Decorative sheet, producing method of decorative sheet, and decorative member

Abstract

To provide a decorative sheet having a surface property of a layer to which a recycled resin was added same as the case where the recycled resin is not added.SOLUTION: In a decorative sheet 10 that includes a laminate formed by stacking a colored thermoplastic resin layer 1, a transparent adhesive resin layer 3, and a transparent thermoplastic resin layer 4 in this order, the colored thermoplastic resin layer 1 comprises a core layer 12 made of a colored resin, and a surface skin layer 11 and a rear skin layer 13 made of a transparent resin and provided on both sides of the core layer 12. The ratio of the thicknesses of the surface skin layer 11, core layer 12, and rear skin layer 13 is within the range of surface skin layer 11 / core layer 12 / rear skin layer 13=1 / 4 / 1 or more and 1 / 10 / 1 or less. The core layer 12 contains more than or equal to 30% of the recycled resin from the colored resin that constitutes the core layer 12, and the surface skin layer 11 and rear skin layer 13 are made of a virgin resin of the transparent resin.SELECTED DRAWING: Figure 1

Description

Technical Field

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

Background Art

[0002] Conventionally, cosmetic sheets are often formed using virgin materials derived from petroleum. However, in recent years, due to the improvement of recycling technology and the consideration for environmental concerns, the substitution with recycled materials has attracted attention. For example, a cosmetic sheet containing a recycled resin and a virgin resin made of a vinyl chloride-based resin (see, for example, Patent Document 1), a cosmetic sheet containing a recycled PET-based resin and a virgin resin (see, for example, Patent Document 2), etc. have been proposed.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] When a resin sheet is formed using a recycled resin, there are concerns such as affecting the surface physical properties. Therefore, the present invention has been made by paying attention to the above conventional problems, and an object thereof is to provide a cosmetic sheet, a method for manufacturing a cosmetic sheet, and a cosmetic member capable of making the surface characteristics of a layer added with a recycled resin equivalent to those in the case where no recycled resin is added.

Means for Solving the Problems

[0005] The cosmetic sheet according to one aspect of the present invention is a cosmetic sheet including a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order. The colored thermoplastic resin layer includes a core layer made of a colored thermoplastic resin, and a first skin layer and a second skin layer provided on both surfaces of the core layer and both made of a transparent thermoplastic resin. The ratio of the layer thicknesses of the first skin layer, the core layer, and the second skin layer is in the range of first skin layer / core layer / second skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less. In the core layer, 30% or more of the colored thermoplastic resin constituting the core layer is made of a recycled resin of the colored thermoplastic resin, and the first skin layer and the second skin layer are made only of virgin resin of the transparent thermoplastic resin.

[0006] Moreover, a method for manufacturing a cosmetic sheet according to another aspect of the present invention is a method for manufacturing a cosmetic sheet including a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order. The colored thermoplastic resin layer includes a core layer made of a colored thermoplastic resin, and a first skin layer and a second skin layer provided on both surfaces of the core layer and both made of a transparent thermoplastic resin. The colored thermoplastic resin layer is formed such that the ratio of the layer thicknesses of the first skin layer, the core layer, and the second skin layer is in the range of first skin layer / core layer / second skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less, and the core layer is formed of the colored thermoplastic resin containing 30% or more of recycled resin, and the first skin layer and the second skin layer are formed of the transparent thermoplastic resin consisting only of virgin resin.

[0007] Furthermore, a cosmetic member according to another aspect of the present invention includes a base material and the cosmetic sheet of the above aspect laminated on at least one surface of the base material.

Advantages of the Invention

[0008] According to one aspect of the present invention, even when a recycled resin is added, a cosmetic sheet having surface physical properties equivalent to those of virgin resin can be realized.

Brief Description of the Drawings

[0009]

Figure 1

Modes for Carrying Out the Invention

[0010] Hereinafter, embodiments of the present technology will be described with reference to the drawings. Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thicknesses of the respective layers, etc. are different from the actual ones. Further, the embodiments shown below are examples of configurations for embodying the technical idea of the present invention, and the technical idea of the present invention is not limited to the materials, shapes, structures, etc. of the constituent parts being the following. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

[0011] 〔Cosmetic Sheet〕 As shown in FIG. 1, the cosmetic sheet 10 according to the embodiment of the present invention includes a colored thermoplastic resin layer 1, a pattern layer 2, a transparent adhesive resin layer (adhesive resin layer) 3, a transparent thermoplastic resin layer 4, and a surface protective layer 5, and these layers are laminated in this order. Further, the cosmetic sheet 10 includes a primer layer 6 on the surface of the colored thermoplastic resin layer 1 opposite to the pattern layer 2. The thickness of the cosmetic sheet 10 is preferably 40 μm or more and 300 μm or less.

[0012] Further, the surface protective layer 5 is provided with uneven portions 7 formed by embossing that reach the transparent thermoplastic resin layer 4. As the uneven portions 7, for example, a pattern synchronized with the pattern of the pattern layer 2 may be used, or a pattern non-synchronized with the pattern may be used. The depth of the unevenness of the uneven portions 7 is preferably 10 μm or less from the viewpoints of stain resistance performance, touch feeling performance, etc.

[0013] 〔Colored Thermoplastic Resin Layer〕 The colored thermoplastic resin layer 1 according to this embodiment is, for example, a so-called two-layer three-layer laminate in which a surface skin layer (first skin layer) 11, a core layer 12, and a back skin layer (second skin layer) 13 are laminated in this order. The back skin layer 13 and the primer layer 6 are in contact with each other, and the surface skin layer 11 and the pattern layer 2 are in contact with each other. The core layer 12 is formed of a colored thermoplastic resin, and the surface skin layer 11 and the back skin layer 13 are formed of transparent thermoplastic resin layers.

[0014] Hereinafter, the configurations of the above-described respective layers will be described in detail. (Core layer) The core layer 12 according to this embodiment is a layer that serves as a base material of the colored thermoplastic resin layer 1. The core layer 12 is composed of a colored thermoplastic resin, and 30% or more of the thermoplastic resin constituting the core layer 12 is composed of recycled resin. The content of the recycled resin in the colored thermoplastic resin layer 1 may be within the range of 30% or more and 100% or less. However, since there are variations in the quality of the recycled resin, the upper limit value is preferably about 65% or more and 70% or less, and more preferably about 67%.

[0015] For the core layer 12, for example, an olefin-based thermoplastic resin can be used. Among olefin-based thermoplastic resins, an ethylene-methacrylic acid copolymer is particularly preferable. For example, a material in which a copolymer of ethylene and an unsaturated carboxylic acid is partially neutralized (neutralization degree: 50 mol%) with Zn metal ions is preferable. That is, the core layer 12 according to this embodiment may be formed of an ionomer resin. Further, the core layer 12 according to this embodiment may be formed of a polypropylene (PP) resin.

