Decorative sheet, method for manufacturing a decorative sheet, and decorative component

Abstract

To provide a decorative sheet with a higher proportion of recycled resin while suppressing a decrease in productivity and pinking resistance. [Solution] The decorative sheet 10 is configured to include only a colored thermoplastic resin layer 1 as the thermoplastic resin layer, and the colored thermoplastic resin layer 1 is configured to include an intermediate layer 12 made of colored thermoplastic resin and surface skin layers 11 and 13 provided on both sides of the intermediate layer 12 and both made of transparent thermoplastic resin, and furthermore, only the intermediate layer 12 contains recycled resin, the mass ratio of recycled resin in the intermediate layer 12 is 5% by mass or more and 30% by mass or less, and the ratio of the layer thickness of the surface skin layer 11, the intermediate layer 12 and the surface skin layer 13 is formed to be within the range of surface skin layer 11 / intermediate layer 12 / surface skin layer 13 = 1 / 4 / 1 or more and 1 / 10 / 1 or less.

Description

Technical Field

[0005] ,

[0001] The present invention relates to a cosmetic sheet, a method for manufacturing the 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 of 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] However, in recycled materials, a considerable amount of foreign matter is mixed in during the process from waste materials to recycled materials. When a recycled material is added to a cosmetic sheet, there is a concern that defects caused by foreign matter (such as printing omission) may occur during printing, resulting in a decrease in productivity. There is also a concern that the pinholing resistance deteriorates due to the recycling aids added to the recycled materials. Therefore, there has been a demand for a cosmetic sheet with a higher usage ratio of recycled materials while suppressing the decrease in productivity and pinholing resistance.

[0005] Therefore, this invention was made in view of the above-mentioned conventional problems, and aims to provide a decorative sheet, a method for manufacturing a decorative sheet, and a decorative component that have a higher proportion of recycled materials used while suppressing a decrease in productivity and pinking resistance. [Means for solving the problem]

[0006] According to one aspect of the present invention, a decorative sheet is provided which comprises only a colored thermoplastic resin layer as a thermoplastic resin layer, wherein the colored thermoplastic resin layer comprises an intermediate layer composed of a colored thermoplastic resin, and a first surface skin layer and a second surface skin layer provided on both sides of the intermediate layer and both composed of transparent thermoplastic resin, wherein only the intermediate layer contains recycled resin, the mass ratio of recycled resin in the intermediate layer is 5% by mass or more and 30% by mass or less, and the ratio of the layer thickness of the first surface skin layer, the intermediate layer and the second surface skin layer is within the range of first surface skin layer / intermediate layer / second surface skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less.

[0007] Furthermore, according to another aspect of the present invention, a method for manufacturing a decorative sheet comprising only a colored thermoplastic resin layer as the thermoplastic resin layer is provided, wherein the colored thermoplastic resin layer is composed of three layers: an intermediate layer containing a colored thermoplastic resin, and a first surface skin layer and a second surface skin layer provided on both sides of the intermediate layer and composed of a transparent thermoplastic resin, and the first surface skin layer, the intermediate layer and the second surface skin layer are formed into a film using the same thermoplastic resin by co-extrusion so that the ratio of the layer thicknesses of the first surface skin layer, the intermediate layer and the second surface skin layer is in the range of first surface skin layer / intermediate layer / second surface skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less, and only the intermediate layer contains a colored pigment and recycled thermoplastic resin, and the mass ratio of recycled resin in the intermediate layer is 5% by mass or more and 30% by mass or less. Furthermore, according to another aspect of the present invention, a decorative member is provided comprising a base material and the decorative sheet laminated on at least one surface of the base material. [Effects of the Invention]

[0008] According to one aspect of the present invention, a decorative sheet, a method for manufacturing a decorative sheet, and a decorative component can be obtained that have a higher proportion of recycled materials used while suppressing a decrease in productivity and pinking resistance. [Brief explanation of the drawing]

[0009] [Figure 1] This is a schematic cross-sectional view showing an example of a decorative sheet and decorative component according to one embodiment of the present invention. [Modes for carrying out the invention]

[0010] The embodiments of this technology will be described below with reference to the drawings. Here, the drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc., may differ from reality. Furthermore, the embodiments shown below illustrate configurations for realizing the technical idea of ​​the present invention, and the technical idea of ​​the present invention is not limited to the materials, shapes, and structures of the components described below. The technical idea of ​​the present invention can be modified in various ways within the technical scope defined by the claims described in the patent claims.

[0011] [Decorative sheet 10] As shown in Figure 1, a decorative sheet 10 according to one embodiment of the present invention comprises a colored thermoplastic resin layer 1, a pattern layer 2, and a surface protection layer 3, and these layers are laminated in this order. Furthermore, the decorative sheet 10 has a primer layer 4 on the side of the colored thermoplastic resin layer 1 opposite to the pattern layer 2. The decorative sheet 10 has only the colored thermoplastic resin layer 1 as the thermoplastic resin layer. Furthermore, the surface protective layer 3 is provided with uneven surfaces 5 formed by embossing. For example, the uneven surfaces 5 may be a pattern that matches the pattern of the pattern layer 2, or a pattern that does not match the pattern.

[0012] [Colored thermoplastic resin layer 1] The colored thermoplastic resin layer 1 according to this embodiment is a so-called two-type, three-layer laminate, for example, in which a surface skin layer (first surface skin layer) 11, an intermediate layer 12, and a surface skin layer (second surface skin layer) 13 are laminated in this order, and the surface skin layer 11 is in contact with the primer layer 4, and the surface skin layer 13 is in contact with the pattern layer 2. The intermediate layer 12 is formed of a colored thermoplastic resin containing recycled resin, and the surface skin layers 11 and 13 are formed of virgin resin of transparent thermoplastic resin.

[0013] The following provides a detailed explanation of the structure of each layer mentioned above. (Middle class 12) The intermediate layer 12 according to this embodiment is a base layer for the colored thermoplastic resin layer 1. The intermediate layer 12 is composed of a colored thermoplastic resin, but it is composed of recycled thermoplastic resin. The mass ratio of recycled resin in the intermediate layer 12 is in the range of 5% by mass or more and 30% by mass or less.

[0014] The intermediate layer 12 can be made of, for example, an olefin-based thermoplastic resin. Among olefin-based thermoplastic resins, ethylene-methacrylic acid copolymers are particularly preferred, and for example, a material obtained by partially neutralizing (degree of neutralization 50 mol%) a copolymer of ethylene and an unsaturated carboxylic acid with Zn metal ions is preferred. In other words, the intermediate layer 12 according to this embodiment may be made of an ionomer resin. Alternatively, the intermediate layer 12 according to this embodiment may be made of polypropylene (PP) resin.

