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

Abstract

The present invention provides a decorative sheet that suppresses a decrease in productivity even when recycled materials are incorporated, and has a level of pinking resistance equivalent to that of a sheet without recycled materials. [Solution] A colored thermoplastic resin layer 1, a pattern layer 2, a transparent adhesive resin layer 3, a transparent thermoplastic resin layer 4, and a surface protection layer 5 are laminated in this order, and a primer layer 6 is provided on the side of the colored thermoplastic resin layer 1 opposite to the pattern layer 2. The colored thermoplastic resin layer 1 includes a surface skin layer 11, a core layer 12, and a back surface skin layer 13, and the ratio of the layer thicknesses of the surface skin layer 11, the core layer 12, and the back surface skin layer 13 is in the range of 1 / 4 / 1 or more and 1 / 10 / 1 or less, 5% to 30% of the colored thermoplastic resin constituting the core layer 12 is composed of recycled resin of colored thermoplastic resin, and the surface skin layer 11 and the back surface skin layer 13 are composed only of virgin resin of transparent thermoplastic resin.

Description

Technical Field

[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 for environmental protection, the substitution with recycled materials has attracted attention. For example, cosmetic sheets containing recycled resin and virgin resin made of vinyl chloride-based resin (see, for example, Patent Document 1), cosmetic sheets containing recycled PET-based resin and 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] In recycled materials, foreign substances are inevitably mixed in the process from waste materials to recycled materials. Therefore, when a recycled material is blended as a material for a cosmetic sheet, there is a concern that defects such as printing dropout due to foreign substances may occur when printing on the cosmetic sheet, resulting in a decrease in productivity. There is also a concern that the resistance to pinkening (coloring in pink color) deteriorates due to the recycling aids added to the recycled materials.

[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 suppress the decrease in productivity caused by incorporating recycled materials as a material for decorative sheets, and have a level of pinking resistance equivalent to that of a sheet without recycled materials. [Means for solving the problem]

[0006] According to one aspect of the present invention, a decorative sheet is provided which includes a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, wherein the colored thermoplastic resin layer includes a core layer made of colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer and both made of transparent thermoplastic resin, the ratio of the layer thickness 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, the core layer is made of recycled colored thermoplastic resin in proportion to 5% to 30% of the colored thermoplastic resin constituting the core layer, and the first skin layer and the second skin layer are made only of virgin transparent thermoplastic resin.

[0007] Furthermore, according to another aspect of the present invention, a method for manufacturing a decorative sheet is provided, which includes a laminate in which a colored thermoplastic resin layer, an adhesive resin layer, and a transparent thermoplastic resin layer are laminated in this order, wherein the colored thermoplastic resin layer includes a core layer made of colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer and both made of transparent thermoplastic resin, and 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 within 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 a colored thermoplastic resin containing 5% to 30% recycled resin, and the first skin layer and the second skin layer are formed of a transparent thermoplastic resin made only of virgin resin.

[0008] Furthermore, according to another aspect of the present invention, a decorative member is provided comprising a base material and a decorative sheet according to the above aspect laminated on at least one surface of the base material. [Effects of the Invention]

[0009] According to one aspect of the present invention, even when recycled materials are incorporated into the material of the decorative sheet, it is possible to realize a decorative sheet that can suppress a decrease in productivity and suppress a deterioration in pinking resistance. [Brief explanation of the drawing]

[0010] [Figure 1] This is a schematic cross-sectional view showing an example of a decorative sheet according to one embodiment of the present invention. [Modes for carrying out the invention]

[0011] 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.

[0012] [Decorative sheet] As shown in Figure 1, the decorative sheet 10 according to an embodiment of the present invention comprises 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 protection layer 5, with these layers laminated in this order. Furthermore, the decorative sheet 10 includes a primer layer 6 on the side of the colored thermoplastic resin layer 1 opposite to the pattern layer 2. The thickness of the decorative sheet 10 is preferably 40 μm or more and 300 μm or less.

[0013] Furthermore, the surface protective layer 5 is provided with embossed areas 7 that reach the transparent thermoplastic resin layer 4. For example, the embossed areas 7 may have a pattern that matches the pattern of the pattern layer 2, or a pattern that does not match the pattern. The depth of the embossed areas 7 is preferably 10 μm or less, from the standpoint of stain resistance and tactile performance. The decorative sheet 10 only needs to include at least a colored thermoplastic resin layer 1, a transparent adhesive resin layer 3, and a transparent thermoplastic resin layer 4.