[0016] The core layer 12 only needs to contain at least titanium oxide as a coloring pigment. The content of titanium oxide contained in the core layer 12 may be within the range of 10 parts by mass or more and 50 parts by mass or less, more preferably within the range of 20 parts by mass or more and 40 parts by mass or less, and even more preferably within the range of 25 parts by mass or more and 35 parts by mass or less, based on 100 parts by mass of the resin component constituting the core layer 12. If the content of titanium oxide is less than 10 parts by mass, the coloring in the core layer 12 may not be sufficient and sufficient hiding power may not be imparted to the core layer 12. Also, if the content of titanium oxide exceeds 50 parts by mass, the proportion of the resin component constituting the core layer 12 relatively decreases, and thus the strength required for printing may not be imparted to the core layer 12.

[0017] The average particle diameter (D50) of the titanium oxide contained in the core layer 12 is preferably within the range of 10 nm or more and 100 nm or less. The thickness of the core layer 12 may be within the range of 4 times or more and 10 times or less with respect to the thicknesses of the surface skin layer 11 and the back skin layer 13. That is, the ratio of the layer thicknesses of the surface skin layer 11, the core layer 12, and the back skin layer 13 (surface skin layer 11 / core layer 12 / back skin layer 13) may be within the range of 1 / 4 / 1 to 1 / 10 / 1. Preferably, the ratio of the layer thicknesses of the surface skin layer 11, the core layer 12, and the back skin layer 13 (surface skin layer 11 / core layer 12 / back skin layer 13) is within the range of 1 / 7 / 1 to 1 / 9 / 1. If the thickness of the core layer 12 is within the above numerical range, high hiding power can be imparted to the colored thermoplastic resin layer 1 (core layer 12) itself, and surface stability such as printability, light resistance, and surface inferiority of the colored thermoplastic resin layer 1 can be ensured. From the viewpoint of surface stability, it is preferable that the ratio of the layer thicknesses is about surface skin layer 11 / core layer 12 / back skin layer 13 = 1 / 8 / 1.

[0018] The thickness of the core layer 12 may be, for example, within the range of 10 μm or more and 250 μm or less, more preferably within the range of 30 μm or more and 100 μm or less, and even more preferably within the range of 40 μm or more and 60 μm or less. If the thickness of the core layer 12 is within the above numerical range, high hiding power can be imparted to the colored thermoplastic resin layer 1 (core layer 12) itself.

[0019] Further, the core layer 12 may contain an ultraviolet absorber. The content of the ultraviolet absorber contained in the core layer 12 may be in the range of 0.001 part by mass or more and 10 parts by mass or less, more preferably in the range of 0.05 part by mass or more and 5 parts by mass or less, and even more preferably in the range of 0.5 part by mass or more and 3 parts by mass or less, based on 100 parts by mass of the resin component constituting the core layer 12. If the content of the ultraviolet absorber is less than 0.001 part by mass, the ultraviolet absorption performance in the core layer 12 may not be sufficient and sufficient durability may not be imparted to the core layer 12. Further, if the content of the ultraviolet absorber exceeds 10 parts by mass, the proportion of the resin component constituting the core layer 12 relatively decreases, so that powder wiping or the like may occur in the core layer 12, and the strength required for printing may not be imparted, or the film formation itself may not be possible.

[0020] As the ultraviolet absorber that can be used in the present embodiment, for example, benzotriazole-based, hydroxyphenyltriazine-based, benzophenone-based, etc. can be used. Examples of the benzotriazole-based ultraviolet absorber include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumenylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole, etc., but are not limited thereto.

[0021] In addition, if a hydroxyphenyltriazine-based ultraviolet absorber is selected as the ultraviolet absorber to be added to the core layer 12, the triazine skeleton suppresses bleeding, and the triazine skeleton is chemically more stable than the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers. Therefore, it becomes possible to maintain the ultraviolet absorption performance over a long period of time.

[0022] Examples of the hydroxyphenyltriazine-based ultraviolet absorber include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethyl-hexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and the like. In this embodiment, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine may be contained in the core layer 12.

[0023] Furthermore, by using a hydroxyphenyltriazine-based ultraviolet absorber and a benzotriazole-based ultraviolet absorber in combination as the ultraviolet absorber, better weather resistance can be imparted due to their interaction. This is because the benzotriazole-based ultraviolet absorber has an absorption peak on the longer wavelength side than the hydroxyphenyltriazine-based ultraviolet absorber, so that the wavelength region for absorbing ultraviolet rays can be further widened by the combination. The addition amount of the benzotriazole-based ultraviolet absorber is preferably in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the resin component constituting the core layer 12. By adding 0.001 parts by mass or more, the desired effect can be obtained, and by setting it to 10 parts by mass or less, bleed-out of the ultraviolet absorber can be suppressed. However, since the benzotriazole-based ultraviolet absorber has an absorption peak on the longer wavelength side, it may have a yellowish color, and when attention is required for the hue, the addition amount may be suppressed.

[0024] As the benzophenone-based ultraviolet absorber, for example, octabenzone, modified products, polymers, derivatives, etc. can be used. In addition, the core layer 12 may contain a light stabilizer such as a hindered amine-based radical scavenger. The content of the light stabilizer contained in the core layer 12 may be in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the resin component constituting the core layer 12, more preferably in the range of 0.05 to 5 parts by mass, and even more preferably in the range of 0.5 to 3 parts by mass. If the content of the light stabilizer is less than 0.001 parts by mass, the stability against ultraviolet rays in the core layer 12 may not be sufficient and sufficient durability may not be imparted to the core layer 12. Also, if the content of the light stabilizer exceeds 10 parts by mass, the proportion of the resin component constituting the core layer 12 relatively decreases, so that powdering or the like may occur in the core layer 12, and the strength required for printing may not be imparted, or the film itself may not be formed.

[0025] Examples of hindered amine radical scavengers that can be used in this embodiment include bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / succinic acid diethyl polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl〕-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl〕-1,5,8-12-tetraazadodecane, 1,6,11-tris〔2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate cyclohexane and the reaction product of N-butyl 2,2,6,6-tetramethyl-4-piperidineamine with 2,4,6-trichloro-1,3,5-triazine and the reaction product with 2-aminoethanol, etc., but not limited thereto.,

[0026] An antioxidant may be added to the core layer 12. Among antioxidants, phenolic ones are preferably used. In this embodiment, for example, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis〔(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide〕, 4,4’-thiobis(6-tert-butyl-m-cresol), 2,2’-methylenebis(4-methyl-6-tert-butylphenol), 2,2’-methylenebis(4-ethyl-6-tert-butylphenol), 4,4’-butylidenebis(6-tert-butyl-m-cresol), 2,2’-ethylidenebis(4,6-di-tert-butylphenol), 2,2’-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis〔3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid methyl〕 methane, thiodiethylene glycol bis〔(3,5-di-tert-butyl-4-hydroxyphenyl) propionate〕, 1,6-hexamethylenebis〔(3,5-di-tert-butyl-4-hydroxyphenyl) propionate〕, bis〔3,3-bis(4-hydroxy-3-tert-butylphenyl) butyric acid〕 glycol ester, bis〔2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl〕 terephthalate, 1,3,5-tris〔(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl〕 isocyanurate, 3,9-bis〔1,1-dimethyl-2-{[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and the like. Further, the content of the above antioxidant is preferably in the range of 0.001 part by mass or more and 10 parts by mass or less, more preferably in the range of 0.05 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the resin component constituting the core layer 12.,

[0027] A processing stabilizer may be added to the core layer 12. Among the processing stabilizers, phosphorus-based ones are preferably used. In this embodiment, for example, tris(nonylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, di(decyl) monophenyl phosphite, di(tridecyl) pentaerythritol diphosphite, di(nonylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, tetra(tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, tetrakis(2,4-di-tert-butylphenyl) biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, and the like can be mentioned. Further, the content of the above-described processing stabilizer is preferably in the range of 0.001 part by mass or more and 10 parts by mass or less, more preferably in the range of 0.05 part by mass or more and 5 parts by mass or less, based on 100 parts by mass of the resin component constituting the core layer 12.