[0015] The intermediate layer 12 should contain at least titanium dioxide as a coloring pigment. The coloring pigment is contained only in the intermediate layer 12 and not in the surface skin layers 11 and 13. The titanium dioxide content in the intermediate layer 12 should be within the range of 10 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the resin components constituting the intermediate layer 12, 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. If the titanium dioxide content is less than 10 parts by mass, the coloring of the intermediate layer 12 may not be sufficient, and it may not be possible to give the intermediate layer 12 sufficient opacity. Also, if the titanium dioxide content exceeds 50 parts by mass, the proportion of the resin components constituting the intermediate layer 12 will relatively decrease, and it may not be possible to give the intermediate layer 12 the strength necessary for printing.

[0016] The average particle size (D50) of titanium dioxide contained in the intermediate layer 12 is preferably within the range of 10 nm to 100 nm. The thickness of the intermediate layer 12 may be within the range of 4 to 10 times the thickness of each of the surface skin layers 11 and 13. In other words, the ratio of the thicknesses of each layer (surface skin layer 11 / intermediate layer 12 / surface skin layer 13) may be within the range of 1 / 4 / 1 to 1 / 10 / 1. Preferably, the ratio of the thicknesses of each layer (surface skin layer 11 / intermediate layer 12 / surface skin layer 13) may be within the range of 1 / 7 / 1 to 1 / 9 / 1. If the thickness of the intermediate layer 12 is within the above numerical range, the colored thermoplastic resin layer 1 (intermediate layer 12) itself can be given high opacity, 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 thicknesses of each layer is approximately 1 / 8 / 1.

[0017] The thickness of the intermediate 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 intermediate layer 12 is within the above numerical range, high hiding power can be imparted to the colored thermoplastic resin layer 1 (intermediate layer 12) itself.

[0018] Further, the intermediate layer 12 may contain an ultraviolet absorber. The content of the ultraviolet absorber contained in the intermediate layer 12 may be within the range of 0.001 part by mass or more and 10 parts by mass or less, more preferably within the range of 0.05 part by mass or more and 5 parts by mass or less, and even more preferably within 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 intermediate layer 12. If the content of the ultraviolet absorber is less than 0.001 part by mass, the ultraviolet absorption performance in the intermediate layer 12 may not be sufficient and sufficient durability may not be imparted to the intermediate layer 12. Further, if the content of the ultraviolet absorber exceeds 10 parts by mass, the proportion of the resin component constituting the intermediate layer 12 relatively decreases, so that wiping or the like may occur in the intermediate layer 12, and the strength required for printing may not be imparted, or the film formation itself may not be possible.

[0019] Examples of the ultraviolet absorber that can be used in the present embodiment include benzotriazole-based, hydroxyphenyltriazine-based, benzophenone-based, and the like. 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, and the like, but are not limited thereto.

[0020] In addition, if a hydroxyphenyltriazine-based ultraviolet absorber is selected as the ultraviolet absorber added to the intermediate layer 12, the triazine skeleton suppresses bleeding, and the triazine skeleton is chemically stable compared to 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.

[0021] Examples of hydroxyphenyltriazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-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-triazine-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]triazine-2-yl) Examples include -3-hydroxyphenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazine-2-yl)-3-hydroxyphenoxy]-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-isooctyloxyphenyl)-s-triazine, and 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine. In this embodiment, the intermediate layer 12 may contain 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine.

[0022] Furthermore, by using both hydroxyphenyltriazine-based and benzotriazole-based UV absorbers in combination, even better weather resistance can be provided due to their interaction. This is because benzotriazole-based UV absorbers have an absorption peak at longer wavelengths than hydroxyphenyltriazine-based UV absorbers, thus broadening the wavelength range over which ultraviolet light is absorbed when used in combination. The amount of benzotriazole-based UV absorber to be added is preferably in the range of 0.001 parts by mass to 10 parts by mass per 100 parts by mass of the resin component constituting the intermediate layer 12. Adding 0.001 parts by mass or more will yield the desired effect, while adding 10 parts by mass or less will suppress the bleed-out of the UV absorber. However, because benzotriazole-based UV absorbers have an absorption peak at longer wavelengths, they may have a yellowish tint. If color is a concern, the amount added should be reduced. Examples of benzophenone-based UV absorbers that can be used include octabenzone, modified versions, polymers, and derivatives.

[0023] Furthermore, the intermediate layer 12 may contain a light stabilizer such as a hindered amine-based radical scavenger. The amount of light stabilizer contained in the intermediate layer 12 should be within the range of 0.001 parts by mass to 10 parts by mass, more preferably within the range of 0.05 parts by mass to 5 parts by mass, and even more preferably within the range of 0.5 parts by mass to 3 parts by mass, per 100 parts by mass of the resin component constituting the intermediate layer 12. If the amount of light stabilizer is less than 0.001 parts by mass, the stability of the intermediate layer 12 against ultraviolet light may not be sufficient, and it may not be possible to impart sufficient durability to the intermediate layer 12. Also, if the amount of light stabilizer exceeds 10 parts by mass, the proportion of the resin component constituting the intermediate layer 12 will relatively decrease, which may cause powdering or other issues in the intermediate layer 12, making it impossible to impart the strength necessary for printing, or even to form a film at all.

[0024] Examples of hindered amine-based radical scavengers usable 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, and bis(2,2,6,6-tetramethyl-4-piperidyl benzoate). Methyl-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 Silate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-diter-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate 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- Third 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,Examples include, but are not limited to, reaction products of 6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatecyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro1,3,5-triazine and 2-aminoethanol.

[0025] An antioxidant may be added to the intermediate layer 12. Phenolic antioxidants are preferably used. In this embodiment, for example, 2,6-diter-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl(3,5-diter-butyl-4-hydroxybenzyl)phosphonate, 1,6-hexamethylenebis[(3,5-diter-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) Tris(2-butyl-m-cresol), 4,4′-butylidenebis(6-tertiary butyl-m-cresol), 2,2′-ethylidenebis(4,6-ditertiary butylphenol), 2,2′-ethylidenebis(4-secondary butyl-6-tertiary butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tertiary butylbenzyl)isocyanurate, 1,3,5-tris(3,5-ditertiary butyl-4-hydroxybenzyl)isocyanurate 1,3,5-Tris(3,5-Di-Tri-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-Tri-butyl-4-methyl-6-(2-acryloyloxy-3-Tri-butyl-5-methylbenzyl)phenol, Stearyl(3,5-Di-Tri-butyl-4-hydroxyphenyl)propionate, Tetrakis[3-(3,5-Di-Tri-butyl-4-hydroxyphenyl)propionate methyl]methane, Thiodiethylene glycol bis[(3,5-Di-Tri-butyl-4-hydroxyphenyl) [Propionate], 1,6-Hexamethylenebis[(3,5-Diter-butyl-4-hydroxyphenyl)propionate], Bis[3,3-Bis(4-hydroxy-3-ter-butylphenyl)butyric acid] glycol ester, Bis[2-ter-butyl-4-methyl-6-(2-hydroxy-3-ter-butyl-5-methylbenzyl)phenyl] terephthalate, 1,3,5-Tris[(3,5-Diter-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, 3,9-Bis[1,Examples include 1-dimethyl-2-{(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane and triethylene glycol bis[(3-tertiary butyl-4-hydroxy-5-methylphenyl)propionate]. Furthermore, the content of the above-mentioned antioxidant is preferably in the range of 0.001 parts by mass to 10 parts by mass, and more preferably in the range of 0.05 parts by mass to 5 parts by mass, per 100 parts by mass of the resin component constituting the intermediate layer 12.

