene resin alone may be enough to achieve the desired effect.

[0070] Among the inorganic antibacterial and antiviral agents mentioned above, silver-based antibacterial and antiviral agents are preferred from the viewpoint of having no biotoxicity and excellent safety. Among these, phosphate-based silver-supported glass compounds, silver zeolite compounds, and molybdenum-silver oxide double salt compounds are even more preferred because they exhibit antibacterial and antiviral properties even in small amounts, thus allowing for a reduction in the amount added. The average particle size of the above-mentioned inorganic antibacterial and antiviral agents is preferably, for example, 0.1 to 10 μm. With the above average particle size, the above antibacterial and antiviral agents can be suitably dispersed, and antibacterial and antiviral properties can be suitably imparted without unevenness.

[0071] When the above-mentioned silver-based antibacterial or antiviral agents are added to the transparent surface protective layer 2, discoloration may occur depending on the transparent surface protective layer 2 (discoloration may occur due to heat and light in the state of the paint to which the agents are added, or due to heat and light after the transparent surface protective layer 2 has been formed). In this case, it is possible to improve the situation by adding UV inhibitors, light stabilizers, etc., in a timely manner. For example, using a benzotriazole compound can be expected to improve the discoloration of the above-mentioned silver molybdenum oxide compound.

[0072] The amount of the above-mentioned antibacterial and antiviral agents is, for example, about 0.1 to 10 parts by mass per 100 parts by mass of ionizing radiation-curable resin.

[0073] The above-mentioned anti-allergen agent contains at least one of either an inorganic compound or an organic compound, and may be used alone or in combination of two or more. The above-mentioned anti-allergen agent may also be an antibacterial agent or an antiviral agent.

[0074] The inorganic compound described above is preferably a material on which a metal is supported. As materials supporting the above metals, at least one selected from the group consisting of titanium oxide, calcium phosphate, calcium silicate, zirconium phosphate, zeolite, silica alumina, magnesium silicate, and magnesium phosphate is preferred, among which titanium oxide and zirconium phosphate are preferred. The metal supported on the material comprising the above-mentioned metal is preferably at least one selected from the group consisting of gold, silver, platinum, zinc, and copper, with silver, zinc, and the like being preferred among these. Commercially available products such as "Parafine ANV-100: Silver supported on an inorganic compound" manufactured by Ohara Palladium Co., Ltd. and "Atomyball TZ-R: Zinc supported on titanium dioxide" manufactured by JGC Catalysts Co., Ltd. can be suitably used, and this anti-allergen agent is effective against various allergens such as dust mites and pollen.

[0075] The above organic compound is preferably a polymer containing at least one monomer component selected from the group consisting of a water-insoluble polymer containing a phenolic hydroxyl group, a polyphenol compound supported on an inorganic solid acid, styrene sulfonic acid, and its salts.

[0076] As the non-water-soluble polymer containing the phenolic hydroxyl group mentioned above, commercially available products such as "Allerbuster (product name)" manufactured by Sekisui Chemical Co., Ltd. and "Marukalinker M (product name)" manufactured by Maruzen Petroleum Co., Ltd. can be used.

[0077] Examples of polyphenol compounds supported on inorganic solid acids include combinations of polyphenol compounds and zirconium compounds, and commercially available products include "AllerRemove" (trade name) manufactured by Toagosei Co., Ltd. These anti-allergen agents are effective against various allergens such as dust mites and pollen.

[0078] As the styrenesulfonic acid and its salts mentioned above, materials such as those shown in Japanese Patent No. 6136433 can be used, and preferred examples include styrenesulfonate homopolymers, styrenesulfonate-styrenesulfonic acid copolymers, styrenesulfonate-styrene copolymers, styrenesulfonic acid-styrene copolymers, and styrenesulfonate-styrenesulfonic acid-styrene terpolymers.

[0079] The above-mentioned anti-allergen agent may be a mixture of an organic compound and an inorganic compound, for example, a mixture of an anionic phenolic material and a zinc-based material having anti-allergenic properties.

[0080] Examples of the above-mentioned anionic phenolic materials include tannins, tannic acid / tartrate, phenolsulfonic acid formaldehyde resins, sulfone compounds of novolac-type resins, methanesulfonic acid of novolac-type resins, methanesulfonic acid of resol-type resins, benzylated phenolsulfonic acid, thiophenol compounds, dihydroxy and diphenylsulfone compounds, ligant compounds, and their metal chelate compounds.

[0081] The zinc-based material may be appropriately selected from water-soluble zinc compounds, water-insoluble zinc compounds, zinc / metal oxide composite materials, etc. Preferably, the water-insoluble zinc compound and / or water-insoluble zinc-metal oxide composite particles are dispersed in water, the average particle size is 50 μm or less, and the metal oxide contains at least one of titania, silica, or alumina.

[0082] The amount of the above-mentioned anti-allergen agent is, for example, about 0.1 to 10 parts by mass per 100 parts by mass of ionizing radiation-curable resin.

[0083] The thickness of the transparent surface protective layer 2 is not particularly limited, but a preferred lower limit is 0.1 μm, a preferred upper limit is 50 μm, a more preferred lower limit is 1 μm, and a more preferred upper limit is 30 μm. If the thickness of the transparent surface protective layer 2 is less than 0.1 μm, it may not be possible to provide sufficient durability (scratch resistance, stain resistance, weather resistance, etc.), and if it exceeds 50 μm, the transmittance of the transparent resin film 10 of the present invention may decrease, and the visibility of the pattern on the pattern layer may decrease.

[0084] Furthermore, the transparent surface protective layer 2 may contain various additives as needed. Examples of these additives include thermoplastic resins such as urethane resin, polyvinyl acetal resin, polyester resin, polyolefin resin, styrene resin, polyamide resin, polycarbonate resin, acetal resin, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, and cellulose resin; lubricants such as silicone resin, wax, and fluorine resin; light stabilizers such as hindered amine radical scavengers; gloss and texture modifiers such as silica, acrylic beads, and mica; and colorants such as dyes and pigments.