[0028] (Front skin layer and back skin layer) The front skin layer 11 according to this embodiment is a layer formed so as to be in contact with one surface of the core layer 12. Further, the back skin layer 13 according to this embodiment is a layer formed so as to be in contact with the other surface of the core layer 12.

[0029] Each of the front skin layer 11 and the back skin layer 13 does not contain a coloring pigment such as titanium oxide. Each of the front skin layer 11 and the back skin layer 13 is composed of only the virgin resin of a transparent thermoplastic resin.

[0030] Each of the front skin layer 11 and the back skin layer 13 may be composed of the same thermoplastic resin as the thermoplastic resin constituting the core layer 12 described above. That is, the material constituting each of the front skin layer 11 and the back skin layer 13 is not particularly limited as long as it is a thermoplastic resin. For example, an olefin-based thermoplastic resin can be used in the same manner as the core layer 12. Among olefin-based resins, an ethylene-methacrylic acid copolymer is particularly preferable. For example, a material obtained by partially neutralizing (neutralization degree: 50 mol%) a copolymer of ethylene and an unsaturated carboxylic acid with Zn metal ions is preferable. That is, at least one of the front skin layer 11 and the back skin layer 13 according to this embodiment may be formed of an ionomer resin. Further, at least one of the front skin layer 11 and the back skin layer 13 according to this embodiment may be formed of a polypropylene (PP) resin.

[0031] The thickness of each of the front skin layer 11 and the back skin layer 13 may be, for example, in the range of 1 μm or more and 20 μm or less, more preferably in the range of 4 μm or more and 10 μm or less, and even more preferably in the range of 5 μm or more and 8 μm or less. If the thickness of each of the front skin layer 11 and the back skin layer 13 is within the above numerical range, high hiding power can be imparted to the colored thermoplastic resin layer 1 itself.

[0032] Further, the thickness of the front skin layer 11 and the thickness of the back skin layer 13 may be the same. Each of the surface skin layer 11 and the back skin layer 13 may contain an ultraviolet absorber that can be added to the core layer 12 described above. By adding an ultraviolet absorber to each of the surface skin layer 11 and the back skin layer 13, the durability (weather resistance) of the colored thermoplastic resin layer 1 itself can be improved.

[0033] Also, the content of the ultraviolet absorber contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the content of the ultraviolet absorber contained in the core layer 12 described above. Also, the type of the ultraviolet absorber contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the type of the ultraviolet absorber contained in the core layer 12 described above.

[0034] Also, each of the surface skin layer 11 and the back skin layer 13 may contain a light stabilizer such as a hindered amine-based radical scavenger that can be added to the core layer 12 described above. By adding a light stabilizer to each of the surface skin layer 11 and the back skin layer 13, cracks and chalking of the colored thermoplastic resin layer 1 itself can be improved. Also, by adding a light stabilizer to each of the surface skin layer 11 and the back skin layer 13, deterioration of the pattern layer, primer layer, or coating layer provided as necessary that is in contact with the surface skin layer 11 or the back skin layer 13 can be suppressed.

[0035] Also, the content of the light stabilizer contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the content of the light stabilizer contained in the core layer 12 described above. Also, the type of the light stabilizer contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the type of the light stabilizer contained in the core layer 12 described above.

[0036] Further, each of the surface skin layer 11 and the back skin layer 13 may contain an antioxidant that can be added to the core layer 12 described above. Also, the content of the antioxidant contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the content of the antioxidant contained in the core layer 12 described above. Also, the type of antioxidant contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the type of antioxidant contained in the core layer 12 described above.

[0037] Further, each of the surface skin layer 11 and the back skin layer 13 may contain a processing stabilizer that can be added to the core layer 12 described above. Also, the content of the processing stabilizer contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the content of the processing stabilizer contained in the core layer 12 described above. Also, the type of processing stabilizer contained in each of the surface skin layer 11 and the back skin layer 13 may be the same as the type of processing stabilizer contained in the core layer 12 described above.

[0038] (Modification example) In this embodiment, the case where an ultraviolet absorber and a light stabilizer are added to each of the surface skin layer 11 and the back skin layer 13 has been described, but the present invention is not limited thereto. For example, an ultraviolet absorber and a light stabilizer may be added only to one skin layer (for example, the surface skin layer 11), or at least one of an ultraviolet absorber and a light stabilizer may be added only to one skin layer (for example, the surface skin layer 11).

[0039] Also, the thickness of the colored thermoplastic resin layer 1 is preferably in the range of 25 μm or more and 200 μm or less. If the thickness of the colored thermoplastic resin layer 1 is within the above numerical range, higher hiding properties can be imparted to the colored thermoplastic resin layer 1 itself.

[0040] In addition, in the present embodiment, as the core layer 12, at least one of a hindered phenolic antioxidant, an ultraviolet absorber, and a hindered amine light stabilizer is added to the above-described random or homopolymer polypropylene resin or polyethylene resin, and as a coloring pigment, at least one of iron oxide, carbon black, titanium oxide, phthalocyanine blue, and isoindolinone may be added. Further, in addition to the above-described resins, a copolymer polyester resin, a foamed type polyester resin, an acrylic resin, or the like may be used. Further, as the resin constituting the colored thermoplastic resin layer 1, resins such as polybutylene terephthalate (PBT), polyethylene terephthalate (PET), and polyvinyl chloride may be used. If the core layer 12 has the above configuration, effects equivalent to those of the decorative sheet 10 and the decorative member 20 in the present embodiment can be obtained.

[0041] (Method for manufacturing colored thermoplastic resin layer) Hereinafter, an example of a method for manufacturing the colored thermoplastic resin layer 1 according to the present embodiment will be briefly described. The colored thermoplastic resin layer 1 is formed into a film shape by a coextrusion method in which the above-described surface skin layer 11, core layer 12, and back skin layer 13 are coextruded in this order. In this way, the two-layer three-layer colored thermoplastic resin layer 1 according to the present embodiment is formed.

[0042] (Pattern layer) The pattern layer 2 is a layer for imparting concealment or design, and can be provided by printing pattern ink entirely or partially on the colored thermoplastic resin layer 1.

[0043] As the binder of the pattern ink, for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester-based, etc. may be appropriately selected from among them alone or their modified products. These may be aqueous, solvent-based, or emulsion-based, and there is no problem, and the curing method can be arbitrarily selected as either a one-component type or a two-component type using a curing agent. Further, it is also possible to cure the ink by irradiation with active energy rays such as ultraviolet rays or electron beams.