[0026] A processing stabilizer may be added to the intermediate layer 12. A phosphorus-based processing stabilizer is preferably used. In this embodiment, for example, trisnonylphenyl phosphite, tris[2-tertiary-butyl-4-(3-tertiary-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-ditertiary-butylphenyl)pentaerythritol diphosphite, bis(2,6-ditertiary-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-tritertiary-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4′-n-butylidenebis(2-tertiary-butylphenyl) (Tyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tertiary butylphenyl)butane triphosphite, tetrakis(2,4-ditertiary butylphenyl) biphenylenediphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis(4,6-tertiary butylphenyl)-2-ethylhexyl phosphite, 2,2 Examples include '-methylenebis(4,6-tertiary butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-ditertiary butylphenyl)fluorophosphite, tris(2-[(2,4,8,10-tetrakistertiary butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl)oxy]ethyl)amine, and phosphites of 2-ethyl-2-butylpropylene glycol and 2,4,6-tritertiary butylphenol. Furthermore, the content of the above-mentioned processing stabilizers is preferably in the range of 0.001 parts by mass to 10 parts by mass, and more preferably in the range of 0.05 parts by mass to 5 parts by mass, per 100 parts by mass of the resin component constituting the intermediate layer 12.

[0027] (Surface skin layers 11, 13) The surface skin layer 11 according to this embodiment is a layer formed so as to be in contact with one surface of the intermediate layer 12. The surface skin layer 13 according to this embodiment is a layer formed so as to be in contact with the other surface of the intermediate layer 12. Each of the surface skin layers 11 and 13 does not contain coloring pigments such as titanium dioxide. Each of the surface skin layers 11 and 13 is composed of virgin resin of transparent thermoplastic resin and does not contain recycled resin.

[0028] Each of the surface skin layers 11 and 13 may be composed of the same thermoplastic resin as the intermediate layer 12 described above. In other words, the material constituting each of the surface skin layers 11 and 13 is not particularly limited as long as it is a thermoplastic resin, and for example, an olefin-based thermoplastic resin can be used, similar to the intermediate layer 12. Among olefin-based resins, ethylene-methacrylic acid copolymers are particularly preferred, and for example, a material obtained by partially neutralizing (degree of neutralization 50 mol%) a copolymer of ethylene and an unsaturated carboxylic acid with Zn metal ions is preferred. In other words, at least one of the surface skin layer 11 and surface skin layer 13 according to this embodiment may be formed of an ionomer resin. Also, at least one of the surface skin layer 11 and surface skin layer 13 according to this embodiment may be formed of polypropylene (PP) resin.

[0029] The thickness of each of the surface skin layers 11 and 13 may be, for example, within the range of 1 μm to 20 μm, more preferably within the range of 4 μm to 10 μm, and even more preferably within the range of 5 μm to 8 μm. If the thickness of each of the surface skin layers 11 and 13 is within the above numerical range, the colored thermoplastic resin layer 1 itself can be given high opacity. Furthermore, the thickness of the surface skin layer 11 and the thickness of the surface skin layer 13 may be the same.

[0030] Each of the surface skin layers 11 and 13 may contain an ultraviolet absorber that can be added to the intermediate layer 12 described above. By adding an ultraviolet absorber to each of the surface skin layers 11 and 13, the durability (weather resistance) of the colored thermoplastic resin layer 1 itself can be improved. Furthermore, the amount of UV absorber contained in each of the surface skin layers 11 and 13 may be the same as the amount of UV absorber contained in the intermediate layer 12 described above. Also, the type of UV absorber contained in each of the surface skin layers 11 and 13 may be the same as the type of UV absorber contained in the intermediate layer 12 described above.

[0031] Furthermore, each of the surface skin layers 11 and 13 may contain a light stabilizer such as a hindered amine-based radical scavenger that can be added to the intermediate layer 12 described above. By adding a light stabilizer to each of the surface skin layers 11 and 13, cracking and chalking of the colored thermoplastic resin layer 1 itself can be improved. In addition, by adding a light stabilizer to each of the surface skin layers 11 and 13, deterioration of the pattern layer 2, primer layer 4, or any additional coating layer in contact with the surface skin layers 11 and 13 can be suppressed.

[0032] Furthermore, the amount of light stabilizer contained in each of the surface skin layers 11 and 13 may be the same as the amount of light stabilizer contained in the intermediate layer 12 described above. Also, the type of light stabilizer contained in each of the surface skin layers 11 and 13 may be the same as the type of light stabilizer contained in the intermediate layer 12 described above.

[0033] Furthermore, each of the surface skin layers 11 and 13 may contain antioxidants that can be added to the intermediate layer 12 as described above. Also, the amount of antioxidant contained in each of the surface skin layers 11 and 13 may be the same as the amount of antioxidant contained in the intermediate layer 12 as described above. Furthermore, the type of antioxidant contained in each of the surface skin layers 11 and 13 may be the same as the type of antioxidant contained in the intermediate layer 12 as described above.

[0034] Furthermore, each of the surface skin layers 11 and 13 may contain processing stabilizers that can be added to the intermediate layer 12 as described above. Also, the amount of processing stabilizers contained in each of the surface skin layers 11 and 13 may be the same as the amount of processing stabilizers contained in the intermediate layer 12 as described above. Furthermore, the type of processing stabilizer contained in each of the surface skin layers 11 and 13 may be the same as the type of processing stabilizer contained in the intermediate layer 12 as described above.

[0035] (modified version) In this embodiment, the case in which an ultraviolet absorber and a light stabilizer are added to each of the surface skin layers 11 and 13 has been described, but the present invention is not limited thereto. For example, the ultraviolet absorber and light stabilizer may be added to only one of the skin layers (e.g., the surface skin layer 11), or at least one of the ultraviolet absorber and the light stabilizer may be added to only one of the skin layers (e.g., the surface skin layer 11). Furthermore, the thickness of the colored thermoplastic resin layer 1 is preferably within the range of 25 μm to 200 μm. If the thickness of the colored thermoplastic resin layer 1 is within the above numerical range, the colored thermoplastic resin layer 1 itself can be given even higher opacity.

