JP7121065B2 - Decorative sheet, decorative member, and method for manufacturing decorative sheet - Google Patents

Description

TECHNICAL FIELD The present invention relates to a decorative sheet, a decorative member, and a method for producing a decorative sheet, and is particularly used for construction materials such as interior and exterior building materials, surfaces and frame materials for fittings, surface materials for home electric appliances, flooring materials, and the like. The present invention relates to a decorative sheet, a decorative member, and a method for manufacturing a decorative sheet.

Conventionally, vinyl chloride sheets have been used as decorative sheets for construction materials and the like. However, vinyl chloride resin generates chlorine gas when incinerated, and is said to be a factor in acid rain and dioxin. From the viewpoint of environmental problems, there is a growing demand for decorative sheets that do not use vinyl chloride resin.

For the above reasons, in recent years, many decorative sheets using olefin-based resins have been proposed as decorative sheets to replace vinyl chloride decorative sheets. Examples of decorative sheets using olefin resins are those described in Patent Documents 1 to 5.
However, in these cases, since a general polyolefin sheet or soft polyolefin sheet is used, the scratch resistance and weather resistance are poor, and the surface scratch resistance is significantly inferior to the surface scratch resistance of conventional vinyl chloride decorative sheets. Therefore, if a material with high crystallization and high isotacticity is used to improve the scratch resistance of the surface, the deterioration of the weather resistance may be severe.

Therefore, it is attempted to improve surface gloss adjustment and surface scratch resistance by providing a resin as a topcoat on the surface of a polyolefin sheet. In addition, since weather resistance is also required, a weather resistance agent is present in the olefin resin and the weather resistance agent is also included in the topcoat agent. However, depending on the type of weathering agent, there are not a few weathering agents that do not fully function as a weathering agent or that bleed out to cause other problems.

Also, some decorative sheets are embossed with a wood grain pattern in order to improve their design. This embossed portion may have a thinner layer thickness than other portions, and in that case, the weather resistance is also weakened, and deterioration starts from that portion, and whitening and breakage of the conduit portion often occur.

JP-A-2-128843 JP-A-4-83664 JP-A-6-1881 JP-A-6-198831 JP-A-9-328562

The present invention has been made to solve such problems, and an object of the present invention is to provide a decorative sheet made of an olefin resin and having excellent weather resistance. and a method for manufacturing a decorative sheet.

In order to solve the above problems, a decorative sheet according to one aspect of the present invention includes an olefin resin layer having an uneven pattern formed on the surface thereof, and a surface protective layer formed on the surface of the olefin resin layer. In the sheet, the surface protective layer is mainly composed of an acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component, and contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following formula (1): It is characterized in that the surface protective layer is embedded in the recessed portions of the olefin resin layer that comprise one or more kinds of the surface protective layer.

A decorative sheet according to another aspect of the present invention is characterized in that the surface protective layer further contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following formula (2).

Further, a decorative member according to an aspect of the present invention includes a base material and the above-described decorative sheet provided on at least one surface of the base material, and the base material is a metal-based base material or a wood-based base material. It is characterized by being a base material or a resin-based base material.

Further, a method for manufacturing a decorative sheet according to one aspect of the present invention includes the step of forming the uneven pattern on the surface of the olefin resin layer by embossing; and a step of forming a protective layer, wherein the step of forming the surface protective layer includes embedding the surface protective layer in recesses forming the uneven pattern of the olefin resin layer.

According to one aspect of the present invention, there is provided a decorative sheet which is an olefin-based resin decorative sheet and has excellent weather resistance, in particular, a decorative sheet which reduces the occurrence of whitening and breakage in uneven pattern areas, and the decorative sheet. It is possible to provide a decorative member and a method for manufacturing a decorative sheet.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows one structural example of the decorative sheet and decorative member which concern on embodiment of this invention.