[0044] As the pigments of the pattern ink, for example, various known pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, pearl pigments such as mica, etc. can be used. For these ink materials, it is necessary to select them in consideration of the adhesiveness to the colored thermoplastic resin layer 1 under the pattern layer 2 and the resin laminated on the pattern layer 2.

[0045] In the pattern layer 2, various additives such as the above-mentioned ultraviolet absorber, radical scavenger, dispersant, etc. may be added as necessary. As a method of providing the pattern layer 2, for example, it can be directly applied to the colored thermoplastic resin layer 1 by known printing techniques such as gravure printing, offset printing, screen printing, flexographic printing, silk printing, electrostatic printing, inkjet printing, etc. In addition, it is also possible to apply a metallic design property by vapor deposition or sputtering of various metals separately from the application of the ink.

[0046] (Transparent adhesive resin layer) The transparent adhesive resin layer 3 is a layer for bonding the colored thermoplastic resin layer 1 and the transparent thermoplastic resin layer 4. In the present embodiment, the colored thermoplastic resin layer 1 laminated with the pattern layer 2 and the transparent thermoplastic resin layer 4 may be joined via the transparent adhesive resin layer 3, and various lamination methods such as thermal lamination, extrusion lamination, dry lamination, and sand lamination can be used for the joining method. Here, considering the various performances of the decorative sheet 10 according to the present embodiment, the dry lamination method is preferable for the joining method. For this reason, the transparent adhesive resin layer 3 is preferably a dry lamination adhesive layer using a dry lamination adhesive. Further, the transparent adhesive resin layer 3 is formed by using a normal coating method such as gravure coating, microgravure coating, comma coating, knife coating, die coating, etc.

[0047] Further, the transparent adhesive resin layer 3 is preferably formed of a polyolefin-based thermoplastic resin. For example, it preferably contains at least one of a maleic acid-modified random polypropylene resin and an ethylene-propylene copolymer resin. When the transparent adhesive resin layer 3 contains both a maleic acid-modified random polypropylene resin and an ethylene-propylene copolymer resin, it is preferable that the content of the maleic acid-modified random polypropylene resin is more than that of the ethylene-propylene copolymer resin. Specifically, it is preferable that the content of the maleic acid-modified random polypropylene resin is in the range of 1.1 times or more and 10 times or less in terms of mass ratio compared to the content of the ethylene-propylene copolymer resin. If the content of the maleic acid-modified random polypropylene resin is within the above numerical range, the adhesive strength between the colored thermoplastic resin layer 1 and the transparent thermoplastic resin layer 4 can be enhanced.

[0048] The transparent adhesive resin layer 3 may be formed using a composition in which an ultraviolet absorber and a light stabilizer are added to the above-described polyolefin resin. The ultraviolet absorber contained in the transparent adhesive resin layer 3 may be the ultraviolet absorber listed as an ultraviolet absorber that can be added to the colored thermoplastic resin layer 1. Also, the content of the ultraviolet absorber contained in the transparent adhesive resin layer 3 may be the same as the content of the ultraviolet absorber contained in the colored thermoplastic resin layer 1.

[0049] Also, the light stabilizer contained in the transparent adhesive resin layer 3 may be the light stabilizer listed as a light stabilizer that can be added to the colored thermoplastic resin layer 1. Also, the content of the light stabilizer contained in the transparent adhesive resin layer 3 may be the same as the content of the light stabilizer contained in the colored thermoplastic resin layer 1.

[0050] (Transparent thermoplastic resin layer) The transparent thermoplastic resin layer 4 is a layer for improving the weather resistance of the decorative sheet 10. The transparent thermoplastic resin layer 4 is formed using, for example, a polyolefin-based thermoplastic resin (hereinafter also referred to as a polyolefin resin). There are no particular restrictions on the polyolefin resin, and the same polyolefin resin as that used for the transparent thermoplastic resin layer in conventional decorative sheets can be used. For example, a homopolypropylene resin with low stereoregularity can be used as the polyolefin resin constituting the transparent thermoplastic resin layer 4. Also, the type of polyolefin resin constituting the transparent thermoplastic resin layer 4 may be one type or a plurality of types. And, an ultraviolet absorber and a light stabilizer may be added to this polypropylene resin. That is, the transparent thermoplastic resin layer 4 may be formed of a polypropylene resin composition (polyolefin resin composition) containing an ultraviolet absorber and a light stabilizer.

[0051] The ultraviolet absorber contained in the transparent thermoplastic resin layer 4 may be an ultraviolet absorber listed as an ultraviolet absorber that can be added to the colored thermoplastic resin layer 1, preferably a benzotriazole-based ultraviolet absorber. Also, the content of the ultraviolet absorber in the transparent thermoplastic resin layer 4 is preferably in the range of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polypropylene resin (resin component). When the content of the ultraviolet absorber in the transparent thermoplastic resin layer 4 is less than 0.1 part by mass, sufficient weather resistance may not be obtained. Also, when the content of the ultraviolet absorber in the transparent thermoplastic resin layer 4 exceeds 10 parts by mass, the content rate of the polypropylene resin (resin component) becomes relatively low, and problems may occur during the formation of the transparent thermoplastic resin layer 4.

[0052] The light stabilizer contained in the transparent thermoplastic resin layer 4 may be a light stabilizer listed as a light stabilizer that can be added to the colored thermoplastic resin layer 1, that is, a hindered amine-based radical scavenger or the like.

[0053] Also, the content of the light stabilizer in the transparent thermoplastic resin layer 4 is preferably in the range of 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the polypropylene resin (resin component). When the content of the light stabilizer in the transparent thermoplastic resin layer 4 is less than 0.1 part by mass, sufficient weather resistance may not be obtained. Further, when the content of the light stabilizer in the transparent thermoplastic resin layer 4 exceeds 10 parts by mass, the content rate of the polypropylene resin (resin component) becomes relatively low, and thus problems may occur during the formation of the transparent thermoplastic resin layer 4.

[0054] Also, the thickness of the transparent thermoplastic resin layer 4 is preferably in the range of 1 μm or more and 10 μm or less. If the thickness of the transparent thermoplastic resin layer 4 is within the above numerical range, sufficient weather resistance can be surely obtained.

[0055] (Modification example) In this embodiment, the case where a polyolefin-based resin is used for the transparent thermoplastic resin layer 4 has been described, but the present invention is not limited thereto. The transparent thermoplastic resin layer 4 may be, for example, a synthetic resin such as polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, or a foam of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, polyurethane, or the like. Further, various additives such as the above-described ultraviolet absorber, radical scavenger, antioxidant, processing stabilizer, etc. may be added to these resins as necessary.

[0056] In addition, as the ultraviolet absorber that can be added to the transparent thermoplastic resin layer 4, in addition to 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), etc., which are the ultraviolet absorbers listed as the ultraviolet absorber that can be added to the colored thermoplastic resin layer 1, for example, benzoates, substituted oxanilides, cyanoacrylates, triaryl triazines, etc. can be used.

[0057] As the benzoates, for example, phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tertamylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, etc. can be used.