[0036] Furthermore, in this embodiment, the intermediate layer 12 may be made by adding at least one of the following to the random or homo-polypropylene resin or polyethylene resin described above: a hindered phenol-based antioxidant, an ultraviolet absorber, and a hindered amine-based light stabilizer, and then adding at least one of the following as a coloring pigment: iron oxide, carbon black, titanium dioxide, phthalocyanine blue, and isoindolinone. In addition to the resins described above, copolymerized polyester resins, foamed polyester resins, acrylic resins, etc., may also be used. Furthermore, 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 intermediate layer 12 has the above configuration, the same effects as the decorative sheet 10 and the decorative member 20 described later in this embodiment can be obtained.

[0037] (Method for manufacturing the colored thermoplastic resin layer 1) Below, an example of a method for manufacturing the colored thermoplastic resin layer 1 according to this embodiment will be briefly described. The colored thermoplastic resin layer 1 is formed by co-extruding the surface skin layer 11, the intermediate layer 12, and the surface skin layer 13 in that order to create a film. In this way, the two-type, three-layer colored thermoplastic resin layer 1 according to this embodiment is formed.

[0038] (Picture layer) The pattern layer 2 is a layer that provides opacity or design, and can be provided by printing a pattern ink on the entire surface or partially on the colored thermoplastic resin layer 1. For the binder of the pattern ink, you can choose from a selection of materials such as nitrated cotton, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, and polyester, either individually or as modified versions of each. These can be water-based, solvent-based, or emulsion-based, and the curing method can be either a one-component type or a two-component type using a curing agent. Furthermore, it is also possible to cure the ink by irradiation with active energy rays such as ultraviolet light or electron beams.

[0039] As pigments for the pattern ink, various known pigments can be used, such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolon, cobalt, phthalocyanine, carbon, titanium dioxide, iron oxide, mica, and other pearl pigments. When selecting these ink materials, it is necessary to consider their adhesion to the colored thermoplastic resin layer 1 beneath the pattern layer 2 and to the resin laminated on top of the pattern layer 2.

[0040] The pattern layer 2 may contain various additives as needed, such as the UV absorbers, radical scavengers, and dispersants mentioned above. The pattern layer 2 can be applied directly to the colored thermoplastic resin layer 1 using known printing techniques such as gravure printing, offset printing, screen printing, flexographic printing, silk screen printing, electrostatic printing, and inkjet printing. In addition to ink application, it is also possible to apply metallic-looking designs by vapor deposition or sputtering of various metals.

[0041] (Surface protective layer) The surface protection layer 3 is a layer for improving the weather resistance of the decorative sheet 10. The surface protection layer 3 is formed using, for example, an acrylic resin. There are no particular restrictions on the acrylic resin, and the same type of acrylic resin used for the surface protection layer in conventional decorative sheets can be used. For example, an acrylic resin consisting of a mixture of methyl methacrylate monomer and cyclohexyl methacrylate can be used as the acrylic resin constituting the surface protection layer 3. Furthermore, there may be one type or multiple types of acrylic resin constituting the surface protection layer 3. The acrylic resins that can be used in the surface protection layer 3 of this embodiment will be described in detail below.

[0042] In this embodiment, the surface protection layer 3 may be mainly composed of an acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component. In this embodiment, cyclohexyl (meth)acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By including cyclohexyl (meth)acrylate as a monomer component, the affinity for water can be reduced, and deterioration due to hydrolysis and other factors can be suppressed. It is desirable that the cyclohexyl (meth)acrylate content be within the range of 5% by mass or more and 50% by mass or less of the monomer components of the entire acrylic resin composition. By setting the cyclohexyl (meth)acrylate content to 5% by mass or more, a sufficient deterioration suppression effect can be obtained, and by setting the content to 50% by mass or less, it is possible to impart high weather resistance over time without significantly changing the various properties of the surface protection layer 3, such as maintaining and improving surface hardness, improving stain resistance, and adjusting surface gloss.

[0043] In addition to the cyclohexyl (meth)acrylate mentioned above, other monomer components of the acrylic resin composition that can be used for the surface protective layer 3 include, 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, and methoxycyclohexylmethyl (meth)acrylate. Of these, those containing isomers may be used either as individual isomers or as mixtures of isomers.

[0044] Furthermore, as a method for forming the surface protective layer 3, for example, a coating liquid made of an acrylic resin composition containing the above-mentioned cyclohexyl (meth)acrylate as a monomer component is applied to the pattern layer 2. As for the type of coating liquid, for example, a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type cured by irradiation with ultraviolet light or ionizing radiation can all be used. However, considering weather resistance, a two-component curing type or an active energy ray curing type is preferred, and if post-processing after bonding to various substrates to become decorative components is considered, a two-component curing type that is crosslinked by isocyanate curing is desirable.

[0045] As the two-component curing type acrylic resin composition described above, a composition containing, for example, an acrylic resin having two or more functional groups selected from hydroxyl groups, amino groups, and carboxyl groups in one molecule, and a polyisocyanate compound having two or more isocyanate groups that can react with the functional groups in one molecule is preferred. Particularly preferred is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

[0046] As acrylic polyols having two or more hydroxyl groups in a single molecule, for example, (meth)acrylic acid ester copolymers containing hydroxyethyl (meth)acrylate as a monomer component in addition to the cyclohexyl (meth)acrylate mentioned above can be used. On the other hand, as polyisocyanate compounds having two or more isocyanate groups in a single molecule, for example, tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, and burette types synthesized by known techniques from one or more compounds selected from these. Furthermore, compositions by mixing one or more of these different types of polyisocyanates can be used. Among these, HDI, or the trimer type, TMP adduct type, and burette type of HDI are preferred from the viewpoint of weather resistance. The content of the isocyanate compound relative to the resin component described above can be set arbitrarily, but it is desirable to set it so that the hydroxyl group / isocyanate group equivalent ratio is about 1 / 1 to 1 / 3. In particular, if the equivalent amount of hydroxyl groups is greater than the equivalent amount of isocyanate groups, crosslinking will not proceed sufficiently, and the desired performance will not be added to the surface protective layer 3, which is undesirable.

[0047] Furthermore, as the active energy ray curing type acrylic resin composition, for example, known monomers and oligomers having (meth)acryloyl groups can be used, and in addition to these monomers and oligomers, the above-mentioned cyclohexyl (meth)acrylate may be added. The acrylic resin described above may have an ultraviolet absorber and a light stabilizer added to it. In other words, the surface protective layer 3 may be formed from an acrylic resin composition containing an ultraviolet absorber and a light stabilizer. The ultraviolet absorber contained in the surface protective layer 3 may be one of the ultraviolet absorbers listed as an ultraviolet absorber that can be added to the colored thermoplastic resin layer 1, preferably a benzotriazole-based ultraviolet absorber.