[0014] [Colored thermoplastic resin layer] 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 skin layer) 11, a core layer 12, and a back surface skin layer (second skin layer) 13 are laminated in this order, and the back surface skin layer 13 is in contact with the primer layer 6, and the surface skin layer 11 is in contact with the pattern layer 2. The core layer 12 is made of a colored thermoplastic resin, and the surface skin layer 11 and the back surface skin layer 13 are made of transparent thermoplastic resin layers.

[0015] The following provides a detailed explanation of the structure of each layer mentioned above. (Core layer) The core layer 12 according to this embodiment is a base layer for the colored thermoplastic resin layer 1. The core layer 12 is composed of a colored thermoplastic resin, and 5% to 30% of the thermoplastic resin constituting the core layer 12 is composed of recycled resin.

[0016] The core 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 core layer 12 according to this embodiment may be made of an ionomer resin. Alternatively, the core layer 12 according to this embodiment may be made of polypropylene (PP) resin. Among the surface skin layer 11, the core layer 12, and the back skin layer 13 that constitute the colored thermoplastic resin layer 1, only the core layer 12 contains a coloring pigment, and the surface skin layer 11 and the back skin layer 13 do not contain a coloring pigment.

[0017] The core layer 12 contains, for example, 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 with respect to 100 parts by mass of the resin component constituting the core 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 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. Further, 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.

[0018] 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 deterioration 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 1 / 8 / 1 for the surface skin layer 11 / core layer 12 / back skin layer 13.

[0019] 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.

[0020] In addition, the core layer 12 may contain an ultraviolet absorber. The content of the ultraviolet absorber contained in the core 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 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 dust 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.

[0021] 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.

[0022] Furthermore, by selecting a hydroxyphenyltriazine-based UV absorber as the UV absorber added to the core layer 12, it becomes possible to maintain long-term UV absorption performance because the triazine skeleton suppresses bleeding, and the triazine skeleton is chemically more stable compared to the skeletons of benzotriazole-based and benzophenone-based UV absorbers.

[0023] 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 core layer 12 may contain 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine.

[0024] 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 core 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.

[0025] Examples of benzophenone-based UV absorbers that can be used include octabenzone, modified versions, polymers, and derivatives.

[0026] Furthermore, the core layer 12 may contain a light stabilizer such as a hindered amine-based radical scavenger. The amount of light stabilizer contained in the core 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 core layer 12. If the amount of light stabilizer is less than 0.001 parts by mass, the stability of the core layer 12 against ultraviolet light may not be sufficient, and it may not be possible to impart sufficient durability to the core layer 12. Also, if the amount of light stabilizer exceeds 10 parts by mass, the proportion of the resin component constituting the core layer 12 will relatively decrease, which may cause powdering or other issues to occur in the core layer 12, making it impossible to impart the strength necessary for printing, or even to form a film at all.

[0027] 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.

[0028] An antioxidant may be added to the core 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 core layer 12.

[0029] A processing stabilizer may be added to the core 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 core layer 12.

[0030] In addition, inorganic materials may be added to the core layer 12. Examples of inorganic materials include calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides, one or more of which can be used.

[0031] (Surface skin layer and back skin layer) The surface 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. The back surface 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. Each of the surface skin layer 11 and the back skin layer 13 does not contain coloring pigments such as titanium dioxide. Each of the surface skin layer 11 and the back skin layer 13 is composed solely of virgin resin of transparent thermoplastic resin and does not contain recycled resin.

[0032] Preferably, each layer of the surface skin layer 11 and the back skin layer 13 is made of the same thermoplastic resin as the thermoplastic resin that constitutes the core layer 12 described above. In other words, the material that constitutes each layer of the surface skin layer 11 and the back skin layer 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 core layer 12. Among olefin-based resins, ethylene-methacrylic acid copolymer is 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 the back skin layer 13 according to this embodiment may be made of an ionomer resin. Also, at least one of the surface skin layer 11 and the back skin layer 13 according to this embodiment may be made of polypropylene (PP) resin.

[0033] The thickness of each layer, the surface skin layer 11 and the back skin layer 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 layer, the surface skin layer 11 and the back skin layer 13, is within the above numerical range, the colored thermoplastic resin layer 1 itself can be given high opacity.