(Structure of decorative sheet and decorative member)
The decorative sheets and decorative members according to the embodiments of the present invention will be described in detail below with reference to the drawings, but they do not necessarily have to be laminated in this order as long as they are within the scope of the present invention. Also, layers not shown in this drawing may be added.
FIG. 1 shows a cross-sectional structure of an example of a decorative sheet and a decorative member according to this embodiment.
The decorative sheet 10 according to this embodiment is formed by laminating a colored thermoplastic resin layer 1, a pattern layer 2, an adhesive resin layer 3, a transparent thermoplastic resin layer (olefin resin layer) 4, and a surface protective layer 5 in this order. be. A concave-convex pattern is formed on the surface of the transparent thermoplastic resin layer 4 , and resin constituting the surface protective layer 5 is embedded in the depressions (recesses) 8 forming the concave-convex pattern. Also, all the surfaces forming the concave portion 8 may be covered with the resin forming the surface protective layer 5 .
The decorative member 11 according to this embodiment is obtained by laminating a base material 7, an adhesive layer 6, and a decorative sheet 10 in this order.
The configuration of each layer described above will be described in detail below.

[Surface protective layer]
The surface protective layer 5 according to this embodiment is mainly composed of an acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component. In addition, in this embodiment, cyclohexyl (meth)acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By containing cyclohexyl (meth)acrylate as a monomer component, the affinity for water can be reduced, and deterioration due to hydrolysis or the like can be suppressed.
As for the content of cyclohexyl (meth)acrylate, among the monomer components of all the acrylic resin compositions, that is, among the monomer components of the acrylic resin composition that is the main component of the surface protective layer 5, cyclohexyl (meth)acrylate is preferably in the range of 5% by mass or more and 50% by mass or less. By setting the content of cyclohexyl (meth)acrylate to 5% by mass or more, a sufficient deterioration suppressing effect can be obtained. In addition, by setting the content of cyclohexyl (meth)acrylate to 50% by mass or less, various performances of the surface protective layer 5 of the decorative sheet, such as maintenance and improvement of surface hardness, improvement of stain resistance, and adjustment of surface gloss, are not greatly changed. , it becomes possible to impart high weather resistance over time. Here, the above-mentioned "main component" means that the content of the acrylic resin composition constituting the surface protective layer 5 is 50% by mass or more with respect to the total mass of the surface protective layer 5. .

Examples of monomer components of the acrylic resin composition that can be used for the surface protective layer 5 according to the present embodiment include cyclohexyl(meth)acrylate, 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, tetramethylcyclohexanedi(meth)acrylate, tetramethylcyclohexanetri(meth)acrylate, tetramethylcyclohexanetetra(meth)acrylate, dicyclohexylmethyl(meth)acrylate, dicyclohexylmethyl ( meth)acrylate, phenoxycyclohexylmethyl (meth)acrylate, methoxycyclohexylmethyl (meth)acrylate and the like. Among these, those containing isomers may be each isomer alone and/or each isomer mixture.

Further, in the present embodiment, the surface protective layer 5 is formed of a coating liquid containing an acrylic resin composition containing the above-mentioned cyclohexyl (meth)acrylate as a monomer component and a weather resistant agent such as an ultraviolet absorber to be described later. It may be formed by coating the outermost surface of the sheet. For example, after applying a coating liquid containing the above-described acrylic resin composition and a weathering agent onto the transparent thermoplastic resin layer 4 having the recesses 8, the coating liquid is wiped into the recesses 8. may be embedded to form the surface protective layer 5 .
As a method of curing the coating liquid for forming the surface protective layer 5, for example, a one-liquid curing type, a two-liquid curing type using a curing agent, or an active energy ray curing type in which curing is performed by irradiation with ultraviolet rays, ionizing radiation, or the like. However, considering the weather resistance, the two-liquid curing type or the active energy ray curing type is preferable. A two-liquid curing type that is crosslinked by isocyanate curing is desirable.