[0048] Furthermore, the amount of UV absorber in the surface protective layer 3 is preferably within the range of 1 part by mass to 30 parts by mass per 100 parts by mass of acrylic resin (resin component). If the amount of UV absorber in the surface protective layer 3 is less than 1 part by mass, sufficient weather resistance may not be obtained. Also, if the amount of UV absorber in the surface protective layer 3 exceeds 30 parts by mass, bleed-out of the UV absorber may occur. In addition, because the content of acrylic resin (resin component) becomes relatively low, problems may occur during the formation of the surface protective layer 3. The light stabilizer contained in the surface protective layer 3 may be one of the light stabilizers listed as those that can be added to the colored thermoplastic resin layer 1, i.e., a hindered amine-based radical scavenger.

[0049] Furthermore, the content of the light stabilizer in the surface protective layer 3 is preferably within the range of 1 part by mass to 30 parts by mass per 100 parts by mass of acrylic resin (resin component). If the content of the light stabilizer in the surface protective layer 3 is less than 1 part by mass, sufficient weather resistance may not be obtained. Also, if the content of the light stabilizer in the surface protective layer 3 exceeds 30 parts by mass, the content of acrylic resin (resin component) will be relatively low, which may cause problems during the formation of the surface protective layer 3. In addition, if it exceeds 30 parts by mass, bleed-out of the light stabilizer may occur.

[0050] Furthermore, the thickness of the surface protective layer 3 is preferably within the range of 1 μm to 20 μm. If the thickness of the surface protective layer 3 is within the above numerical range, sufficient weather resistance can be reliably obtained, and flexibility is imparted to the surface protective layer 3, thereby reducing the occurrence of cracks in the surface protective layer 3.

[0051] Furthermore, various known coating methods can be used to provide the surface protection layer 3, such as gravure coating, reverse coating, gravure reverse coating, die coating, and flow coating. In addition, various additives such as anti-friction agents, anti-blocking agents, and antistatic agents may be added to the surface protection layer 3 as needed. Furthermore, the surface protective layer 3 may or may not be formed in the region where the uneven portion 5 is formed. However, it is preferable that the surface protective layer 3 be formed in the region where the uneven portion 5 is formed, as this improves durability (weather resistance) compared to when it is not formed.

[0052] (modified version) In this embodiment, a benzotriazole-based ultraviolet absorber was given as a preferred example of the ultraviolet absorber contained in the surface protective layer 3, but the present invention is not limited thereto. For example, a hydroxyphenyltriazine-based ultraviolet absorber, preferably 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which was listed as an ultraviolet absorber that can be added to the colored thermoplastic resin layer 1, may be added to the surface protective layer 3. This point will be explained in detail below.

[0053] The surface protective layer 3 may contain at least one substance having the structure of 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (corresponding to formula (1) below). This is because the hydroxyphenyltriazine-based ultraviolet absorber shown in formula (1) has high ultraviolet absorption capacity in the low wavelength region, which is relatively high energy among ultraviolet rays, and is chemically stable compared to other ultraviolet absorbers that absorb in almost the same wavelength region, thus maintaining long-term ultraviolet absorption performance.

[0054] [ka]

[0055] In this embodiment, it is preferable that the amount of all hydroxyphenyltriazine-based ultraviolet absorbers, including those having the structure of formula (1), added is within the range of 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of acrylic resin (resin composition). By adding 1 part by mass or more of ultraviolet absorber, a weather resistance improvement effect is achieved, and by adding 30 parts by mass or less, the influence on physical properties other than weather resistance of the surface protective layer 3 can be suppressed to a level that does not pose a practical problem. Furthermore, a hydroxyphenyltriazine-based ultraviolet absorber having the structure shown in formula (1) may account for 30% to 95% by mass of all hydroxyphenyltriazine-based ultraviolet absorbers contained in the surface protective layer 3.

[0056] Furthermore, in this embodiment, by using in combination a hydroxyphenyltriazine-based ultraviolet absorber having the structure of formula (1) and a hydroxyphenyltriazine-based ultraviolet absorber having the structure of 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (corresponding to formula (2) below) in the surface protective layer 3, even better weather resistance is provided. 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 of time, and also has a light absorption peak on the longer wavelength side than the one having the structure of formula (1), so the wavelength range over which ultraviolet light is absorbed is broadened when used in combination.

[0057] [ka]

[0058] (Primer layer 4) The primer layer 4 is a layer that improves the adhesion between the decorative sheet 10 and the adhesive used for bonding the decorative sheet 10 to a predetermined substrate 6 when forming the decorative member 20 described later. For example, when the substrate 6 is made of wood-based materials, or metal-based materials such as aluminum or steel plate substrates, preferably metal-based materials, adhesives such as vinyl acetate emulsion or two-component curing urethane adhesives are used, so it is desirable that the primer layer 4 be designed with a resin that matches these adhesives. For example, the primer layer 4 can be made of urethane, acrylic, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester, etc. In particular, a two-component curing urethane primer made by blending polyester polyol and polyisocyanate is preferred. Furthermore, adding inorganic powders such as silica, barium sulfate, or calcium carbonate to these materials when forming the primer layer 4 is effective in preventing blocking during winding and storage, and in improving adhesive strength through an anchoring effect.

[0059] (Uneven part) The uneven surface 5 is intended to give the surface of the decorative sheet 10 a three-dimensional design. Any uneven shape can be used for the uneven surface 5. For example, wood grain tubular shape, stone pattern, cloth pattern, abstract pattern, Japanese paper pattern, suede pattern, leather pattern, pear-skin pattern, sand pattern, hairline pattern, group of parallel lines, or combinations thereof can be used. The uneven surface 5 is formed after the surface protective layer 3 is formed.

[0060] [Effects of the Embodiment] (1) The decorative sheet 10 is configured to include only a colored thermoplastic resin layer 1 as the thermoplastic resin layer, and the colored thermoplastic resin layer 1 is formed to include an intermediate layer 12 made of colored thermoplastic resin and surface skin layers 11 and 13 provided on both sides of the intermediate layer 12 and both made of transparent thermoplastic resin, with only the intermediate layer 12 containing recycled thermoplastic resin, and the mass ratio of recycled resin in the intermediate layer 12 being 5% by mass or more and 30% by mass or less, and furthermore the ratio of the layer thickness of the surface skin layer 11 that does not contain recycled resin, the intermediate layer 12 that contains recycled resin, and the surface skin layer 13 that does not contain recycled resin is within the range of surface skin layer 11 / intermediate layer 12 / surface skin layer 13 = 1 / 4 / 1 or more and 1 / 10 / 1 or less.Therefore, compared to a decorative sheet configured to include a colored thermoplastic resin layer and a transparent thermoplastic resin layer, for example, the proportion of recycled resin used in the entire decorative sheet can be increased (about 10% or more in the entire decorative sheet), and since there is no transparent thermoplastic resin layer, it can be produced with fewer man-hours. Here, recycled materials inevitably contain a certain amount of foreign matter during the process of generating recycled materials from waste materials. Therefore, when decorative sheets are made by adding recycled materials, defects caused by foreign matter, such as printing defects, may occur, potentially leading to reduced printability and productivity. However, since the number of steps required to produce decorative sheets can be reduced, the inclusion of foreign matter can be suppressed, and thus the decline in printability and productivity can be suppressed.