[0034] Furthermore, the thickness of the surface 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 as 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.

[0035] Furthermore, the amount of UV absorber contained in each layer of the surface skin layer 11 and the back skin layer 13 may be the same as the amount of UV absorber contained in the core layer 12 described above. Also, the type of UV absorber contained in each layer of the surface skin layer 11 and the back skin layer 13 may be the same as the type of UV absorber contained in the core layer 12 described above. Furthermore, 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 as described above. By adding a light stabilizer to each of the surface skin layer 11 and the back skin layer 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 layer 11 and the back skin layer 13, deterioration of the pattern layer, primer layer, or any additional coating layer in contact with the surface skin layer 11 or the back skin layer 13 can be suppressed.

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

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

[0038] (modified version) In this embodiment, the case in which 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, the ultraviolet absorber and the 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).

[0039] 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. Furthermore, in this embodiment, the core layer 12 may be made by adding at least one of the following to the above-mentioned random or homo-polypropylene resin or polyethylene resin: 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 mentioned 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 core layer 12 has the above configuration, effects equivalent to those of the decorative sheet 10 and decorative member 20 in this embodiment can be obtained.

[0040] (Method for manufacturing a colored thermoplastic resin layer) Below, an example of a method for manufacturing the colored thermoplastic resin layer 1 according to this embodiment will be briefly described.

[0041] The colored thermoplastic resin layer 1 is formed by co-extruding the surface skin layer 11, core layer 12, and back 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.

[0042] (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.

[0043] 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.

[0044] 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.

[0045] 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.

[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 this embodiment, the colored thermoplastic resin layer 1 on which the pattern layer 2 is laminated and the transparent thermoplastic resin layer 4 only need to be joined via the transparent adhesive resin layer 3, and various lamination methods such as heat lamination, extrusion lamination, dry lamination, and sand lamination can be used for joining. Here, considering the various performances of the decorative sheet 10 according to this embodiment, the dry lamination method is preferred for joining. For this reason, the transparent adhesive resin layer 3 is preferably a dry lamination adhesive layer using a dry lamination adhesive. Furthermore, the transparent adhesive resin layer 3 is formed using conventional coating methods such as gravure coating, microgravure coating, comma coating, knife coating, and die coating.

[0047] Furthermore, the transparent adhesive resin layer 3 is preferably made of a polyolefin-based thermoplastic resin, and 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 greater than the content of the ethylene-propylene copolymer resin. Specifically, it is preferable that the content of the maleic acid-modified random polypropylene resin be within a range of 1.1 to 10 times the mass ratio of 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 increased.

[0048] The transparent adhesive resin layer 3 may be formed using a composition obtained by adding an ultraviolet absorber and a light stabilizer to the polyolefin resin described above. The ultraviolet absorber contained in the transparent adhesive resin 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. Furthermore, the amount of ultraviolet absorber contained in the transparent adhesive resin layer 3 may be the same as the amount of ultraviolet absorber contained in the colored thermoplastic resin layer 1.

[0049] Furthermore, the light stabilizer contained in the transparent adhesive resin layer 3 may be one of the light stabilizers listed as an addable light stabilizer for the colored thermoplastic resin layer 1. Also, the amount of light stabilizer contained in the transparent adhesive resin layer 3 may be the same as the amount of 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 polyolefin resin). There are no particular restrictions on the polyolefin resin, and the same type of polyolefin resin used in the transparent thermoplastic resin layer of 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. Furthermore, there may be one type or multiple types of polyolefin resin constituting the transparent thermoplastic resin layer 4. In addition, ultraviolet absorbers and light stabilizers may be added to this polypropylene resin. That is, the transparent thermoplastic resin layer 4 may be formed from a polypropylene resin composition (polyolefin resin composition) containing ultraviolet absorbers and light stabilizers.

[0051] The ultraviolet absorber contained in the transparent thermoplastic resin layer 4 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. Furthermore, the amount of UV absorber in the transparent thermoplastic resin layer 4 is preferably within the range of 0.1 parts by mass to 10 parts by mass per 100 parts by mass of polypropylene resin (resin component). If the amount of UV absorber in the transparent thermoplastic resin layer 4 is less than 0.1 parts by mass, sufficient weather resistance may not be obtained. Also, if the amount of UV absorber in the transparent thermoplastic resin layer 4 exceeds 10 parts by mass, the content of polypropylene resin (resin component) will be relatively low, which may cause problems during the formation of the transparent thermoplastic resin layer 4. The light stabilizer contained in the transparent thermoplastic resin layer 4 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.