[0085] (Adhesive primer layer) The transparent resin film 10 of the present invention preferably has an adhesive primer layer 3 on the side of the transparent resin layer 1 opposite to the transparent surface protective layer 2. The presence of the adhesive primer layer 3 allows for optimal adhesion between the pattern layer laminated on one side of the substrate and the substrate.

[0086] The adhesive primer layer preferably contains a binder resin. Examples of the binder resins mentioned above include urethane resin, acrylic resin, acrylic-urethane resin, acrylic-urethane copolymer resin, cellulose resin, polyester resin, and vinyl chloride-vinyl acetate copolymer. When a urethane acrylate oligomer is incorporated into the ionizing radiation-curable resin composition of the surface protective layer described above, urethane resin is preferred due to its adhesion to the surface protective layer and production efficiency.

[0087] The adhesive primer layer 3 preferably has a thickness of 0.5 μm or more and 10 μm or less. If it is 0.5 μm or more, suitable adhesion between the transparent resin film 10 and the substrate on which the pattern layer described later is laminated can be adequately ensured. If it is 10 μm or less, the transparent resin film 10 does not become too thick, sufficient transparency is obtained, and the design quality of the decorative panel can be adequately ensured. The adhesive primer layer 3 described above is more preferably 0.8 μm or more and 6 μm or less in thickness. The adhesive primer layer 3 may, if necessary, contain inorganic fine particles such as silica.

[0088] (Transparent adhesive layer) Any known adhesive can be used as the transparent adhesive layer. Examples include polyurethane, acrylic, polyolefin, polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, as well as butadiene-acrylonitrile rubber, neoprene rubber, and natural rubber. These adhesives may be used individually or in combination of two or more types, and may be two-component curing type, moisture curing type, ionizing radiation curing type, or adhesive (tack agent).

[0089] The transparent adhesive layer described above preferably has a thickness of about 0.1 to 30 μm after drying, and more preferably about 1 to 5 μm.

[0090] It is preferable to have a primer layer for the transparent surface protective layer between the transparent surface protective layer 2 and the transparent resin layer 1. By having the above-mentioned primer layer for the transparent surface protection layer, the adhesion between the transparent surface protection layer 2 and the transparent resin layer 1 can be made stronger. The above-mentioned primer layer for the transparent surface protective layer may contain the above-mentioned ultraviolet absorber. As the primer layer for the transparent surface protective layer described above, the same type as the adhesive primer layer described above can be suitably used.

[0091] (uneven shape) The transparent resin film 10 may have an uneven surface on the side on which the pattern layer described later is laminated. If the transparent resin film 10 has an uneven shape on the side on which the pattern layer described later is laminated, the R of that uneven shape as defined in JIS B 0601 (2001) z However, it is preferable that the particle size be 80 μm or less. The R shape of the uneven surface on the side to which the above pattern layer is laminated is defined in JIS B 0601 (2001). z If the thickness exceeds 80 μm, air bubbles are more likely to form between the pattern layer and the transparent resin film 10, which may reduce the aesthetic appeal of the decorative panel of the present invention. The R shape of the uneven surface on the side to which the above pattern layer is laminated is defined in JIS B 0601 (2001). z It is more preferable that the particle size is 60 μm or less, even more preferable that it is 55 μm or less, and particularly preferable that it is 50 μm or less. Furthermore, the R shape of the uneven surface on the side to which the above pattern layer is laminated is defined in JIS B 0601 (2001). z For example, the lower limit is 15 μm. In this specification, the above R z This can be obtained by measuring the surface roughness using a surface roughness measuring instrument ("SURFCOM-FLEX-50A", manufactured by Tokyo Seimitsu Co., Ltd.) under the following conditions. [Measurement conditions] Number of measurements: n=5 (5 arbitrary points) Calculation standard: JIS′01 Measurement type: Roughness measurement Evaluation length: 12.5mm Cutoff value: 2.5mm Measurement speed: 0.60mm / s Filter type: Gaussian Shape removal: straight line λs value: 8.0 μm If the uneven surface has directionality, measure the flow direction and the direction perpendicular to it, and select the one with the larger value in both directions (R). z Let's assume that.

[0092] The method for forming the above-mentioned uneven shape is not particularly limited and includes, for example, embossing by heat, or transferring the uneven shape using a shaping sheet. Examples of heat-induced embossing include embossing using a well-known sheet-fed or rotary embossing machine. Examples of embossed patterns include sand texture, hairline finish, pearlescent finish, wood grain groove, stone surface texture, fabric surface texture, and fine groove. Furthermore, while there are no particular limitations on the temperature used for embossing, a temperature that minimizes the disappearance of the raised and recessed pattern during heat-press molding (so-called embossing reversal) is preferable. Furthermore, if the pattern layer has an uneven shape on the side to which it is laminated, the uneven shape may be formed on both sides of the transparent resin film 10 using the method described above, or an uneven shape may be formed on one side of the transparent resin film 10 using the method described above, and the uneven shape on the other side may be formed to follow the uneven shape formed on the one side.

[0093] It is preferable that the transparent resin film 10 has an uneven surface on the side opposite to the side laminated with the pattern layer described later. On the side opposite to the side laminated with the pattern layer described later, it is preferable to appropriately adjust the uneven shape so that, for example, the average centerline roughness Ra specified in JIS B 0601 (1982) is within the range of 1 μm to 30 μm.