As the two-liquid curing type acrylic resin composition, for example, an acrylic resin having two or more functional groups selected from hydroxyl groups, amino groups and carboxyl groups in one molecule and reacting with the functional groups A composition containing a polyisocyanate compound having two or more isocyanate groups per 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.

As the acrylic polyol having two or more hydroxyl groups in one molecule, in addition to the cyclohexyl (meth)acrylate described above, for example, a (meth)acrylic acid ester copolymer containing hydroxyethyl (meth)acrylate as a monomer component is used. Available. On the other hand, polyisocyanate compounds having two or more isocyanate groups in one molecule include, for example, tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and hydrogenation thereof. Compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), trimer type, TMP adduct type, buret type, etc. synthesized by known techniques from one or more compounds selected from these. Compositions in which one or more selected from these different types of polyisocyanates are mixed can also be used. Among them, HDI, trimer type of HDI, TMP adduct type, and burette type are preferable from the viewpoint of weather resistance. The content of the isocyanate compound with respect to the above resin component can be set arbitrarily, but it is desirable to set the equivalent ratio of hydroxyl group/isocyanate group to about 1/1 to 1/3. In particular, if the equivalent weight of the hydroxyl group is larger than the equivalent weight of the isocyanate group, the cross-linking may not proceed sufficiently, and the desired performance may not be imparted to the surface protective layer 5, which is not preferable in some cases.

When the method of curing the coating liquid for forming the surface protective layer 5 is active energy ray curing, the active energy ray curable acrylic resin composition may be a known (meth)acryloyl group-containing monomer or oligomer. etc. can be used, and in addition to these monomers and oligomers, the above-described cyclohexyl (meth)acrylate may be blended.

<Ultraviolet absorber>
In order to further improve the weather resistance of the decorative sheet 10, the surface protective layer 5 is generally added with a weather resistance agent such as an ultraviolet absorber and a radical scavenger. Known UV absorbers such as benzotriazole, hydroxyphenyltriazine and benzophenone can be used. Among them, if a hydroxyphenyltriazine-based UV absorber is selected, the triazine skeleton suppresses bleeding, and the triazine skeleton is more effective than the benzotriazole-based UV absorber or benzophenone-based UV absorber. By being chemically stable, it becomes possible to maintain the ultraviolet absorption performance over a long period of time.

Hydroxyphenyltriazine-based UV absorbers include, for example, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy] Phenol, 2-(2hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl- 1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl] -4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethyl-hexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5 ]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3 -hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4- Bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6 -(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)- 1,3,5-triazine and the like, and in the present embodiment, the surface protective layer 5 contains 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis It contains at least one compound having a structure of (4-phenylphenyl)-1,3,5-triazine (corresponding to formula (1) above). This is because the ultraviolet absorber having the structure of formula (1) is chemically stable and has the characteristic of maintaining ultraviolet absorption performance over a long period of time, and is characterized by having the structure of formula (2) described above. This is because it has a light absorption peak on the long wavelength side, so that the ultraviolet absorption performance can be maintained for a long period of time.

In the present embodiment, the amount of all hydroxyphenyltriazine-based ultraviolet absorbers, including those having the structure represented by the above formula (1), is 1 part by mass or more with respect to 100 parts by mass of the acrylic resin composition. It is preferably within the range of 30 parts by mass or less. When the amount of the ultraviolet absorber added is 1 part by mass or more, the effect of improving the weather resistance is exhibited, and when it is 30 parts by mass or less, the influence on the physical properties other than the weather resistance of the surface protective layer 5 is practically reduced. You can keep it to a safe level.
Further, when the hydroxyphenyltriazine-based ultraviolet absorber having the structure represented by the above formula (1) is used as the ultraviolet absorber to be added to the surface protective layer 5, the amount added is the same as that of the acrylic resin composition 100 It is preferably in the range of 1 part by mass or more and 20 parts by mass or less, more preferably in the range of 5 parts by mass or more and 15 parts by mass or less, and in the range of 8 parts by mass or more and 12 parts by mass or less. More preferably within By setting the amount of the hydroxyphenyltriazine-based ultraviolet absorber having the structure represented by formula (1) to 1 part by mass or more, the effect of improving the weather resistance is exhibited, and by setting the amount to 20 parts by mass or less, the surface protective layer 5 is improved. The influence on physical properties other than weather resistance can be suppressed to a practically acceptable level.