[0058] In addition, as the substituted oxanilides, for example, 2-ethyl-2'-ethyloxanilide, 2-ethoxy-4'-dodecyloxanilide, etc. can be used. In addition, as the cyanoacrylates, for example, ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, etc. can be used.

[0059] In addition, as the triaryl triazines, for example, 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, etc. can be used.

[0060] (Surface protection layer) The surface protective layer 5 is a layer for improving the weather resistance of the decorative sheet 10. The surface protective layer 5 is formed, for example, using an acrylic resin. There are no particular restrictions on the acrylic resin, and the same acrylic resins as those used for the surface protective layer in conventional decorative sheets can be used. For example, as the acrylic resin constituting the surface protective layer 5, an acrylic resin composed of a mixture of methyl methacrylate monomer and cyclohexyl methacrylate can be used. Also, the type of acrylic resin constituting the surface protective layer 5 may be one type or a plurality of types. Hereinafter, the acrylic resins that can be used for the surface protective layer 5 of the present embodiment will be specifically described.

[0061] In the present embodiment, the surface protective layer 5 may mainly contain an acrylic resin composition containing cyclohexyl (meth) acrylate as a monomer component. In the present embodiment, cyclohexyl (meth) acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By containing cyclohexyl (meth) acrylate as a monomer component, the affinity for water can be reduced, and deterioration due to hydrolysis or the like can be suppressed. The content of cyclohexyl (meth) acrylate is desirably in the range of 5% by mass or more and 50% by mass or less of the monomer components of all the acrylic resin compositions. By setting the content of cyclohexyl (meth) acrylate to 5% by mass or more, a sufficient deterioration suppressing effect can be obtained, and by setting the content to 50% by mass or less, high weather resistance over time can be imparted without significantly changing the various performances of the surface protective layer 5 such as maintaining and improving surface hardness, improving stain resistance, and adjusting the gloss of the surface.

[0062] As monomer components of the acrylic resin composition that can be used for the surface protective layer 5, in addition to the cyclohexyl (meth)acrylate described above, for example, cyclohexylmethyl (meth)acrylate, cyclohexylethyl (meth)acrylate, cyclohexylpropyl (meth)acrylate, cyclohexylbutyl (meth)acrylate, dimethylcyclohexane mono(meth)acrylate, dimethylcyclohexane di(meth)acrylate, trimethylcyclohexane mono(meth)acrylate, trimethylcyclohexane di(meth)acrylate, trimethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane mono(meth)acrylate, tetramethylcyclohexane di(meth)acrylate, tetramethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane tetra(meth)acrylate, dicyclohexylmethyl (meth)acrylate, dicyclohexylmethyl (meth)acrylate, phenoxycyclohexylmethyl (meth)acrylate, methoxycyclohexylmethyl (meth)acrylate, etc. can be mentioned. Among these, those containing isomers may be used with each isomer alone or as a mixture of each isomer.

[0063] Also, as a method for forming the surface protective layer 5, for example, there is a method of coating a coating liquid composed of an acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component on the transparent thermoplastic resin layer 4. Further, as the type of the coating liquid, for example, any of a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type cured by irradiating ultraviolet rays, ionizing radiation, etc. can be used. However, considering weather resistance, the two-component curing type or the active energy ray curing type is preferable. Considering the post-processability after being laminated on various base materials to form a decorative member, the two-component curing type crosslinked by isocyanate curing is desirable.

[0064] As the above-described two-component curable acrylic resin composition, for example, a composition containing an acrylic resin having two or more functional groups selected from a hydroxyl group, an amino group, and a carboxyl group in one molecule and a polyisocyanate compound having two or more isocyanate groups capable of reacting with the functional group in one molecule is preferable. Particularly preferably, it is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

[0065] As the acrylic polyol having two or more hydroxyl groups in one molecule, for example, in addition to the above-described cyclohexyl (meth)acrylate, a (meth)acrylate copolymer containing hydroxyethyl (meth)acrylate as a monomer component can be used. On the other hand, as the polyisocyanate compound having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), and hydrogenated compounds thereof, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, biuret types, etc. synthesized from one or more compounds selected from these by known techniques can be mentioned. Further, a composition in which one or more selected from these different types of polyisocyanates are mixed can be used. Among them, HDI, or a trimer type, TMP adduct type, or biuret type of HDI is preferable from the viewpoint of weather resistance. The content of the isocyanate compound with respect to the above-described resin component can be arbitrarily set, but it is desirable to set it so that the equivalent ratio of hydroxyl group / isocyanate group is about 1 / 1 to 1 / 3. In particular, when the equivalent of the hydroxyl group is more than the equivalent of the isocyanate group, crosslinking does not proceed sufficiently and the desired performance is not added to the surface protective layer 5, which is not preferable.

[0066] In addition, as the active energy ray-curable type acrylic resin composition, for example, known monomers, oligomers, etc. having a (meth)acryloyl group can be used. In addition to these monomers and oligomers, the above-mentioned cyclohexyl (meth)acrylate may be blended. An ultraviolet absorber and a light stabilizer may be added to the above-mentioned acrylic resin. That is, the surface protective layer 5 may be formed of an acrylic resin composition containing an ultraviolet absorber and a light stabilizer.

[0067] The ultraviolet absorber contained in the surface protective layer 5 may be the ultraviolet absorber mentioned as the ultraviolet absorber that can be added to the colored thermoplastic resin layer 1, preferably a benzotriazole-based ultraviolet absorber.

[0068] In addition, the content of the ultraviolet absorber in the surface protective layer 5 is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin (resin component). When the content of the ultraviolet absorber in the surface protective layer 5 is less than 1 part by mass, sufficient weather resistance may not be obtained. When the content of the ultraviolet absorber in the surface protective layer 5 exceeds 30 parts by mass, bleed-out of the ultraviolet absorber may occur. In addition, since the content rate of the acrylic resin (resin component) becomes relatively low, problems may occur during the formation of the surface protective layer 5.

[0069] The light stabilizer contained in the surface protective layer 5 may be the light stabilizer mentioned as the light stabilizer that can be added to the colored thermoplastic resin layer 1, that is, a hindered amine-based radical scavenger or the like. In addition, the content of the light stabilizer in the surface protection layer 5 is preferably in the range of 1 to 30 parts by mass with respect to 100 parts by mass of the acrylic resin (resin component). When the content of the light stabilizer in the surface protection layer 5 is less than 1 part by mass, sufficient weather resistance may not be obtained. Further, when the content of the light stabilizer in the surface protection layer 5 exceeds 30 parts by mass, the content rate of the acrylic resin (resin component) becomes relatively low, and thus problems may occur during the formation of the surface protection layer 5. Also, when it exceeds 30 parts by mass, bleed-out of the light stabilizer may occur.

[0070] Note that the content of the ultraviolet absorber in the surface protection layer 5 may be more than the content of the ultraviolet absorber in the transparent thermoplastic resin layer 4. Also, the content of the light stabilizer in the surface protection layer 5 may be more than the content of the light stabilizer in the transparent thermoplastic resin layer 4. In addition, the thickness of the surface protection layer 5 is preferably in the range of 1 μm or more and 20 μm or less. If the thickness of the surface protection layer 5 is within the above numerical range, sufficient weather resistance can be surely obtained, and flexibility is imparted to the surface protection layer 5, so that the occurrence of cracks in the surface protection layer 5 can be reduced.