[0094] The thickness of the recessed portion of the uneven shape on the side opposite to the side laminated to the pattern layer is preferably 80 μm or more. If the thickness of the recessed portion of the uneven shape of the transparent resin film 10 is less than 80 μm, the decorative panel may not be able to be given sufficient durability (abrasion resistance, scratch resistance). Here, we will explain the "concave shape of the uneven surface" mentioned above. The "recessed portion of the uneven shape" mentioned above refers to the thinnest part of the transparent resin film 10, and as shown in Figure 3, it includes the deepest recess of the uneven shape of the transparent surface protective layer 2, which can be confirmed by microscopic observation of the cross-section of the transparent resin film 10. The length from the bottom of the deepest recess of the uneven shape on the transparent surface protective layer 2 side of the transparent resin layer 1 to the opposite side is the "thickness of the recessed portion of the uneven shape." Furthermore, if the uneven shape is formed on the side of the transparent surface protective layer 2, and the uneven shape extends to the opposite side, as shown in Figure 4, a protrusion will be generated on the opposite side corresponding to the deepest recess of the uneven shape on the transparent surface protective layer 2 side of the transparent resin layer 1. The length from the bottom of the deepest recess of the uneven shape on the transparent surface protective layer 2 side of the transparent resin layer 1 to the opposite side where such a protrusion exists will be the "thickness of the recess of the uneven shape". The upper limit of the thickness of the recesses in the uneven shape of the transparent resin film 10 is not particularly limited, but it is preferably, for example, 500 μm. As shown in Figure 3, the total thickness of the transparent resin film 10 is the length from the side having the transparent surface protective layer 2 to the opposite side. The preferred lower limit of this total thickness is 100 μm, the preferred upper limit is 500 μm, the more preferred lower limit is 140 μm, and the more preferred upper limit is 460 μm.

[0095] The various additives added to each of the above-mentioned layers of the transparent resin film 10 of the present invention (such as inorganic fillers added to the primer layer and surface protective layer) are preferably vesicled. The method for vesicling the various additives is not particularly limited and can be done by known methods, with supercritical reverse-phase evaporation being preferred.

[0096] Other vesicle formation methods include the Bangham method, extrusion method, hydration method, reverse-phase evaporation method, and freeze-thaw method. To briefly explain this vesicle formation method, the Bangham method described above involves placing chloroform or a chloroform / methanol mixed solvent into a container such as a flask, then adding and dissolving phospholipids. Subsequently, the solvent is removed using an evaporator to form a thin film composed of lipids, and after adding a dispersion of additives, the mixture is hydrated and dispersed using a vortex mixer to obtain vesicles. The extrusion method described above involves preparing a phospholipid solution of thin film and passing it through a filter instead of the mixer used as an external perturbation in the Bangham method described above to obtain vesicles. The hydration method described above is almost the same preparation method as the Bangham method, but it is a method of obtaining vesicles by gently stirring and dispersing without using a mixer. The reverse-phase evaporation method described above involves dissolving phospholipids in diethyl ether or chloroform, adding a solution containing additives to create a W / O emulsion, removing the organic solvent from the emulsion under reduced pressure, and then adding water to obtain vesicles. The above freeze-thaw method uses cooling and heating as external perturbations, and vesicles are obtained by repeating this cooling and heating process.

[0097] The supercritical reverse-phase evaporation method will be explained in detail below. The supercritical reverse-phase evaporation method described above is a method of forming capsule-shaped vesicles in which the various additives acting as encapsulating materials are contained within a single membrane by adding an aqueous phase containing various water-soluble or hydrophilic encapsulating materials to a mixture obtained by uniformly dissolving a substance that forms the outer membrane of a vesicle in carbon dioxide under supercritical conditions or at a temperature or pressure above the supercritical point. Supercritical carbon dioxide refers to carbon dioxide in a supercritical state above the critical temperature (30.98°C) and critical pressure (7.3773±0.0030 MPa), while carbon dioxide under temperature or pressure conditions above the critical point refers to carbon dioxide under conditions where only the critical temperature or only the critical pressure exceeds the critical conditions. By this method, single-layer lamellar vesicles with a diameter of 50 to 800 nm can be obtained. Generally, a vesicle is a general term for a small vesicle containing a liquid phase inside a closed, spherical membrane structure. In particular, those whose outer membrane is composed of biolipids such as phospholipids are called liposomes.

[0098] Examples of the phospholipids mentioned above include glycerophospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidic acid, phosphatidylglycerol, phosphatidylinositol, cardiolipin, egg yolk lecithin, hydrogenated egg yolk lecithin, soy lecithin, and hydrogenated soy lecithin, as well as sphingophospholipids such as sphingomyelin, ceramide phosphorylethanolamine, and ceramide phosphorylglycerol.

[0099] The materials that make up the outer film may also include nonionic surfactants or dispersants such as mixtures thereof with cholesterol or triacylglycerols.

[0100] As the nonionic surfactants mentioned above, one or more of the following can be used: polyglycerin ether, dialkylglycerin, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl ether, polyoxyethylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyethylene polyoxypropylene copolymer, polybutadiene-polyoxyethylene copolymer, polybutadiene-poly2-vinylpyridine, polystyrene-polyacrylic acid copolymer, polyethylene oxide-polyethylethylene copolymer, polyoxyethylene-polycaprolactam copolymer, etc.

[0101] The above-mentioned cholesterols may include one or more of the following: cholesterol, α-cholestanol, β-cholestanol, cholestan, desmosterol (5,24-cholestadien-3β-ol), sodium cholate, cholecalciferol, etc.

[0102] The outer membrane of the liposome described above may be formed from a mixture of phospholipid and a dispersant. In the decorative sheet of the present invention, by using liposomes formed from phospholipid for the outer membrane, the compatibility between the resin composition, which is the main component of each layer, and various additives can be improved.

[0103] (Method for manufacturing transparent resin film) The present invention provides a method for producing a transparent resin film 10, comprising a preparation step of preparing a transparent resin layer containing a triazine-based ultraviolet absorber, a coating step of applying an ionizing radiation-curable resin to one surface of the transparent resin layer, and an irradiation step of irradiating the ionizing radiation-curable resin with an electron beam.