[0052] Furthermore, the content of the light stabilizer in the transparent thermoplastic resin layer 4 is preferably within the range of 0.1 parts by mass to 10 parts by mass per 100 parts by mass of polypropylene resin (resin component). If the content of the light stabilizer in the transparent thermoplastic resin layer 4 is less than 0.1 parts by mass, sufficient weather resistance may not be obtained. Also, if the content of the light stabilizer in the transparent thermoplastic resin layer 4 exceeds 10 parts by mass, the content of polypropylene resin (resin component) becomes relatively low, which may cause problems during the formation of the transparent thermoplastic resin layer 4. Furthermore, the thickness of the transparent thermoplastic resin layer 4 is preferably within the range of 1 μm to 10 μm. If the thickness of the transparent thermoplastic resin layer 4 is within the above numerical range, sufficient weather resistance can be reliably obtained.

[0053] (modified version) In this embodiment, the case in which a polyolefin 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, or acrylic, or a foam made from these synthetic resins, or a rubber such as 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, or polyurethane. Furthermore, various additives such as the above-mentioned ultraviolet absorbers, radical scavengers, antioxidants, and processing stabilizers may be added to these resins as needed.

[0054] In addition to the 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis(2-hydroxy-4-methoxybenzophenone) listed as UV absorbers that can be added to the colored thermoplastic resin layer 1, other UV absorbers that can be added to the transparent thermoplastic resin layer 4 include, for example, benzoates, substituted oxanilides, cyanoacrylates, and triaryltriazines.

[0055] Examples of benzoates that can be used include phenyl salicylate, resorcinol monobenzoate, 2,4-diter-butylphenyl-3,5-diter-butyl-4-hydroxybenzoate, 2,4-diter-amylphenyl-3,5-diter-butyl-4-hydroxybenzoate, and hexadecyl-3,5-diter-butyl-4-hydroxybenzoate.

[0056] Furthermore, examples of substituted oxanilides that can be used include 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide. Furthermore, examples of cyanoacrylates that can be used include ethyl-α-cyano-β, β-diphenyl acrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate.

[0057] Furthermore, examples of triaryltriazines that can be used include 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-diter-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-diter-butylphenyl)-s-triazine.

[0058] (Surface protective layer) The surface protection layer 5 is a layer for improving the weather resistance of the decorative sheet 10. The surface protection layer 5 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 5. Furthermore, there may be one type or multiple types of acrylic resin constituting the surface protection layer 5. The acrylic resins that can be used in the surface protection layer 5 of this embodiment will be described in detail below.

[0059] In this embodiment, the surface protection layer 5 may mainly consist 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 the like 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 5, such as maintaining and improving surface hardness, improving stain resistance, and adjusting surface gloss.

[0060] 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 5 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 individually or as a mixture of the isomers.

[0061] Furthermore, as a method for forming the surface protective layer 5, for example, a coating liquid made of an acrylic resin composition containing the above-mentioned cyclohexyl (meth)acrylate as a monomer component is applied onto the transparent thermoplastic resin layer 4. 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.

[0062] 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.

[0063] 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 5, which is undesirable.

[0064] 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 5 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 5 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.

[0065] Furthermore, the amount of UV absorber in the surface protective layer 5 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 5 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 5 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 5.

[0066] The light stabilizer contained in the surface protective layer 5 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. Furthermore, the content of the light stabilizer in the surface protective layer 5 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 5 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 5 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 5. In addition, if it exceeds 30 parts by mass, bleed-out of the light stabilizer may occur.

[0067] Furthermore, the amount of UV absorber in the surface protective layer 5 may be greater than the amount of UV absorber in the transparent thermoplastic resin layer 4. Also, the amount of light stabilizer in the surface protective layer 5 may be greater than the amount of light stabilizer in the transparent thermoplastic resin layer 4. Furthermore, the thickness of the surface protective layer 5 is preferably within the range of 1 μm to 20 μm. If the thickness of the surface protective layer 5 is within the above numerical range, sufficient weather resistance can be reliably obtained, and flexibility is given to the surface protective layer 5, thereby reducing the occurrence of cracks in the surface protective layer 5.