[0071] As a method for providing the surface protection layer 5, for example, various known coating methods such as gravure coating, reverse coating, gravure reverse coating, die coating, and flow coating can be used. Further, various additives such as an antifriction agent, an antiblocking agent, and an antistatic agent may be added to the surface protection layer 5 as necessary. In addition, the surface protection layer 5 may be formed in a region where the uneven portions 7 are formed, or may not be formed. Note that if the surface protection layer 5 is formed in a region where the uneven portions 7 are formed, it is preferable because the durability (weather resistance) is improved as compared with the case where it is not formed.

[0072] (Modification example) In this embodiment, a benzotriazole-based ultraviolet absorber was given as a preferred example of the ultraviolet absorber contained in the surface protective layer 5, but the present invention is not limited thereto. For example, the surface protective layer 5 may be added with a hydroxyphenyltriazine-based ultraviolet absorber mentioned as an ultraviolet absorber that can be added to the colored thermoplastic resin layer 1, preferably 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol. Hereinafter, this point will be specifically described.

[0073] The surface protective layer 5 may contain at least one having a structure of 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (corresponding to the following formula (1)). This is because the hydroxyphenyltriazine-based ultraviolet absorber represented by the formula (1) has high ultraviolet absorption ability in the low wavelength region where the ultraviolet rays have relatively high energy among ultraviolet rays, and is chemically stable compared to other ultraviolet absorbers that absorb in almost the same wavelength region, so the ultraviolet absorption performance over a long period of time is maintained.

[0074]

Chemical formula

[0075] In this embodiment, it is preferable that the addition amount of all hydroxyphenyltriazine-based ultraviolet absorbers including those having the structure of the formula (1) is in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin (resin composition). By setting the addition amount of the ultraviolet absorber to 1 part by mass or more, the effect of improving weather resistance is exhibited, and by setting it to 30 parts by mass or less, the influence on the physical properties other than the weather resistance of the surface protective layer 5 can be suppressed to a practically acceptable level.

[0076] Further, the hydroxyphenyltriazine-based ultraviolet absorber having the structure shown in the formula (1) may account for 30% by mass or more and 95% by mass or less of all the hydroxyphenyltriazine-based ultraviolet absorbers contained in the surface protective layer 5. In addition, in the present embodiment, as the hydroxyphenyltriazine-based ultraviolet absorber in the surface protective layer 5, those having the structure of formula (1) and those having the structure of 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (corresponding to the following formula (2)) are used in combination, thereby imparting even more excellent weather resistance. This is because the ultraviolet absorber having the structure of formula (2) is chemically stable and has the characteristic of maintaining ultraviolet absorption performance over a long period, and has a peak of light absorption on the longer wavelength side than those having the structure of formula (1). Therefore, the wavelength region for absorbing ultraviolet rays becomes wider when used in combination.

[0077]

Chemical formula

[0078] (Primer layer) The primer layer 6 is a layer for improving the adhesion between the adhesive used for adhering to the base material 8 and the decorative sheet 10 when forming the decorative member 20 by laminating the decorative sheet 10 on a predetermined base material 8. For example, when the base material 8 is made of a wood-based material, a metal-based material such as an aluminum base material or a steel plate base material, preferably a metal-based material, adhesives such as vinyl acetate emulsion-based adhesives and two-component curable urethane-based adhesives are used as the adhesive. Therefore, it is desirable that the primer layer 6 has a resin design suitable for these adhesives. For example, the primer layer 6 can adopt urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer-based, polyester-based, etc. In particular, two-component curable urethane-based primer agents prepared by blending polyester polyol and polyisocyanate are preferable. In addition, when forming the primer layer 6 by adding inorganic powders such as silica, barium sulfate, and calcium carbonate to these materials, it is effective for preventing blocking during winding storage and improving the adhesive strength due to the anchoring effect.

[0079] (Uneven portion) The uneven portion 7 is for imparting a three-dimensional design feeling to the surface of the decorative sheet 10. As the uneven portion 7, any uneven shape can be used. For example, a wood grain conduit shape, a stone grain shape, a cloth grain shape, an abstract pattern shape, a Japanese paper shape, a suede shape, a leather shape, a satin finish shape, a sandblasted shape, a hairline shape, a group of parallel straight lines, or a combination thereof can be used. Further, as a method for forming the uneven portion 7, for example, a doubling embossing method, an extrusion lamination simultaneous embossing method, etc., which are performed before, after, or simultaneously with the lamination of the transparent thermoplastic resin layer 4 on the surface 1a of the colored thermoplastic resin layer 1, can be adopted.

[0080] 〔Effects of the Embodiment〕 (1) Only the core layer 12 uses recycled resin, and the surface skin layer 11 and the back skin layer 13 disposed on both sides of the core layer 12 are composed of only virgin resin without using recycled resin. And the surface skin layer 11 and the back skin layer 13 composed of virgin resin are provided on both sides of the core layer 12 containing recycled resin. Since both sides of the colored thermoplastic resin layer 1 are the surface skin layer 11 and the back skin layer 13 made of only virgin resin, the surface physical properties of the colored thermoplastic resin layer 1 can be made equivalent to those in the case where the colored thermoplastic resin layer is composed of only virgin resin without using recycled resin. As a result, even when the colored thermoplastic resin layer 1 is formed using recycled resin, it can be handled equivalently to the case where the colored thermoplastic resin layer is composed of only virgin resin, and good film-forming properties of the colored thermoplastic resin layer 1 can be obtained. At the same time, even when using recycled resin, good production suitability can be obtained in the same manner as when manufacturing the decorative sheet using only virgin resin.

[0081] (2) Further, the ratio of the layer thicknesses of the surface skin layer 11 that does not contain recycled resin, the core layer 12 that contains recycled resin, and the back skin layer 13 that does not contain recycled resin is in the range of surface skin layer 11 / core layer 12 / back skin layer 13 = 1 / 4 / 1 or more and 1 / 10 / 1 or less. Since the surface skin layer 11 and the back skin layer 13 made of virgin resin without containing recycled resin and having a certain thickness are provided on both sides of the core layer 12 with respect to the thickness of the core layer 12 that contains recycled resin, among the thickness of the colored thermoplastic resin layer 1, the portions with a certain thickness on both sides will have the characteristics of virgin resin. Therefore, it is possible to ensure the surface stability such as printability, light resistance, and surface deterioration of the colored thermoplastic resin layer 1, and it is possible to realize a colored thermoplastic resin layer 1 having surface physical properties equivalent to those when using virgin resin although it contains recycled resin. Therefore, even when the colored resin constituting the core layer contains 30% or more of recycled resin, it is possible to realize a colored thermoplastic resin layer 1 having surface physical properties equivalent to those when using virgin resin, and it is possible to realize a colored thermoplastic resin layer 1 with a high recycling ratio.

[0082] (3) The resins constituting each of the surface skin layer 11, the core layer 12, and the back skin layer 13 are the same olefin-based thermoplastic resins as each other and contain a hindered amine-based radical scavenger, so high weather resistance can be imparted to the decorative sheet 10 and the decorative member 20.