Further, in the present embodiment, as the hydroxyphenyltriazine-based UV absorber in the surface protective layer 5, one having the structure represented by the above formula (1) and 2-(4,6-diphenyl-1,3 ,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (corresponding to formula (2) described above) is used in combination to further improve Provides weather resistance. This is because the hydroxyphenyltriazine-based ultraviolet absorber represented by formula (2) has a high ability to absorb ultraviolet rays in the short wavelength region, which is relatively high energy among ultraviolet rays, and absorbs substantially the same wavelength region. This is because they are chemically more stable than UV absorbers, and their combined use broadens the wavelength region in which they absorb UV rays.
In the present embodiment, the added amount of the hydroxyphenyltriazine-based ultraviolet absorber having the structure represented by the above formula (1) is 100 parts by mass of the hydroxyphenyltriazine-based ultraviolet absorber having the structure represented by the above formula (2). , preferably within the range of 10 parts by mass or more and 200 parts by mass or less, more preferably within the range of 20 parts by mass or more and 100 parts by mass or less, and within the range of 40 parts by mass or more and 80 parts by mass or less It is more preferable that By setting the addition amount of the hydroxyphenyltriazine-based ultraviolet absorber having the structure represented by formula (1) within the above numerical range, further excellent weather resistance can be imparted.

(Modification)
Although the hydroxyphenyltriazine-based UV absorbers that can be added to the surface protective layer 5 have been described above, the hydroxyphenyltriazine-based UV absorbers that can be used in the present embodiment are not limited to these. The surface protective layer 5 according to this embodiment may contain, for example, a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (3). Moreover, the surface protective layer 5 may contain an ultraviolet absorber having a structure represented by the following general formula (4). Specifically, it contains 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl)]-6-(4-methoxyphenyl)-s-triazine represented by the following formula (5) or may contain a hydroxyphenyltriazine-based UV absorber represented by the following formula (6).

In general formula (3), R1 to R3 each independently represent a hydrogen atom, a methyl group, a phenyl group, or an alkoxy group, and at least two of them are alkoxy groups having 8 to 18 carbon atoms and not containing a carbonyl group. , R4 and R5 each independently represent a hydroxyl group, a methyl group or a hydrogen atom, and R6 to R8 each independently represent a methyl group or a hydrogen atom.

In general formula (4), R1 and R2 are alkoxy groups having 8 to 18 carbon atoms, R3 is an alkoxy group having 1 to 4 carbon atoms, R4 is a hydroxyl group, and R5 to R8 are hydrogen atoms.

Furthermore, by using a hydroxyphenyltriazine-based and a benzotriazole-based UV absorber in combination, it is possible to impart even better weather resistance due to their interaction. This is because the benzotriazole-based UV absorber has an absorption peak on the longer wavelength side than the hydroxyphenyltriazine-based UV absorber, so that the combined use of these agents further widens the wavelength region in which UV rays are absorbed. . The amount of the benzotriazole-based ultraviolet absorber to be added is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. A desired effect can be obtained, and bleeding out of the weathering agent can be suppressed by setting the amount to 30 parts by mass or less. However, since the benzotriazole-based ultraviolet absorber has an absorption peak on the long wavelength side, it may have a yellowish tinge.

Examples of benzotriazole-based UV absorbers include 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-ditert-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'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazole solyl)phenol), 2-(2′-hydroxy-3′-tert-butyl-5′-carboxyphenyl)benzotriazole, etc., but not limited thereto.