[0068] Furthermore, various known coating methods can be used to provide the surface protection layer 5, 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 5 as needed. Furthermore, the surface protective layer 5 may or may not be formed in the areas where the uneven portion 7 is formed. However, it is preferable that the surface protective layer 5 be formed in the areas where the uneven portion 7 is formed, as this improves durability (weather resistance) compared to when it is not formed.

[0069] (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 5, 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 5. This point will be explained in detail below.

[0070] The surface protective layer 5 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.

[0071] [ka]

[0072] 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 5 can be kept to a level that does not pose a practical problem.

[0073] 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 5. 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 5, 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.

[0074] [ka]

[0075] (Primer layer) The primer layer 6 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 8 when forming a decorative member 20 by laminating the decorative sheet 10 to the substrate 8. For example, when the substrate 8 is made of wood-based materials, or metal-based materials such as aluminum substrates or steel plate substrates, preferably metal-based materials, adhesives such as vinyl acetate emulsion-based adhesives and two-component curing urethane-based adhesives are used, so it is desirable that the primer layer 6 be designed with a resin that matches these adhesives. For example, the primer layer 6 can be made of urethane-based, acrylic-based, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polyester-based adhesives, etc. In particular, a two-component curing urethane-based primer agent made by blending polyester polyol and polyisocyanate is preferred. Furthermore, adding inorganic powders such as silica, barium sulfate, and calcium carbonate to these materials when forming the primer layer 6 is effective in preventing blocking during winding and storage and improving adhesive strength through an anchoring effect.

[0076] (Uneven part) The uneven surface 7 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 7. For example, wood grain tubular shape, stone pattern, cloth pattern, abstract pattern, Japanese paper pattern, suede pattern, leather pattern, pear-textured pattern, sand pattern, hairline pattern, group of parallel lines, or combinations thereof can be used. Furthermore, as a method for forming the uneven surface 7, for example, a doubling embossing method, an extrusion laminate simultaneous embossing method, etc., can be employed, which are performed before, after, or simultaneously with the lamination of the transparent thermoplastic resin layer 4 onto the surface of the colored thermoplastic resin layer 1.

[0077] (Decorative material) The decorative sheet 10 having the above configuration may be bonded to a base material 8, which is a base material for decorative materials, to form a decorative member 20.

[0078] (base material) The base material 8 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. The base material 8 may also be a resin such as plastic, or a composite material thereof. When the base material 8 is a resin-based material, for example, polyvinyl chloride resin can be used. Base material 8 made of polyvinyl chloride resin has high thermal insulation properties and is in high demand as a window frame component (sash). Furthermore, a decorative component 20 made by decorating a polyvinyl chloride resin base material 8 with a decorative sheet 10 allows for the melting and reuse of both the base material 8 and the decorative sheet 10, thus improving recyclability.

[0079] The base material 8 may also be made of, for example, a non-combustible steel plate or a non-combustible material as specified in Ministry of Construction Notification No. 1400. As shown in Figure 1, a decorative sheet 10 is laminated to one side of the base material 8 (the upper side in Figure 1). In other words, the decorative member 20 according to this embodiment comprises a base material 8, which is a base material for decorative materials, and a decorative sheet 10 that is bonded to the base material 8. By laminating the decorative sheet 10 onto the base material 8, a decorative component 20 with excellent recyclability and productivity can be obtained.

[0080] [Effects of the Embodiment] (1) Recycled resin is used only in the core layer 12, and the surface skin layer 11 and back skin layer 13, which are arranged on both sides of the core layer 12, are made only of virgin resin without using recycled resin. The surface skin layer 11 and back skin layer 13, which are made of virgin resin, are provided on both sides of the core layer 12 which contains recycled resin. Since both sides of the colored thermoplastic resin layer 1 are made only of virgin resin, the surface properties of the colored thermoplastic resin layer 1 can be made equivalent to those of a colored thermoplastic resin layer made only of virgin resin without using recycled resin. As a result, even when the colored thermoplastic resin layer 1 is formed using recycled resin (recycled material), it can be treated in the same way as when the colored thermoplastic resin layer is made using only virgin resin, and good film-forming properties of the colored thermoplastic resin layer 1 can be obtained. Furthermore, even when recycled resin is used, good production suitability can be obtained, similar to when a decorative sheet is manufactured using only virgin resin.