[0104] The above preparation step preferably involves preparing a thermoplastic resin and laminating a thermoplastic resin containing a triazine-based ultraviolet absorber onto one of the thermoplastic resins to obtain a transparent resin layer. By including a triazine-based ultraviolet absorber in the transparent resin layer 1a on the side of the transparent resin film 10 having the transparent surface protective layer 2, yellowing caused by electron beam irradiation during the irradiation process can be more effectively suppressed, weather resistance can be more effectively provided, and adhesion to the pattern layer described later can be more effectively provided.

[0105] The above-mentioned ionizing radiation-curable resin preferably contains a triazine-based ultraviolet absorber. In the above coating process, a transparent surface protective layer 2 can be formed by applying an ionizing radiation-curable resin containing a triazine-based ultraviolet absorber. By including a triazine-based ultraviolet absorber in the transparent surface protective layer 2 of the transparent resin film 10, the aforementioned yellowing can be suppressed, and weather resistance can be suitably provided.

[0106] Examples of the coating process include applying a solution of an ionizing radiation-curable resin composition using coating methods such as gravure coating or roll coating. Furthermore, the amount of ionizing radiation-curable resin applied in the above coating process should be controlled to fall within a preferred range of the thickness of the transparent surface protective layer 2 described above.

[0107] As the electron source in the above irradiation process, for example, a Cockcroft-Walton type, Van de Graft type, resonant transformer type, insulated core transformer type, or various electron beam accelerators such as linear type, dynamitron type, and high-frequency type, which can irradiate electrons with an energy of 70 to 1000 keV, can be appropriately selected and used. The dose of ionizing radiation is preferably, for example, around 1 to 10 Mrad. Ultraviolet light can also be used; for example, light sources such as ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arc lamps, black lights, and metal halide lamps may be used, and irradiation may be performed in the wavelength range of 190 to 380 nm.

[0108] Methods for laminating each layer of the transparent resin film 10 include lamination via the transparent adhesive layer or adhesive primer layer, and lamination by a thermal lamination method. As the above-mentioned thermal lamination method, known methods such as molten co-extrusion using a T-die can be used.

[0109] <Decorative panel> As a decorative panel, the transparent resin film of the present invention is laminated on a substrate having a pattern layer. Figure 5 is a schematic cross-sectional view showing an example of a decorative panel. The decorative panel 20 has a pattern layer 12 laminated on one side of the base material 11, and has a structure in which the pattern layer 12 and the transparent resin film 10 of the present invention are laminated together via an adhesive layer 13. The following describes each component.

[0110] (base material) The base material 11 is not particularly limited, but can be appropriately determined, for example, according to the application of the decorative panel. The material constituting the base material 11 is not particularly limited, and known materials such as resin materials, wood materials, and metal materials can be cited. Among these, resin materials and wood materials, which possess rigidity and lightness, are preferred as the material constituting the base material. Composite materials of these materials may also be used. The above-mentioned resin material preferably contains, for example, a thermoplastic resin. The thermoplastic resins mentioned above include polyvinyl resins such as polyvinyl chloride resin, polyvinyl acetate resin, and polyvinyl alcohol resin; polyolefin resins such as polyethylene, polypropylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), and ethylene-(meth)acrylic acid resin; polyester resins such as polyethylene terephthalate resin (PET resin); acrylic resins, polycarbonate resins, polyurethane resins, acrylonitrile-butadiene-styrene copolymer resin (ABS resin), and acrylonitrile-styrene copolymer resin; diene rubbers such as styrene-butadiene rubber, isoprene rubber, and chloroprene rubber; non-diene rubbers such as butyl rubber and ethylene propylene rubber; natural rubber; thermoplastic elastomers; or mixed resins thereof. Among these, polyolefin resins, acrylonitrile-butadiene-styrene copolymer resins, polyvinyl chloride resins, and ionomers are particularly preferred. Furthermore, the above resin material may be foamed.

[0111] Furthermore, examples of the wood-based materials include various materials such as cedar, cypress, zelkova, pine, lauan, teak, and meranti. The core material may be any of the following made from these materials: veneer, wood veneer, wood plywood (including LVL), particleboard, medium-density fiberboard (MDF), high-density fiberboard (HDF), laminated wood, or laminated wood obtained by appropriately laminating these materials. Examples of the above-mentioned metal materials include iron and aluminum.

[0112] Furthermore, the substrate 11 may contain an inorganic compound. Including an inorganic compound can reduce the coefficient of thermal expansion of the substrate, and as a result, the water resistance of the transparent resin film 10 can be improved. Furthermore, the base material 11 may contain various additives as needed, such as colorants (pigments or dyes), fillers such as wood powder or calcium carbonate, matting agents such as silica, foaming agents, flame retardants, lubricants such as talc, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers.

[0113] Furthermore, if the base material 11 has a base material made of multiple resins, the types of resins forming the base material made of multiple resins may be the same or different, and the thickness of the base material made of multiple resins may be the same or different.

[0114] The base material 11 may have a hollow structure, or a slit groove or through hole may be provided in a part of the base material.

[0115] The size of the base material 11 is not particularly limited and can be determined as appropriate depending on the application of the decorative panel. The thickness of the base material 11 is not particularly limited; for example, it is preferably 0.01 mm or more, and more preferably 0.1 mm or more and 50 mm or less. Furthermore, the base material 11 includes not only flat plates but also roughly plate-shaped materials, and may also include those with uneven surfaces or curved surfaces. If the base material 11 is thin, less than 1 mm thick, the adhesive material described later may be provided on the back surface of the base material 11.

[0116] (Picture layer) The pattern layer 12 is a layer that provides decorative properties to the decorative panel. For example, it may be a uniformly colored opaque layer (solid print layer), a pattern layer formed by printing various patterns using ink and a printing press, or a layer that combines an opaque layer and a pattern layer (hereinafter referred to as the pattern layer).