<Radical Scavenger>
Furthermore, by using a hindered amine-based radical scavenger together, the weather resistance performance of the decorative sheet 10 can be further improved. Hindered amine-based radical scavengers that can be used in the present embodiment include, for example, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl -4-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2, 6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2 ,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2 ,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl).di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1, 2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl) )-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / 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-tert-octylamino-s-triazine polycondensate, 1,5,8,12 -tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12 -tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine -6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl- 4-piperidyl)amino)-s-triazin-6-yl]a Minundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl ] aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate cyclohexane and Reaction product with N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine and reaction product with 2-aminoethanol etc., but not limited to these.

The amount of the hindered amine-based radical scavenger to be added is preferably in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. When the content is 30 parts by mass or less, bleeding out of the weathering agent can be suppressed, and the influence on other physical properties of the surface protective layer 5 can be suppressed.

As for the thickness of the surface protective layer 5 in the present embodiment, if the amount of the ultraviolet absorber added is the same, a thicker film can provide better weather resistance, but the flexibility of the decorative sheet 10 is impaired. , the surface layer of the decorative sheet 10 is likely to be cracked during post-processing. Conversely, if the thickness is reduced, there is a problem that the weather resistance performance is impaired. Therefore, the thickness of the surface protective layer 5 is preferably in the range of 2 μm or more and 20 μm or less. For the same reason, if the total thickness of the decorative sheet 10 is in the range of 40 μm or more and 300 μm or less, both weather resistance and post-processability can be achieved.

Various known coating methods such as gravure coating, reverse coating, gravure reverse coating, die coating, and flow coating can be used as a method for providing the surface protective layer 5 in this embodiment. Furthermore, various additives such as antifriction agents, antiblocking agents, and antistatic agents may be added to the surface protective layer 5 in the present embodiment, if necessary.

[Transparent thermoplastic resin layer]
The transparent thermoplastic resin layer (olefin resin layer) 4 can be provided as necessary to protect the pattern layer 2, and may be transparent or translucent as long as the pattern can be utilized. Alternatively, the surface may be provided with unevenness (unevenness pattern) by giving a suitable matte pattern or embossing. Alternatively, the uneven pattern may be filled with a coloring agent.
In this embodiment, the above-described surface protective layer 5 is embedded in the concave portions 8 forming the uneven pattern. This point will be described below.
The shape of the concave-convex pattern provided on the surface of the transparent thermoplastic resin layer 4 is not particularly limited, but the shape of the recesses 8 forming the concave-convex pattern is the back side of the transparent thermoplastic resin layer 4 (adhesiveness It is preferable to have a shape such that the opening diameter increases from the resin layer 3) toward the surface side (surface protective layer 5). With such a shape, when the surface protective layer composition (coating liquid) is embedded in the concave portion 8 by wiping, the embedding is facilitated.

Moreover, it is preferable that the side surface forming the concave portion 8 is an inclined surface. If the side surfaces forming the recesses 8 are inclined surfaces, the recesses 8 can be easily filled with the surface protective layer composition (coating liquid) by wiping.
Also, all of the side surfaces forming the concave portion 8 may be covered with the surface protective layer 5 .
In addition, the depth of the concave portion 8 is preferably in the range of 1 μm or more and 100 μm or less, more preferably in the range of 10 μm or more and 50 μm or less, and in the range of 20 μm or more and 40 μm or less in the thickness direction of the transparent thermoplastic resin layer 4 . Inside is more preferred. If the depth of the concave portions 8 is within the above numerical range, the surface protective layer composition (coating liquid) can be easily filled in the concave portions 8 by wiping, and the peeling of the surface protective layer can be prevented.
The width of the concave portion 8 is preferably in the range of 1 μm to 10 μm, more preferably in the range of 2 μm to 8 μm, and even more preferably in the range of 4 μm to 6 μm. If the width of the concave portion 8 is within the above numerical range, the surface protective layer composition (coating liquid) can be easily filled in the concave portion 8 by wiping, and the surface protective layer embedded in the concave portion 8 can be prevented from peeling off. can be prevented.