[0081] (2) The ratio of the layer thickness of the surface skin layer 11 which does not contain recycled resin, the core layer 12 which contains recycled resin, and the back skin layer 13 which does not contain recycled resin is set to within 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. The surface skin layer 11 and back skin layer 13, which have a certain thickness relative to the thickness of the core layer 12 which contains recycled resin and are made of virgin resin without containing recycled resin, are provided on each side of the core layer 12. As a result, a certain portion of the thickness of the colored thermoplastic resin layer 1 on each side has the properties of virgin resin. Therefore, the printability, light resistance, surface stability such as surface inferiority 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.

[0082] (3) The proportion of recycled resin in the core layer 12 is set to 5% or more and 30% or less. When recycled resin is added to the decorative sheet 10, foreign matter is mixed in during the process of recycling from waste material to recycled material, so when printing on this decorative sheet, defects caused by foreign matter such as printing defects and deterioration of pinking resistance may occur. However, by limiting the proportion of recycled resin in the core layer 12 to 5% or more and 30% or less, it is possible to suppress defects caused by foreign matter and to suppress deterioration of pinking resistance. (4) The resins constituting each layer of the surface skin layer 11, the core layer 12, and the back 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.

[0083] (5) Because the transparent thermoplastic resin layer 4 and the surface protective layer 5 each contain an ultraviolet absorber and a hindered amine-based radical scavenger, the decorative sheet 10 and the decorative component 20 can be given high weather resistance.

[0084] (6) The core 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 composites, and other oxides. Therefore, the opacity of the colored thermoplastic resin layer 1 can be improved. [Examples]

[0085] Examples and comparative examples of the decorative sheet according to the present invention are described below. However, the present invention is not limited to the following embodiments. <Examples> A colored thermoplastic resin layer 1 made of polypropylene resin was used. After corona discharge treatment was applied to one side of the colored thermoplastic resin layer 1, a pattern layer 2 made of urethane printing ink, a urethane 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 corona discharge treatment was applied to the other side of the colored thermoplastic resin layer 1, a primer layer 6 with a thickness of 1 to 2 μm was formed to obtain a decorative sheet 10. Subsequently, a decorative component 20 was obtained by bonding MDF (Medium Density Fiberboard) to the side of the primer layer 6 opposite to the colored thermoplastic resin layer 1 using BA-10L (curing agent: BA-11B) manufactured by Japan Coating Resin Co., Ltd. The structure of each layer was as follows:

[0086] (Colored thermoplastic resin layer 1) Material: Polypropylene Thickness: 60 μm • UV 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 60 μm film was formed by combining a colored thermoplastic resin (polypropylene) to form the core layer 12 and a transparent thermoplastic resin (polypropylene) to form the surface skin layer 11 and back skin layer 13, such that the thickness ratio of the transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 8 / 1. This film was designated as the colored thermoplastic resin layer 1.

[0087] (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 • UV 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

[0088] (Surface protective layer 5) Thickness: 5 μm • 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; manufactured by Mitsui Chemicals, Inc.) ... 10 parts by mass • Solvent (ethyl acetate)...240 parts by mass (Decorative sheet 10) Layer thickness: 135~140μm

[0089] (Example 1) Of the polypropylene used as the colored thermoplastic resin for the core layer 12, 14% was made from recycled polypropylene, and the remainder was made from virgin polypropylene.

[0090] This resulted in obtaining a decorative sheet 10 having a colored thermoplastic resin layer 1 containing 14% recycled resin.

[0091] (Example 2) In the decorative sheet 10 of Example 1, of the polypropylene used as the colored thermoplastic resin for the core layer 12, 5% was made from recycled polypropylene, and the remainder was made from virgin polypropylene. This resulted in obtaining a decorative sheet 10 having a colored thermoplastic resin layer 1 containing 5% recycled resin.

[0092] (Example 3) In the decorative sheet 10 of Example 1, of the polypropylene used as the colored thermoplastic resin for the core layer 12, 29% was made from recycled polypropylene, and the remainder was made from virgin polypropylene.

[0093] This resulted in obtaining a decorative sheet 10 having a colored thermoplastic resin layer 1 containing 29% recycled resin. (Example 4) In the decorative sheet 10 of Example 1, of the polypropylene used as the colored thermoplastic resin for the core layer 12, 30% was made from recycled polypropylene, and the remainder was made from virgin polypropylene.