[0061] Furthermore, since surface skin layers 11 and 13, which do not contain recycled resin and are made of virgin resin, are provided on both sides of the intermediate layer 12, having a certain thickness relative to the thickness of the intermediate layer 12 containing recycled resin, a certain portion of the thickness of the colored thermoplastic resin layer 1 on each side will have the properties of virgin resin. As a result, the printability, light resistance, surface stability, and other properties of the colored thermoplastic resin layer 1 can be ensured, and a colored thermoplastic resin layer 1 can be realized that has surface properties equivalent to those of a layer made of virgin resin, even though it contains recycled resin.

[0062] Furthermore, while the addition of recycling aids to the recycled material may cause issues such as reduced pinking resistance, the mass ratio of recycled resin in the intermediate layer 12 is set to 5% by mass or more and 30% by mass or less. Therefore, it is possible to suppress the reduction in pinking resistance caused by the addition of recycling aids to the recycled material, and to obtain a level of pinking resistance equivalent to that of a decorative sheet using conventional olefin colored film as the base material. In this way, even while using recycled resin, it is possible to obtain decorative sheets with excellent printability (i.e., production suitability) and pinking resistance without a significant decrease in productivity.

[0063] (2) The resins constituting each layer of the surface skin layer 11, the intermediate layer 12, and the surface skin layer 13 are all the same olefin-based thermoplastic resin and contain a hindered amine-based radical scavenger, so that the decorative sheet 10 and the decorative member 20 can be given high weather resistance.

[0064] (3) The intermediate layer 12 contains inorganic material, and the inorganic material includes one or more of the following: calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composite, and other oxides. Therefore, the opacity of the colored thermoplastic resin layer 1 can be improved.

[0065] (4) The outermost layer is a surface protective layer 3, and since at least the surface protective layer 3 contains an ultraviolet absorber and a hindered amine-based radical scavenger, a highly weather-resistant decorative sheet can be obtained.

[0066] [Variation] As shown in Figure 1, the decorative sheet 10 according to the above embodiment may be bonded to a base material 6, which is a base material for decorative materials, to form a decorative member 20. In the decorative member 20, the decorative sheet 10 only needs to be provided on at least one side of the base material 6, or it may be provided on both sides.

[0067] [Base material] The base material 6 can be a wood-based or metal-based material. Examples of wood-based materials include wood veneer, wood plywood, laminated wood, particleboard, medium-density fiberboard, and rigid fiberboard. Examples of metal-based materials include steel plates and aluminum plates. Furthermore, the base material 6 may be a resin such as plastic, or a composite material thereof. In other words, the base material 6 may be a resin-based material. The base material 6 may also be a non-combustible base material composed of, for example, a non-combustible steel plate or a non-combustible material as defined in Ministry of Construction Notification No. 1400. [Examples]

[0068] Examples and comparative examples of the decorative components according to the present invention are described below. However, the present invention is not limited to the following embodiments. (Example 1) A base material made of colored polypropylene resin was used as a colored thermoplastic resin layer. After corona discharge treatment was applied to one side of the base material, a solid ink layer and a patterned ink layer (patterned layer) were formed on the base material using a printing ink made of urethane resin. Furthermore, two layers of silicone-containing acrylic ultraviolet-curing resin were coated on the patterned ink layer, and the resin was crosslinked by irradiation with ultraviolet light to form a surface protective layer with a thickness of 5 μm. This formed a decorative sheet. Next, a primer was applied to the other side of the substrate to form a primer layer, and a decorative component was obtained by laminating MDF (Medium Density Fiberboard) to the side of the primer layer opposite to the substrate using "BA-10L (Hardener: BA-11B)" manufactured by Japan Coating Resin. The structure of each layer was as follows:

[0069] (Colored thermoplastic resin layer) Material: Polypropylene Thickness: 60 μm Using a T-die extruder, a 60 μm film was produced as the colored thermoplastic resin layer, consisting of a colored thermoplastic resin (polypropylene) as the intermediate layer and transparent thermoplastic resins (polypropylene) as surface skin layers on both sides of the intermediate layer, with a thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin of 1 / 8 / 1. In this process, recycled polypropylene resin was added to the colored thermoplastic resin (polypropylene) that forms the intermediate layer, with a mass ratio of 14% by mass relative to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin polypropylene resin.

[0070] (Surface protective layer) Material: Acrylic UV-curing resin • Main ingredient (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 • Hardening agent (Takenate D170; Mitsui Chemicals, Inc.) ... 10 parts by mass • Solvent (ethyl acetate) ... 240 parts by mass

[0071] (Example 2) In the decorative component of Example 1, recycled resin of thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) that forms the intermediate layer of the colored thermoplastic resin layer, with a mass ratio of 12% by mass relative to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin resin of thermoplastic resin (polypropylene). Other than this, it is the same as the decorative component of Example 1.

[0072] (Example 3) In the decorative component of Example 1, a film with a thickness of 125 μm was formed as the colored thermoplastic resin layer, with a colored thermoplastic resin (polypropylene) forming the intermediate layer and transparent thermoplastic resins (polypropylene) forming the surface skin layers on both sides of the intermediate layer, such that the thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 16 / 93 / 16. At this time, recycled thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) forming the intermediate layer, with a mass ratio of 14% by mass to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin thermoplastic resin (polypropylene). Other than this, it is the same as the decorative component of Example 1.

[0073] (Example 4) In the decorative component of Example 1, recycled resin of thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) that forms the intermediate layer of the colored thermoplastic resin layer, with a mass ratio of 5% by mass relative to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin resin of thermoplastic resin (polypropylene). Otherwise, it is the same as the decorative component of Example 1.

[0074] (Example 5) In the decorative component of Example 1, recycled resin of thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) that forms the intermediate layer of the colored thermoplastic resin layer, with a mass ratio of 30% by mass relative to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin resin of thermoplastic resin (polypropylene). Otherwise, it is the same as the decorative component of Example 1.