[0083] (4) Since each of the transparent thermoplastic resin layer 4 and the surface protective layer 5 contains an ultraviolet absorber and a hindered amine-based radical scavenger, high weather resistance can be imparted to the decorative sheet 10 and the decorative member 20.

[0084] (5) The core layer 12 contains an inorganic substance, and as the inorganic substance, it contains any one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composite, and other oxides. Therefore, the hiding property of the colored thermoplastic resin layer 1 can be enhanced.

Example

[0085] Examples and comparative examples of the cosmetic sheet according to the present invention will be described below. Note that the present invention is not limited to the following examples.

[0086] 〔Example〕 Using a colored thermoplastic resin layer 1 made of polypropylene resin, after subjecting one surface of the colored thermoplastic resin layer 1 to corona discharge treatment, a pattern layer 2 made of urethane-based printing ink, a urethane-based adhesive layer, a transparent adhesive resin layer 3, a transparent thermoplastic resin layer 4, and a surface protection layer 5 mainly composed of an acrylic resin composition were laminated in this order. After subjecting the other surface of the colored thermoplastic resin layer 1 to corona discharge treatment, a primer layer 6 with a thickness of 1 to 2 μm was formed to obtain a cosmetic sheet 10.

[0087] The configuration of each layer was as follows. (Colored thermoplastic resin layer 1) Material: Polypropylene Thickness: 60 μm · Ultraviolet absorber (Tinuvin 326; manufactured by BASF Japan Ltd.)... 0.25 parts by mass · Light stabilizer (Tinuvin XT55; manufactured by BASF Japan Ltd.)... 0.5 parts by mass Using a T-die extruder, a colored thermoplastic resin (polypropylene) that becomes the core layer 12 and a transparent thermoplastic resin (polypropylene) that becomes the surface skin layer 11 and the back skin layer 13 were made into a 60-μm film as the colored thermoplastic resin layer 1 so that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 8 / 1.

[0088] (Transparent thermoplastic resin layer 4) Material: Polypropylene Thickness: 70 μm · Transparent homopolypropylene resin (Prime PP; manufactured by Prime Polymer Co., Ltd.)... 99 parts by mass · Ultraviolet absorber (Tinuvin 326; manufactured by BASF Japan Ltd.)... 0.5 parts by mass · Light stabilizer (Tinuvin XT55; manufactured by BASF Japan Ltd.)... 0.5 parts by mass

[0089] (Surface protective layer 5) Thickness: 5 μm · Main agent (methyl methacrylate / cyclohexyl methacrylate = 80 / 20) … 90 parts by mass · UV absorber (Tinuvin 329; manufactured by BASF Japan Ltd.) … 6 parts by mass · Light stabilizer (Tinuvin 292; manufactured by BASF Japan Ltd.) … 4 parts by mass · Curing agent (Takenate D170; manufactured by Mitsui Chemicals, Inc.) … 10 parts by mass · Solvent (ethyl acetate) … 240 parts by mass (Cosmetic sheet 10) Layer thickness: 135 - 140 μm

[0090] (Example 1) Among the polypropylene as the colored thermoplastic resin that becomes the core layer 12, 40% is polypropylene made from recycled resin, and the rest is polypropylene made from virgin resin.

[0091] As a result, a cosmetic sheet 10 having a colored thermoplastic resin layer 1 containing 40% recycled resin was obtained.

[0092] (Example 2) In the cosmetic sheet 10 of Example 1, among the polypropylene as the colored thermoplastic resin that becomes the core layer 12, 65% is polypropylene made from recycled resin, and the rest is polypropylene made from virgin resin. As a result, a cosmetic sheet 10 having a colored thermoplastic resin layer 1 containing 65% recycled resin was produced.

[0093] (Example 3) In the cosmetic sheet 10 of Example 1, among the polypropylene as the colored thermoplastic resin that becomes the core layer 12, 70% is polypropylene made from recycled resin, and the rest is polypropylene made from virgin resin. As a result, a cosmetic sheet 10 having a colored thermoplastic resin layer 1 containing 70% recycled resin was produced.

[0094] (Example 4) A decorative sheet 10 was produced in the same procedure as in Example 1, except that in the colored thermoplastic resin layer 1 in Example 1, a film as the colored thermoplastic resin layer 1 was formed such that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 7 / 1.

[0095] (Example 5) A decorative sheet 10 was produced in the same procedure as in Example 1, except that in the colored thermoplastic resin layer 1 in Example 1, a film as the colored thermoplastic resin layer 1 was formed such that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 9 / 1.

[0096] (Example 6) A decorative sheet 10 was produced in the same procedure as in Example 1, except that in the colored thermoplastic resin layer 1 in Example 1, a film as the colored thermoplastic resin layer 1 was formed such that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 10 / 1.

[0097] (Example 7) A decorative sheet 10 was produced in the same procedure as in Example 1, except that in the colored thermoplastic resin layer 1 in Example 1, a film as the colored thermoplastic resin layer 1 was formed such that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 4 / 1.

[0098] [Comparative Example] (Comparative Example 1) A decorative sheet was obtained in the same procedure as in Example 1, except that the colored thermoplastic resin layer was a single-layer thermoplastic resin layer (thickness: 60 μm) consisting only of the core layer described in Example 1. (Comparative Example 2) A decorative sheet was produced in the same procedure as in Example 1, except that in the colored thermoplastic resin layer 1 in Example 1, a film as the colored thermoplastic resin layer was formed such that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 58 / 1. (Comparative Example 3) In the colored thermoplastic resin layer 1 in Example 1, a film as the colored thermoplastic resin layer was formed in the same procedure as in Example 1, except that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was set to 1 / 1 / 1.

[0099] 〔Evaluation method〕 (Wettability) The wettability of the surface physical properties of the colored thermoplastic resin layer was evaluated. As an index representing the wettability, the wetting tension (JIS K 6768:1999) was measured. The wettability of the colored thermoplastic resin layer 3 months after film formation was measured. 〇: 45 mN / m or more ×: Less than 45 mN / m

[0100] (Light resistance performance) The light resistance performance of the colored thermoplastic resin layer was evaluated. The evaluation of the light resistance performance was visually confirmed for the state after testing with a sunshine weather meter (black panel 63 ± 3 °C, 120-minute cycle: 102 minutes of light irradiation, 18 minutes of light irradiation + water spray) in accordance with JIS B7753. ◎: No change after 2000 h of SWOM (sunshine weather meter) 〇: No change after 1500 h of SWOM △: There is a visually confirmable change after 1500 h of SWOM ×: There is a visually confirmable change after 1000 h of SWOM

[0101] (Concealability) The concealability of the decorative sheet was evaluated. The evaluation of the concealability was visually confirmed using black and white base papers. ◎: Current equivalent level 〇: Inferior to the current level but no problem ×: There is a problem with concealability

[0102] 〔Evaluation results〕 The evaluation results of the decorative sheets of the examples and comparative examples are shown in Table 1.