[0094] This resulted in obtaining a decorative sheet 10 having a colored thermoplastic resin layer 1 containing 30% recycled resin. (Example 5) In Example 1, a decorative sheet 10 was obtained using the same procedure as in Example 1, except that the film as the colored thermoplastic resin layer 1 was formed such that the thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin was 1 / 4 / 1.

[0095] (Example 6) In Example 1, the decorative sheet 10 was prepared using the same procedure as in Example 1, except that the film as the colored thermoplastic resin layer 1 was formed with a thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin of 1 / 10 / 1.

[0096] <Comparative Example> (Comparative Example 1) A decorative sheet was obtained using the same procedure as in Example 1, except that the colored thermoplastic resin layer was a single-layer thermoplastic resin layer (60 μm thick) consisting only of the core layer described in Example 2. (Comparative Example 2) In Example 2, a decorative sheet was obtained using the same procedure as in Example 1, except that in the colored thermoplastic resin layer 1, a film was formed as the colored thermoplastic resin layer with a thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin of 1 / 1 / 1. (Comparative Example 3) In Example 1, a decorative sheet was obtained using the same procedure as in Example 1, except that in the colored thermoplastic resin layer 1, a film was formed as the colored thermoplastic resin layer with a thickness ratio of transparent thermoplastic resin / colored thermoplastic resin / transparent thermoplastic resin of 1 / 18 / 1.

[0097] (Reference example 1) In the decorative sheet 10 of Example 1, only polypropylene made of virgin resin was used as the colored thermoplastic resin for the core layer 12. This resulted in obtaining a decorative sheet having a colored thermoplastic resin layer that does not contain recycled resin. (Reference example 2) In the decorative sheet 10 of Example 1, of the polypropylene used as the colored thermoplastic resin for the core layer 12, 40% was made from recycled polypropylene, and the remainder was made from virgin polypropylene. This resulted in obtaining a decorative sheet having a colored thermoplastic resin layer containing 40% recycled resin. (Reference example 3) In the decorative sheet 10 of Example 1, of the polypropylene used as the colored thermoplastic resin for the core layer 12, 70% was made from recycled polypropylene, and the remainder was made from virgin polypropylene. This resulted in obtaining a decorative sheet having a colored thermoplastic resin layer containing 70% recycled resin.

[0098] [Evaluation Method] (Production suitability (printing suitability)) The printable pattern layers printed on the raw materials (colored thermoplastic resin layers) of the examples and comparative examples were confirmed to be suitable for production (printability). The evaluation criteria are as follows: ○: Although there are printing defects (such as missing prints) caused by foreign matter in the raw material, the number of defects is small and stable production is possible (acceptable). △: There are many printing defects (such as missing prints) caused by foreign matter in the raw material, but it is still production-ready (acceptable). ×: Too many flaws (failed)

[0099] (Pinking resistance) NOx was generated by dropwise adding a saturated sodium nitrite solution to sulfuric acid in a desiccator. The cosmetic components of the examples and comparative examples were placed in this solution, sealed, and left at 60°C for 20 hours. Then, color difference measurements were performed. A Konica Minolta CR-400 colorimeter was used.

[0100] The evaluation criteria are as follows: ○: No discoloration observed (Pass) △: Discoloration is present, but it does not affect production (acceptable) ×: Discoloration is visible and there are production issues (failed).

[0101] (Wettability) The wettability of the colored thermoplastic resin layer was evaluated as a surface property. Wetting tension (JIS K 6768:1999) was measured as an index of wettability. The wettability of the colored thermoplastic resin layer was measured 3 months after film formation. 〇:45mN / m or more ×: Less than 45 mN / m

[0102] (Concealing ability) The opacity of the decorative sheet was evaluated. The opacity was visually confirmed using black and white base paper. ○: Equivalent to or better than conventional olefin colored film raw materials. ×: Conventional olefin colored film raw material or less

[0103] [Evaluation Results] The evaluation results for the decorative sheets of the examples and comparative examples are shown in Table 1.