[0075] (Example 6) In the decorative component of Example 1, a film with a thickness of 36 μm was formed as the colored thermoplastic resin layer, with a colored thermoplastic resin (polypropylene) forming the intermediate layer and transparent thermoplastic resins (polypropylene) forming the surface skin layers on both sides of the intermediate layer, such that the thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 6 / 24 / 6. At this time, recycled thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) forming the intermediate layer, with a mass ratio of 14% by mass to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin thermoplastic resin (polypropylene). Other than this, it is the same as the decorative component of Example 1.

[0076] (Example 7) In the decorative component of Example 1, a film with a thickness of 72 μm was formed as the colored thermoplastic resin layer, with a colored thermoplastic resin (polypropylene) forming the intermediate layer and transparent thermoplastic resins (polypropylene) forming the surface skin layers on both sides of the intermediate layer, such that the thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 6 / 60 / 6. At this time, recycled thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) forming the intermediate layer, with a mass ratio of 14% by mass to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin thermoplastic resin (polypropylene). Other than this, it is the same as the decorative component of Example 1.

[0077] (Comparative Example 1) In the decorative component of Example 1, recycled resin of thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) that forms the intermediate layer of the colored thermoplastic resin layer, with a mass ratio of 40% by mass relative to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin resin of thermoplastic resin (polypropylene). Otherwise, it is the same as the decorative component of Example 1.

[0078] (Comparative Example 2) In the decorative component of Example 1, the only difference is that the colored thermoplastic resin layer is a single layer consisting only of the intermediate layer described in Example 1, with a thickness of 60 μm.

[0079] (Comparative Example 3) In the decorative component of Example 1, the colored thermoplastic resin layer is identical to that of Example 1, except that the colored thermoplastic resin (polypropylene) forming the intermediate layer and the transparent thermoplastic resin (polypropylene) forming the surface skin layers on both sides of the intermediate layer are formed as a film with a thickness of 60 μm, with a thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin of 1 / 1 / 1.

[0080] (Comparative Example 4) In the decorative component of Example 1, recycled resin of thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) that forms the intermediate layer of the colored thermoplastic resin layer, with a mass ratio of 3% by mass relative to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin resin of thermoplastic resin (polypropylene). Other than this, it is the same as the decorative component of Example 1.

[0081] (Comparative Example 5) In the decorative component of Example 1, recycled resin of thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) that forms the intermediate layer of the colored thermoplastic resin layer, with a mass ratio of 33% by mass relative to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin resin of thermoplastic resin (polypropylene). Otherwise, it is the same as the decorative component of Example 1.

[0082] (Comparative Example 6) In the decorative component of Example 1, a film with a thickness of 30 μm was formed as the colored thermoplastic resin layer, with a colored thermoplastic resin (polypropylene) forming the intermediate layer and transparent thermoplastic resins (polypropylene) forming the surface skin layers on both sides of the intermediate layer, such that the thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 6 / 18 / 6. At this time, recycled thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) forming the intermediate layer, with a mass ratio of 14% by mass to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin thermoplastic resin (polypropylene). Other than this, it is the same as the decorative component of Example 1.

[0083] (Comparative Example 7) In the decorative component of Example 1, a film with a thickness of 78 μm was formed as the colored thermoplastic resin layer, with a colored thermoplastic resin (polypropylene) forming the intermediate layer and transparent thermoplastic resins (polypropylene) forming the surface skin layers on both sides of the intermediate layer, such that the thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 6 / 66 / 6. At this time, recycled thermoplastic resin (polypropylene) was added to the colored thermoplastic resin (polypropylene) forming the intermediate layer, with a mass ratio of 14% by mass to the total colored thermoplastic resin constituting the intermediate layer. The remainder was virgin thermoplastic resin (polypropylene). Other than this, it is the same as the decorative component of Example 1.

[0084] 〔evaluation〕 For the decorative components of Examples 1-7 and Comparative Examples 1-7, the petroleum dependence of the entire decorative sheet, production suitability (printability), pinking resistance, surface properties (wettability) of the colored thermoplastic resin layer, and the opacity of the decorative sheet were evaluated. The test methods and evaluation methods are as follows. (Oil dependence) We evaluated the petroleum dependence of decorative sheets. Specifically, for each decorative sheet constituting a decorative component, we evaluated it as "○" if it was considered to have low petroleum dependence and "×" if it was considered to have high petroleum dependence.

[0085] (Production suitability (printing suitability)) For each decorative component in the examples and comparative examples, printing was performed on a substrate consisting of a colored thermoplastic resin layer, and its production suitability (printability) was confirmed at the point when the pattern layer was formed. Specifically, it was visually confirmed whether the printing was done according to the plate design. If the printing resin coating was printed onto the substrate according to the plate design, and even if there were printing defects (missing or missing prints) caused by foreign matter in the substrate in the areas that were supposed to be printed according to the plate design, a plate with a small number of defects that could be produced stably was evaluated as "○ (Pass)", and a plate with a large number of defects was evaluated as "× (Fail)".

[0086] (Pinking resistance) For each decorative component in the examples and comparative examples, a substrate was prepared as a sample to serve as a colored thermoplastic resin layer. NOx (nitrogen oxides) was generated by dropping a saturated aqueous solution of sodium nitrite into sulfuric acid in a desiccator, and the substrate sample was placed in the desiccator and sealed. This desiccator was left at 60°C for 20 hours, and the sample was removed and color difference measurement was performed. A CR-400 colorimeter manufactured by Konica Minolta, Inc. was used as the colorimeter. If the color difference of the sample before and after being left for 20 hours was equal to or less than the color difference of conventional olefin colored film raw material, it was marked as "○ (Pass)". If the color difference was greater than that of conventional olefin colored film raw material, it was marked as "× (Fail)".

[0087] (Wettability) For each decorative component in the examples and comparative examples, the wettability of the substrate as a colored thermoplastic resin layer was evaluated as a surface property. Wetting tension (JIS K 6768:1999) was measured as an index representing wettability. A wetting tension of 45 mN / m or higher was marked as "○ (Pass)", and a wetting tension of less than 45 mN / m was marked as "× (Fail)".

[0088] (The opacity of decorative sheets) The opacity was evaluated by visually checking the opacity using black and white base paper. Specifically, a decorative sheet was placed on opacity test paper manufactured by BYK, and the degree of opacity of the test paper was visually checked. The evaluation criteria are as follows: ○ (Pass): Equivalent to or better than conventional olefin colored film raw materials. × (Failure): Below the standard olefin colored film base roll. [Evaluation Results] The evaluation results for the decorative sheets of the examples and comparative examples are shown in Table 1.