[0117] By providing the aforementioned concealing layer, if the substrate is colored or has uneven coloring, the intended color can be given and the surface color can be evened out. Furthermore, by adding a pattern layer, decorative panels can be given patterns such as wood grain, marble patterns (e.g., travertine marble patterns) that mimic the surface of rocks, fabric patterns that mimic the texture of cloth or cloth, tile patterns, brick patterns, or combinations thereof such as marquetry, patchwork, letters, symbols, abstract patterns, floral patterns, landscapes, and characters. These patterns can be formed by multicolor printing using standard yellow, red, blue, and black process colors, or by multicolor printing using spot colors, where separate plates are prepared for each color that makes up the pattern.

[0118] The ink composition used in the pattern layer 12 is a binder resin mixed with colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, and curing agents as appropriate. There are no particular restrictions on the binder resin, but examples of preferred binder resins include urethane resin, acrylic resin, urethane-acrylic resin, urethane-acrylic copolymer resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, acrylic resin, polyester resin, and nitrocellulose resin. Any of these binder resins can be used individually or in combination of two or more. Furthermore, preferred colorants include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, lead yellow, titanium yellow, iron oxide, cadmium red, ultramarine, and cobalt blue; organic pigments such as quinacridone red, isoindolinone yellow, and phthalocyanine blue; or dyes; metallic pigments consisting of flaky foil pieces such as aluminum and brass; and pearlescent pigments consisting of flaky foil pieces such as titanium dioxide-coated mica and basic lead carbonate.

[0119] The thickness of the pattern layer 12 is not particularly limited, but is preferably 0.1 μm or more, and more preferably 0.5 μm or more and 600 μm or less. If the thickness of the pattern layer 12 is within the above range, it is possible to provide the decorative panel with an excellent design and also with opacity.

[0120] The decorative panel 20 may further have an adhesive layer, a primer layer, a backing layer, etc., as needed. In this case, the adherend may be provided on the back side of the adhesive layer, primer layer, backing layer, etc. The adhesive layer and primer layer described above can preferably be the same as those described for the transparent resin film 10.

[0121] (Backers) Examples of the above-mentioned backer layer include resin backer layers such as synthetic resin backer layers and foamed resin backer layers, wood-based backer layers such as cork, and nonwoven fabric backer layers, and it is preferable that it be located at the bottom layer of the base material 11 (on the side opposite to the side on which the transparent resin film 10 is laminated). By having the above-mentioned backer layer on the base material 11, the scratch resistance and impact resistance of the decorative panel can be further improved.

[0122] Examples of resins that make up the synthetic resin backer layer include polypropylene, ethylene-vinyl alcohol copolymer, polyethylene, polymethylpentene, polyethylene terephthalate, highly heat-resistant polyalkylene terephthalate (for example, polyethylene terephthalate in which part of the ethylene glycol is replaced with 1,4-cyclohexanedimethanol or diethylene glycol, so-called trade name PET-G (manufactured by Eastman Chemical Company)), polybutylene terephthalate, polyethylene naphthalate, polyethylene naphthalate-isophthalate copolymer, amorphous polyester (A-PET), polycarbonate, polyarylate, polyimide, polystyrene, polyamide, ABS, diene rubbers such as styrene-butadiene rubber, isoprene rubber, and chloroprene rubber, non-diene rubbers such as butyl rubber and ethylene propylene rubber, natural rubber, and thermoplastic elastomers. These resins can be used individually or in combination of two or more.

[0123] The above synthetic resin backer layer may contain hollow beads. The type, particle size, and content of the hollow beads described above can be those specified in Japanese Patent Publication No. 2014-188941.

[0124] The above backer layer may contain a flame retardant. As the above-mentioned flame retardant, one of those described for the transparent resin film 10 can be appropriately selected and used.

[0125] The thickness of the synthetic resin backer layer is not particularly limited, but for example, 100 to 600 μm is preferred, and 150 to 450 μm is more preferred.

[0126] Methods for forming the above-mentioned synthetic resin backer layer include calendering and extrusion molding of molten resin. Among these, extrusion molding of molten resin is preferred, and for example, extrusion molding using a T-die is more preferred.

[0127] The foamed resin backer layer may be located even lower than the synthetic resin backer layer (on the side opposite to the side with the uneven shape). The foamed resin backer layer described above can be the one described in Japanese Patent Publication No. 2014-188941.

[0128] (adherent material) If the base material 11 is thin (for example, 1 mm or less), the adhesive may be placed on the back side (the side opposite to the side with the transparent resin film 10).

[0129] The materials of the above-mentioned adherends include, for example, wood-based boards such as wood veneer, wood plywood, particleboard, MDF (medium-density fiberboard), HDF (high-density fiberboard); gypsum-based boards such as gypsum board and gypsum slag board; cement boards such as calcium silicate board, asbestos slate board, lightweight foamed concrete board, and hollow extruded cement board; fiber cement boards such as pulp cement board, asbestos cement board, and wood chip cement board; ceramic boards such as pottery, porcelain, earthenware, glass, and enamel; metal boards such as iron board, galvanized steel board, polyvinyl chloride sol coated steel board, aluminum board, and copper board; polyolefin resin board, acrylic resin board, ABS board, and more. Examples include thermoplastic resin sheets such as recarbonate sheets and polyvinyl chloride resin sheets; thermosetting resin sheets such as phenolic resin sheets, urea resin sheets, unsaturated polyester resin sheets, polyurethane resin sheets, epoxy resin sheets, and melamine resin sheets; and so-called FRP sheets, which are composites obtained by impregnating and curing resins such as phenolic resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, and diallyl phthalate resin into glass fiber nonwoven fabrics, cloths, paper, and other various fibrous substrates. These may be used individually or as composite substrates by laminating two or more of these types. The thickness of the adherend is not particularly limited.

[0130] Thermoplastic resin sheets and thermosetting resin sheets may contain various additives as needed, such as colorants (pigments or dyes), fillers such as wood powder or calcium carbonate, matting agents such as silica, foaming agents, flame retardants, lubricants such as talc, antistatic agents, antioxidants, ultraviolet absorbers, and light stabilizers.