[0104] [Table 1]

[0105] As shown in Table 1, good decorative components could be obtained regardless of whether the amount of recycled resin added to the core layer was 14%, 5%, 28%, or 30%. In other words, it was confirmed that decorative components with excellent production suitability and pinking resistance could be obtained when the amount was between 5% and 30%. Furthermore, it was confirmed that good results could be obtained in both the wettability of the colored thermoplastic resin layer 1 and the opacity of the decorative component when the layer thickness ratio "surface skin layer 11 / core layer 12 / backside skin layer 13" was within the range of "1 / 4 / 1 to 1 / 10 / 1".

[0106] Furthermore, the present invention can take the following configuration, for example. (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 colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer, both made of transparent thermoplastic resin. 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. The core layer is composed of a recycled resin of the colored thermoplastic resin, where 5% to 30% of the colored thermoplastic resin constituting the core layer is made up of the recycled resin of the colored thermoplastic resin. A decorative sheet characterized in that the first skin layer and the second skin layer are composed solely of virgin resin of the transparent thermoplastic resin. (2) The decorative sheet according to (1) above, characterized in that of the first skin layer, the core layer, and the second skin layer, only the core layer contains a pigment. (3) The decorative sheet according to (1) or (2) above, characterized in that the resins constituting each of the layers, the first skin layer, the core layer, and the second skin layer, are all the same thermoplastic resin. (4) The decorative sheet according to (3) above, characterized in that the resin constituting each layer 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) The decorative sheet according to any one of (1) to (4) above, characterized in that the resin constituting each layer of the adhesive resin layer and the transparent thermoplastic resin layer is a polyolefin-based thermoplastic resin. (6) The transparent thermoplastic resin layer has a surface protective layer as its outermost layer, The decorative sheet according to any one of (1) to (5) above, characterized in that at least the transparent thermoplastic resin layer and the surface protective layer each contain an ultraviolet absorber and a hindered amine-based radical scavenger. (7) The decorative sheet according to any one of the above (1) to (6), characterized in that the core 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. (8) A method for manufacturing 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 colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer, both made of transparent thermoplastic resin. A method for manufacturing a decorative sheet, characterized in that 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 within 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 of the colored thermoplastic resin containing 5% or more and 30% or less recycled resin, and the first skin layer and the second skin layer are formed of the transparent thermoplastic resin consisting only of virgin resin. (9) The first skin layer, the core layer, and the second skin layer are composed of the same thermoplastic resin. A method for manufacturing a decorative sheet according to (8) above, characterized in that the first skin layer, the core layer, and the second skin layer are formed into a film by co-extrusion to form the colored thermoplastic resin layer in a film-like form. (10) 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]

[0107] 1 Colored thermoplastic resin layer 2 Image Layers 3 Transparent adhesive resin layer 4 Transparent thermoplastic resin layer 5 Surface protective layer 6. Primer layer 7 Uneven part 8 Base material 10 decorative sheets 11 Surface skin layer 12 core layers 13. Backside skin layer 20 Decorative components

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 colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer, both made of transparent thermoplastic resin. 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. The core layer is composed of 5% to 30% of the colored thermoplastic resin constituting the core layer, which is made up 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 solely of virgin resin of the transparent thermoplastic resin.

2. The cosmetic sheet according to claim 1, characterized in that, of the first skin layer, the core layer, and the second skin layer, only the core layer contains a pigment.

3. The decorative sheet according to claim 1 or 2, characterized in that the resins constituting each of the layers, 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 layer 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. The decorative sheet according to claim 1 or 2, characterized in that the resins constituting each layer of the adhesive resin layer and the transparent thermoplastic resin layer are polyolefin-based thermoplastic resins.

6. The transparent thermoplastic resin layer has a surface protective layer as its outermost layer, The decorative sheet according to claim 1 or 2, characterized in that at least the transparent thermoplastic resin layer and the surface protective layer each contain an ultraviolet absorber and a hindered amine-based radical scavenger.

7. The decorative sheet according to claim 1 or 2, characterized in that the core 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.

8. A method for manufacturing 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 colored thermoplastic resin, and a first skin layer and a second skin layer provided on both sides of the core layer, both made of transparent thermoplastic resin. A method for manufacturing a decorative sheet, characterized in that 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 within 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 of the colored thermoplastic resin containing 5% to 30% recycled resin, and the first skin layer and the second skin layer are formed of the transparent thermoplastic resin consisting only of virgin resin.

9. The first skin layer, the core layer, and the second skin layer are composed of the same thermoplastic resin. The method for manufacturing a decorative sheet according to claim 8, 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 co-extrusion method.

10. 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.

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