[0089] [Table 1]

[0090] In decorative sheets having only a colored thermoplastic resin layer as the thermoplastic resin layer, the colored thermoplastic resin layer comprises an intermediate layer 12 made of colored thermoplastic resin and surface skin layers 11 and 13 provided on both sides of the intermediate layer 12 and both made of transparent thermoplastic resin, with only the intermediate layer 12 containing recycled resin, the mass ratio of recycled resin in the intermediate layer 12 being 5% by mass or more and 30% by mass or less, and the ratio of the layer thickness of the surface skin layer 11, intermediate layer 12, and surface skin layer 13 being within the range of surface skin layer 11 / intermediate layer 12 / surface skin layer 13 = 1 / 4 / 1 or more and 1 / 10 / 1 or less, it was confirmed that the decorative sheets of Examples 1 to 7 have a high proportion of recycled resin used, possess surface properties equivalent to those of decorative sheets that do not use recycled resin, and also achieve good production suitability, pinking resistance, and opacity of the decorative sheet.

[0091] Furthermore, the present invention can take the following configuration, for example. (1) A decorative sheet comprising only a colored thermoplastic resin layer as the thermoplastic resin layer, The colored thermoplastic resin layer includes an intermediate layer made of colored thermoplastic resin, and a first surface skin layer and a second surface skin layer provided on both sides of the intermediate layer, both made of transparent thermoplastic resin, wherein only the intermediate layer contains recycled resin. The mass ratio of the recycled resin in the intermediate layer is 5% by mass or more and 30% by mass or less. A decorative sheet characterized in that the ratio of the layer thicknesses of the first surface skin layer, the intermediate layer, and the second surface skin layer is within the range of first surface skin layer / intermediate layer / second surface skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less.

[0092] (2) The decorative sheet according to (1) above, characterized in that the intermediate layer, the first surface skin layer, and the second surface skin layer are composed of the same thermoplastic resin. (3) The decorative sheet according to (1) or (2), characterized in that the colored thermoplastic resin layer contains a coloring pigment, and the coloring pigment is contained only in the intermediate layer of the colored thermoplastic resin layer.

[0093] (4) The decorative sheet according to any one of (1) to (3) above, characterized in that the colored thermoplastic resin layer comprises an olefin-based thermoplastic resin and a hindered amine-based radical scavenger. (5) The decorative sheet according to any one of the above (1) to (4), characterized in that the colored thermoplastic resin layer contains an inorganic substance, and the inorganic substance is one or more of the following: calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0094] (6) The decorative sheet according to any one of (1) to (5) above, characterized in that a primer layer, the colored thermoplastic resin layer, the pattern layer, and the surface protection layer are laminated in this order. (7) It has a surface protective layer as its outermost layer, The decorative sheet according to any one of (1) to (6) above, characterized in that at least the surface protective layer contains an ultraviolet absorber and a hindered amine-based radical scavenger.

[0095] (8) A method for manufacturing a decorative sheet, comprising only a colored thermoplastic resin layer as the thermoplastic resin layer, The colored thermoplastic resin layer is composed of three layers: an intermediate layer containing a colored thermoplastic resin, and a first surface skin layer and a second surface skin layer provided on both sides of the intermediate layer and made of transparent thermoplastic resin. A method for manufacturing a decorative sheet, characterized in that the first surface skin layer, the intermediate layer, and the second surface skin layer are formed into a film using the same thermoplastic resin by co-extrusion so that the ratio of the layer thicknesses of the first surface skin layer, the intermediate layer, and the second surface skin layer is in the range of first surface skin layer / intermediate layer / second surface skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less, and only the intermediate layer contains a coloring pigment and recycled resin of the thermoplastic resin, and the mass ratio of the recycled resin in the intermediate layer is 5% by mass or more and 30% by mass or less. (9) Substrate and A decorative member characterized by comprising a decorative sheet according to any one of the above items (1) to (7) laminated on at least one surface of the base material. [Explanation of Symbols]

[0096] 1 Colored thermoplastic resin layer 2 Image Layers 3 Surface protective layer 4. Primer layer 5 Uneven part 6 Base material 10 decorative sheets 11 Surface skin layer 12 Middle Class 13. Surface skin layer 20 Decorative components

Claims

1. A decorative sheet comprising only a colored thermoplastic resin layer as the thermoplastic resin layer, The colored thermoplastic resin layer comprises an intermediate layer made of colored thermoplastic resin, and a first surface skin layer and a second surface skin layer provided on both sides of the intermediate layer, both made of transparent thermoplastic resin, wherein only the intermediate layer contains recycled resin. The mass ratio of the recycled resin in the intermediate layer is 5% by mass or more and 30% by mass or less. A decorative sheet characterized in that the ratio of the layer thicknesses of the first surface skin layer, the intermediate layer, and the second surface skin layer is within the range of first surface skin layer / intermediate layer / second surface skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less.

2. The decorative sheet according to claim 1, characterized in that the intermediate layer, the first surface skin layer, and the second surface skin layer are composed of the same thermoplastic resin.

3. The decorative sheet according to claim 1 or 2, wherein the colored thermoplastic resin layer contains a coloring pigment, and the coloring pigment is contained only in the intermediate layer of the colored thermoplastic resin layer.

4. The decorative sheet according to claim 1 or 2, characterized in that the colored thermoplastic resin layer comprises an olefin-based thermoplastic resin and a hindered amine-based radical scavenger.

5. The decorative sheet according to claim 1 or 2, characterized in that the colored thermoplastic resin layer contains an inorganic substance, and the inorganic substance is one or more of the following: calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

6. The decorative sheet according to claim 1 or 2, characterized in that the primer layer, the colored thermoplastic resin layer, the pattern layer, and the surface protection layer are laminated in this order.

7. It has a surface protective layer as its outermost layer, The decorative sheet according to claim 1 or 2, characterized in that at least the surface protective layer contains an ultraviolet absorber and a hindered amine-based radical scavenger.

8. A method for manufacturing a decorative sheet, comprising only a colored thermoplastic resin layer as the thermoplastic resin layer, The colored thermoplastic resin layer is composed of three layers: an intermediate layer containing a colored thermoplastic resin, and a first surface skin layer and a second surface skin layer, each provided on both sides of the intermediate layer and made of transparent thermoplastic resin. A method for manufacturing a decorative sheet, characterized in that the first surface skin layer, the intermediate layer, and the second surface skin layer are formed into a film using the same thermoplastic resin by co-extrusion so that the ratio of the layer thicknesses of the first surface skin layer, the intermediate layer, and the second surface skin layer is in the range of first surface skin layer / intermediate layer / second surface skin layer = 1 / 4 / 1 or more and 1 / 10 / 1 or less, and only the intermediate layer contains a coloring pigment and recycled resin of the thermoplastic resin, and the mass ratio of the recycled resin in the intermediate layer is 5% by mass or more and 30% by mass or less.

9. Substrate and A decorative member comprising a decorative sheet according to claim 1 or claim 2 laminated on at least one surface of the base material.

Images