[0131] (Manufacturing method for decorative panels) The present invention relates to a method for manufacturing a decorative laminate, comprising, in this order, a substrate on which a pattern layer is laminated and a transparent resin film of the present invention, characterized by comprising the steps of: forming an adhesive layer on the side of the transparent resin film on which the pattern layer is laminated, and bonding the transparent resin film and the pattern layer via the adhesive layer.

[0132] In the transparent resin film 10, when forming the uneven shape on the side opposite to the side laminated with the pattern layer 12, embossing or the like is applied to create the uneven shape. However, some unevenness is formed on the opposite side (base layer side) to the embossed side, following the uneven shape on the embossed side. In such cases, air can get trapped in the uneven shape on the side of the transparent resin film 10 where the pattern layer is laminated, resulting in what is known as air bubbles, which can reduce the aesthetic appeal. The manufacturing method for the decorative panel 20 of the present invention includes a step of forming an adhesive layer 13 on the side of the transparent resin film 10 that is laminated onto the pattern layer 12. This allows the adhesive layer 13 to penetrate into the recesses of the uneven shape on the side laminated onto the pattern layer 12, thereby preventing the occurrence of air bubbles and suppressing a decrease in design quality. The thickness of the decorative panel 20 is not particularly limited, but is preferably 0.05 mm or more, and more preferably 1 mm or more and 50 mm or less. [Examples]

[0133] Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0134] (Example 1) A transparent polypropylene film (60 μm thick, also called transparent resin layer b) was prepared, and a two-component curing urethane resin adhesive primer was applied to one side of transparent resin layer b to form an adhesive primer layer (2 μm thick). Next, a transparent polypropylene resin (100 μm thick, also called transparent resin layer a) containing a triazine-based UV absorber was laminated to one side of transparent resin layer b (the side opposite the adhesive primer layer) using an extruded heat lamination method. After corona treatment was applied to the surface of transparent resin layer a, a two-component curable urethane acrylic copolymer resin primer (2 μm thick) was applied to form a primer layer for surface protection. Subsequently, an ionizing radiation-curable resin (15 μm application amount) containing a triazine-based ultraviolet absorber was applied to the surface of the primer layer for the surface protection layer using a gravure coating method. Then, an electron beam was irradiated using an electron irradiation device under the conditions of an acceleration voltage of 165 keV and 30 kGy to form a transparent surface protection layer. Subsequently, the transparent surface protective layer was heated with an infrared non-contact heater to soften transparent resin layer a and transparent resin layer b. Immediately afterward, embossing was performed using heat and pressure to create an uneven shape, thereby producing a transparent resin film. Table 1 shows the thickness of the transparent resin layers (a and b) and the UV absorber content of the transparent surface protective layer. Furthermore, the thickness of the recesses in the uneven shape on the side of the transparent resin film opposite to the side laminated with the pattern layer was 100 μm. In addition, the uneven shape on the side of the transparent resin film where the pattern layer is laminated was defined as R as defined in JIS B 0601 (2001). z However, it was 40 μm. The above "thickness of the recessed part of the uneven shape" and R z This was measured using the method described herein.

[0135] (Example 2) A transparent resin film was prepared in the same manner as in Example 1, except that the extrusion thickness of the transparent resin layer a, which was laminated using an extrusion heat lamination method, was set to 60 μm. The thickness of the recesses in the uneven shape of the resulting transparent resin film, and the R as defined in JIS B 0601 (2001) on the side where the pattern layer of the transparent resin film is laminated. z The results were as shown in Table 3.

[0136] (Example 3) A transparent resin film was prepared in the same manner as in Example 1, except that the content of the ultraviolet absorber was changed as shown in Table 1.

[0137] (Comparative Example 1) A transparent resin film was prepared in the same manner as in Example 1, except that the thickness of the transparent resin layers (a and b) and the ultraviolet absorber contained in the transparent surface protective layer were changed to a benzotriazole-based ultraviolet absorber, and its content was changed as shown in Table 1.

[0138] (Comparative Example 2) A transparent resin film was prepared in the same manner as in Comparative Example 1, except that the content of the ultraviolet absorber was changed as shown in Table 1.

[0139] (Reference example 1) A transparent resin film was prepared in the same manner as in Comparative Example 1, except that the thickness of the transparent resin layers (a and b) was changed and the transparent surface protective layer did not contain an ultraviolet absorber.

[0140] (Example 4) A transparent resin film was prepared in the same manner as in Example 1, except that in the transparent resin layer a laminated by the extrusion heat lamination method, 10 parts of a phosphinate metal salt-based flame retardant (Pekoflam STC, manufactured by Arkroma Co., Ltd.) was added to 100 parts of transparent polypropylene resin. The flame retardant content was 5.7% by mass, with the total mass of the transparent resin layers (a and b) being 100% by mass.

[0141] (Example 5) A transparent resin film was prepared in the same manner as in Example 4, except that the flame retardant was changed to a phosphazene-based flame retardant (Rabitol FP-100, manufactured by Fushimi Pharmaceutical Co., Ltd.). The flame retardant content was 5.7% by mass, with the total mass of the transparent resin layers (a and b) being 100% by mass.

[0142] (Example 6) A transparent resin film was prepared in the same manner as in Example 1, except that in the transparent resin layer a, 30 parts of a phosphinate metal salt-based flame retardant (Pekoflam STC, manufactured by Arkroma) was added to 100 parts of transparent polypropylene resin. The flame retardant content was 14.4% by mass, with the total mass of the transparent resin layers (a and b) being 100% by mass.

[0143] (Example 7) A transparent resin film was prepared in the same manner as in Example 1, except that embossing was performed using a deeper embossing plate than in Example 1. The thickness of the recesses in the uneven shape of the obtained transparent resin film, and the R as defined in JIS B 0601 (2001) on the side where the pattern layer of the transparent resin film is laminated. z The results were as shown in Table 3.

[0144] (Example 8) A transparent resin film was prepared in the same manner as in Example 2, except that the same deep embossing plate as in Example 7 was used. The thickness of the recesses in the uneven shape of the resulting transparent resin film, and the R as defined in JIS B 0601 (2001) on the side where the pattern layer of the transparent resin film is laminated. z The results were as shown in Table 3.