[0103]

Table 1

[0104] As shown in Table 1, when the ratio of the layer thicknesses “surface skin layer 11 / core layer 12 / rear skin layer 13” is within the range of “1 / 4 / 1 to 1 / 10 / 1”, good results can be obtained in terms of the wettability of the colored thermoplastic resin layer 1, the light resistance performance, and the concealability of the decorative sheet. It was confirmed that even better results can be obtained when the ratio is within the range of “1 / 7 / 1 to 1 / 9 / 1”. Further, when the addition amount of the recycled resin to the core layer is 40% or more, even better results can be obtained.

[0105] Incidentally, the present invention can be configured as follows, for example. (1) A decorative sheet including a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, The colored thermoplastic resin layer includes a core layer made of a colored thermoplastic resin, and a first skin layer and a second skin layer that are both made of a transparent thermoplastic resin and are provided on both sides of the core layer, respectively, The ratio of the layer thicknesses of the first skin layer, the core layer, and the second skin layer is within the range of first skin layer / core layer / second skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less, In the core layer, 30% or more of the colored thermoplastic resin constituting the core layer is made of a recycled resin of the colored thermoplastic resin, The decorative sheet is characterized in that the first skin layer and the second skin layer are made only of a virgin resin of the transparent thermoplastic resin. (2) The decorative sheet according to (1) above, wherein only the core layer among the first skin layer, the core layer, and the second skin layer contains a pigment. (3) The decorative sheet according to (1) or (2) above, wherein the resins constituting each of the first skin layer, the core layer, and the second skin layer are the same thermoplastic resin as each other. (4) The resins constituting each of the first skin layer, the core layer, and the second skin layer are olefin-based thermoplastic resins, and are characterized by containing a hindered amine-based radical scavenger. The cosmetic sheet according to (3) above. (5) The resins constituting each of the adhesive resin layer and the transparent thermoplastic resin layer are polyolefin-based thermoplastic resins. The cosmetic sheet according to any one of (1) to (4) above. (6) It has a surface protection layer as the outermost layer on the side of the transparent thermoplastic resin layer. At least the transparent thermoplastic resin layer and the surface protection layer each contain an ultraviolet absorber and a hindered amine-based radical scavenger. The cosmetic sheet according to any one of (1) to (5) above. (7) The core layer contains an inorganic substance, and the inorganic substance is any one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composite, and other oxides. The cosmetic sheet according to any one of (1) to (6) above. (8) When the colored thermoplastic resin layer is subjected to a 1000-hour test using a sunshine weather meter conforming to JIS B7753 at a black panel temperature of 63 ± 3 °C in a 120-minute cycle of 102 minutes of light irradiation and 18 minutes of light irradiation + water spray, the color difference is ΔE = 4 or less and no cracking is observed. The cosmetic sheet according to any one of (1) to (7) above. (9) A method for manufacturing a cosmetic sheet including a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order. The colored thermoplastic resin layer includes a core layer made of a colored thermoplastic resin, and a first skin layer and a second skin layer, both of which are made of a transparent thermoplastic resin and are provided on both sides of the core layer. The colored thermoplastic resin layer is formed such that the ratio of the layer thicknesses of the first skin layer, the core layer, and the second skin layer is in the range of first skin layer / core layer / second skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less, and the core layer is formed of the colored thermoplastic resin containing 30% or more of recycled resin, and the first skin layer and the second skin layer are formed of the transparent thermoplastic resin consisting only of virgin resin. A method for manufacturing a decorative sheet, characterized in that. (10) As the resins constituting the first skin layer, the core layer, and the second skin layer, the same thermoplastic resin is used for each other. The method for manufacturing a decorative sheet according to (9) above, characterized in that the first skin layer, the core layer, and the second skin layer are formed into a film-like colored thermoplastic resin layer by a coextrusion manufacturing method. (11) A base material, A decorative member comprising the decorative sheet according to any one of (1) to (8) above laminated on at least one surface of the base material.

Explanation of symbols

[0106] 1 Colored thermoplastic resin layer 2 Pattern layer 3 Transparent adhesive resin layer 4 Transparent thermoplastic resin layer 5 Surface protection layer 6 Primer layer 7 Concavo-convex portion 8 Base material 10 Decorative sheet 20 Decorative member

Claims

1. A decorative sheet comprising a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, the colored thermoplastic resin layer includes a core layer made of a colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer, both of which are made of a transparent thermoplastic resin; a layer thickness ratio of the first skin layer to the core layer to the second skin layer, i.e., first skin layer / core layer / second skin layer, is in the range of 1 / 4 / 1 to 1 / 10 / 1; The core layer is made of 30% or more of the colored thermoplastic resin constituting the core layer, and is made of recycled resin of the colored thermoplastic resin, A decorative sheet, characterized in that the first skin layer and the second skin layer are composed only of virgin resin of the transparent thermoplastic resin.

2. 2. The decorative sheet according to claim 1, wherein, of the first skin layer, the core layer and the second skin layer, only the core layer contains a pigment.

3. 2. The decorative sheet according to claim 1, wherein the resins constituting the first skin layer, the core layer and the second skin layer are the same thermoplastic resin.

4. The decorative sheet according to claim 3, characterized in that the resin constituting each of the first skin layer, the core layer and the second skin layer is an olefin-based thermoplastic resin and contains a hindered amine-based radical scavenger.

5. 2. The decorative sheet according to claim 1, wherein the resin constituting each of said adhesive resin layer and said transparent thermoplastic resin layer is a polyolefin-based thermoplastic resin.

6. a surface protective layer as the outermost layer on the transparent thermoplastic resin layer side; 2. The decorative sheet according to claim 1, wherein at least said transparent thermoplastic resin layer and said surface protective layer each contain an ultraviolet absorbing agent and a hindered amine radical scavenger.

7. 2. The decorative sheet according to claim 1, wherein the core layer contains an inorganic material, the inorganic material being one or more of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

8. The decorative sheet according to claim 1, characterized in that the colored thermoplastic resin layer has a color difference of ΔE = 4 or less and no cracks are observed when tested for 1,000 hours using a sunshine weather meter conforming to JIS B7753, with a black panel temperature of 63 ± 3°C and a 120-minute cycle of 102 minutes of light irradiation and 18 minutes of light irradiation + water spray.

9. A method for producing a decorative sheet comprising a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, comprising: the colored thermoplastic resin layer includes a core layer made of a colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer, both of which are made of a transparent thermoplastic resin; A method for manufacturing a decorative sheet, characterized in that the colored thermoplastic resin layer is formed so that the layer thickness ratio of the first skin layer, the core layer and the second skin layer is in the range of first skin layer / core layer / second skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less, the core layer is formed from the colored thermoplastic resin containing 30% or more recycled resin, and the first skin layer and the second skin layer are formed from the transparent thermoplastic resin consisting only of virgin resin.

10. The first skin layer, the core layer, and the second skin layer are made of the same thermoplastic resin, The method for producing a decorative sheet according to claim 9, characterized in that the first skin layer, the core layer and the second skin layer are produced by a co-extrusion method to form the colored thermoplastic resin layer in a film form.

11. A substrate; A decorative member comprising: the decorative sheet according to claim 1 laminated on at least one surface of the substrate.

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