[0145] (Example 9) A transparent resin film was prepared in the same manner as in Example 1, except that 3 parts by mass of a phosphate-based glass silver-supported compound (PG-711, manufactured by Koa Glass Co., Ltd.) was added as an antiviral agent to 100 parts by weight of an ionizing radiation-curable resin.

[0146] (Example 10) A transparent resin film was prepared in the same manner as in Example 1, except that an anionic phenolic material with anti-allergenic properties (DIC Corporation's "EXP20530A") was blended with an ionizing radiation-curable resin at a solid content ratio of 23% by mass, and an anti-allergenic zinc-based material (DIC Corporation's "EXP20530B") was blended with an ionizing radiation-curable resin at a solid content ratio of 23% by mass.

[0147] (Color difference before and after irradiation with an electron beam) In the examples and comparative examples, the test film was the state before the application of the ionizing radiation-curable resin (the state in which the transparent resin layer (a and b) and the adhesive primer layer were formed). Place the test film on a standard white board and perform L1 using the following method. * a1 * , and b1 * We measured it. Next, the test film was irradiated with an electron beam using an electron irradiation device under the conditions of an acceleration voltage of 165 keV and 30 kGy. After that, the test film irradiated with the electron beam was placed on a standard white plate and L2 was performed using the method described below. * a2 * , and b2 * We measured it. Note that the above "L * a * , b * " is a color system standardized by the CIE (International Commission on Illumination) and adopted in JIS Z8781-4:2013, and is called "L" * a * , b * It means "...". [Measurement method] A colorimeter (Konica Minolta Japan, Inc. CR-400) was used to irradiate the surface of the transparent resin layer b side of the transparent resin film with light (D65 light source) at an incident angle of 10 degrees (with the normal direction to the surface being 0 degrees), and measurements were taken based on the total reflected light (specular reflection + diffuse reflection). The measured values ​​were substituted into the following formula to calculate ΔE, and ΔE was evaluated according to the evaluation criteria below. The results are shown in Table 1. Color difference ΔE=((L1 * -L2 * ) 2 +(a1 * -a2 * ) 2 +(b1 * -b2 * ) 2 ) 1 / 2 Δb=b1 * -b2 * [Evaluation Criteria] (Evaluation criteria for ΔE) ++:ΔE<1.0 +:1.0≦ΔE≦2.0 -:2.0<ΔE

[0148] <Fabrication of decorative panels> The resulting transparent resin film was laminated so that the adhesive primer layer side was in contact with the decorative surface (pattern layer) of the wood substrate that had been directly printed, thereby creating a decorative panel.

[0149] (Flame retardant) [Horizontal flammability test (flame retardancy: resistance to fire spreading)] The decorative panels obtained in Examples 1, 4-6 were cut to a size of 9 cm x 30 cm and used as test specimens. As shown in Figures 6(a) and (b), a rectangular metal stand 103 was placed on the base 102 of a commercially available household heater 101 (voltage AC100V, power consumption 1200W), and a test piece 105 was placed inside a metal frame 104 installed on the stand. A test to determine how difficult it was for the flame to spread was conducted with a heater angle of 45° and a heater output of 4 / 5. In detail, the test specimen was preheated for 2 minutes using the household heater described above. Then, as shown in Figure 6(a), the heater-side end 106 of the test specimen in the longitudinal direction was heated with a lighter 107 for 1 minute to ignite it, and the fire spread along the longitudinal direction of the test specimen 105 as shown in Figure 6(b). Next, the fire spread was visually observed, and the fire spread distance (L1) and burning duration were evaluated as follows. The results are shown in Table 2. [Fire spread distance (L1)] The test specimen was ignited, and after removing the lighter flame, the distance the fire spread from the initial ignition was measured and defined as the fire spread distance (L1). This distance was then evaluated according to the following evaluation criteria. A rating of + or higher indicates that there are no problems in actual use. +: L1 is less than 10 cm -: L1 is 10cm or larger [Burning time] The test specimen was ignited, the lighter flame was removed, and the burning time from initial ignition to self-extinguishing was measured and evaluated according to the following evaluation criteria. A rating of + or higher indicates that there are no problems in actual use. +++: The burning time is less than 100 seconds, or it does not ignite. ++: Burning duration is 100 seconds or more but less than 300 seconds. +: Burning duration is 300 seconds or more but less than 600 seconds. -: The burning time is 600 seconds or more (it does not self-extinguish after 600 seconds).

[0150] <Abrasion resistance (Taber abrasion test)> The decorative panels obtained in Examples 1-2 and 7-8 were tested in accordance with the Japanese Agricultural Standards for Flooring; Abrasion Test A. A Taber abrasion tester (manufactured by Rigaku Kogyo Co., Ltd.) and an abrasion wheel (S-42) was used with a load of 1 kg, and the remaining pattern of the design layer after 1000 rotations was evaluated. The results are shown in Table 3. ++: More than 80% of the pattern layer remains. +: More than half but less than 80% of the pattern layer remains. -: Less than half of the pattern layer remains

[0151] <Design> The printed patterns of the decorative panels obtained in Examples 1-2 and 7-8 were visually evaluated. The results are shown in Table 3. ++: The printed pattern is clearly visible. +: The printed pattern appears slightly cloudy. -: The printed pattern is not clearly visible.

[0152] <Antiviral> The transparent resin films prepared in Example 1 and Example 9 were subjected to antiviral performance tests in accordance with the antiviral test method (ISO 21702), and their antiviral activity against influenza viruses was evaluated. The results are shown in Table 4. +: Antiviral activity value of 2.0 or higher -: Antiviral activity value less than 2.0

[0153] <Antiallergen> The transparent resin films prepared in Example 1 and Example 10 were cut into small pieces, and the amount of allergens after immersion in an aqueous solution of dust mite allergens for one day was visually confirmed using horizontal chromatography (Mighty Checker). The results are shown in Table 5. +: A decrease in allergen levels was confirmed. -: No decrease in allergen levels was observed.

[0154] [Table 1]

[0155] [Table 2]

[0156] [Table 3]

[0157] [Table 4]

[0158] [Table 5]

[0159] In the transparent resin film obtained in the examples, it was confirmed that yellowing could be suppressed even when irradiated with an electron beam during the formation of the transparent surface protective layer, thus preventing a decrease in design quality. Furthermore, in Examples 4-6, where the transparent resin layer contained a flame retardant, excellent flame retardancy was confirmed. Furthermore, Examples 1, 2, and 8, in which the thickness of the recesses in the uneven shape of the transparent resin film is 80 μm or more, also exhibit excellent abrasion resistance, and the R of the uneven shape on the side where the pattern layer is laminated z Examples 1, 2, and 7, in which the size is 80 μm or less, are excellent in terms of design, R z Example 1, in which the particle size was 50 μm or less, exhibited particularly excellent design qualities. Furthermore, in Example 9, where the transparent surface protective layer contained an antibacterial agent or antiviral agent, it was confirmed that it possessed antibacterial and antiviral properties, and in Example 10, where the transparent surface protective layer contained an anti-allergen agent, it was confirmed that it possessed anti-allergen properties. On the other hand, in a comparative example where the transparent resin film contained a benzotriazole-based ultraviolet absorber, yellowing occurred when the transparent surface protective layer was formed by irradiation with an electron beam. [Industrial applicability]

[0160] According to the present invention, a transparent resin film can be obtained that has excellent design properties due to its uneven surface, and that suppresses yellowing even when irradiated with an electron beam, thereby preventing a decrease in design properties, while also providing weather resistance. Furthermore, the decorative panels of the present invention, which utilize the transparent resin film of the present invention, can be suitably used, for example, as interior materials for buildings such as walls, ceilings, and floors; fittings such as window frames, doors, and handrails; furniture; casings for home appliances, office automation equipment, etc.; and exterior materials such as entrance doors. [Explanation of Symbols]

[0161] 1 Transparent resin layer 1a Transparent resin layer 1b Transparent resin layer 2 Transparent surface protective layer 3. Adhesive primer layer 10 Transparent resin film 11 Base material 12 Image Layers 13 Adhesive layer 20 decorative panels 101 Household Heater 102 Household heater stand 103 Rectangular stand 104 Metal frame 105 Test specimens 106 End 107 Writers

Claims

1. A transparent resin film for protecting a pattern layer laminated on one side of a substrate, The side opposite to the side laminated on the pattern layer has an uneven shape. At least a transparent resin layer and a transparent surface protective layer are laminated in this order. The aforementioned transparent surface protective layer is made of an ionizing radiation-curable resin. The transparent resin layer and / or the transparent surface protective layer contains a triazine-based ultraviolet absorber in an amount of 0.1% by mass or more and 3% by mass or less. The transparent resin film has an uneven surface on the side on which the pattern layer is laminated, and the Rz of the uneven surface on the side on which the pattern layer is laminated is 15 μm or more and 80 μm or less, as defined in JIS B 0601 (2001). A transparent resin film characterized by the following features.

2. The transparent resin film according to claim 1, wherein the thickness of the recesses in the aforementioned uneven shape is 80 μm or more.

3. The transparent resin film according to claim 1 or 2, having an adhesive primer layer on the side of the transparent resin layer opposite to the transparent surface protective layer side.

4. The transparent resin film according to any one of claims 1 to 3, wherein the transparent resin layer is made of a thermoplastic resin.

5. The transparent resin film according to any one of claims 1 to 4, wherein the transparent resin layer has a configuration of at least two layers.

6. The transparent resin film according to any one of claims 1 to 5, wherein the transparent resin layer contains a flame retardant.

7. The transparent resin film according to any one of claims 1 to 6, wherein the transparent surface protective layer contains a flame retardant.

8. The transparent resin film according to claim 6, wherein the layer containing the flame retardant among the transparent resin layers contains a filler.

9. The transparent resin film according to any one of claims 6 to 8, wherein the flame retardant is at least one selected from the group consisting of phosphinate metal salt flame retardants, phosphazene flame retardants, and NOR-type hindered amine flame retardants.

10. The transparent resin film according to any one of claims 1 to 9, wherein the transparent surface protective layer contains at least one of an antibacterial agent, an antiviral agent, and an anti-allergen agent.

11. A decorative panel comprising a transparent resin film according to any one of claims 1 to 10 and a substrate having a pattern layer.

12. Preparation steps for preparing a transparent resin layer containing a triazine-based ultraviolet absorber in an amount of 0.1% to 3% by mass, A coating step of applying an ionizing radiation-curable resin to one side of the transparent resin layer, and The process includes an irradiation step of irradiating the ionizing radiation-curable resin with an electron beam, The transparent resin layer has an uneven surface on the side opposite to the surface coated with the ionizing radiation-curable resin, and the Rz of the uneven surface, as defined in JIS B 0601 (2001), is 15 μm or more and 80 μm or less. A method for manufacturing a transparent resin film for protecting a pattern layer laminated on one side of a substrate.

13. The method for producing a transparent resin film according to claim 12, wherein the preparation step is to prepare a thermoplastic resin, and to laminate a thermoplastic resin containing a triazine-based ultraviolet absorber onto one of the thermoplastic resins to obtain a transparent resin layer.

14. The method for producing a transparent resin film according to claim 12 or 13, wherein the ionizing radiation-curable resin contains a triazine-based ultraviolet absorber.

15. A method for manufacturing a decorative panel comprising, in this order, a substrate on which a pattern layer is laminated and a transparent resin film according to any one of claims 1 to 10, The steps include forming an adhesive layer on the side of the transparent resin film where the pattern layer is laminated, and The process involves bonding the transparent resin film and the pattern layer via the adhesive layer. A method for manufacturing decorative laminates, characterized by the above.

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