In addition, the recesses 8 are preferably completely filled (filled) with the surface protective layer composition (coating liquid), but the filling rate of the surface protective layer 5 with respect to the volume of the recesses 8 may be 10% or more. preferred. If the filling ratio of the surface protective layer 5 to the volume of the recess 8 is 10% or more, the weather resistance of the recess 8 can be improved. That is, if the filling rate of the surface protective layer 5 with respect to the volume of the concave portion 8 is 10% or more, it is possible to reduce the occurrence of whitening and breakage in the conduit portion. Further, as described above, the filling rate of the surface protective layer 5 with respect to the volume of the recesses 8 is preferably 100%, but it is more preferable that the filling rate of the surface protective layer 5 with respect to the volume of the recesses 8 is 80% or less. It is more preferable that the filling rate of the surface protective layer 5 with respect to the volume of the concave portion 8 is 60% or less. If the filling ratio of surface protective layer 5 to the volume of recess 8 is 80% or less, sufficient tactile sensation can be obtained in recess 8 .
By setting the filling rate of the surface protective layer 5 to 100% with respect to the volume of the recesses 8, the surface of the surface protective layer 5 filled in the recesses 8 and the transparent thermoplastic resin layer 4 in the regions not provided with the recesses 8 The surface may be so-called flush.

As the transparent thermoplastic resin layer 4, for example, synthetic resins such as polyolefin, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, foams of these synthetic resins, ethylene-propylene copolymers, etc. polymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene block copolymer rubber, and rubber such as polyurethane. Among them, polyolefin-based resins are particularly preferably used. Specifically, it is preferable to use a homopolymer of ethylene, propylene, or butene, a copolymer resin of two or more of these, or a mixed resin thereof. In addition, various additives such as ultraviolet absorbers, radical scavengers, antioxidants, and processing stabilizers may be added to these resins, if necessary.

Among the above, examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5′-methylenebis(2-hydroxy-4 2-hydroxybenzophenones such as -methoxybenzophenone); 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-ditert-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'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazole 2-(2'-hydroxyphenyl)benzotriazoles such as solyl)phenol), 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole; phenyl salicylate, resorcinol monobenzoate , 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl -benzoates such as 3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanylide and 2-ethoxy-4'-dodecyloxanilide; ethyl- Cyanoacrylates such as α-cyano-β, β-diphenyl acrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl) acrylate; 2-(2-hydroxy-4-octoxyphenyl)- 4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, 2-(2-hydroxy -4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine and other triaryltriazines. In addition, the content of the above-mentioned ultraviolet absorber is preferably in the range of 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the acrylic resin. It is within the range of part or less.
In the case of the above-described benzotriazole-based ultraviolet absorber, the content is preferably in the range of 0.5 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the acrylic resin, and more preferably, It is in the range of 1 part by mass or more and 30 parts by mass or less.

Among the above, hindered amine compounds are preferably used as the radical scavenger. In this embodiment, for example, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2, 6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2 ,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2 ,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl).di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1, 2,2,6,6-pentamethyl-4-piperidyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl) )-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / 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-tert-octylamino-s-triazine polycondensate, 1,5,8,12 -tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12 -tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine -6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl- 4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl) -4-piperidyl)amino)-s-triazin-6-yl]aminoundecane and other hinders A doamine-based compound can be mentioned. In addition, the content of the radical scavenger described above is preferably in the range of 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the acrylic resin. It is within the range of part or less.

Among the above antioxidants, phenolic antioxidants are preferably used. In this embodiment, for example, 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide], 4,4′-thiobis(6-tert-butyl-m-cresol), 2, 2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol ), 2,2′-ethylidenebis(4,6-di-tert-butylphenol), 2,2′-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2 -methyl-4-hydroxy-5-tert-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5- Tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene , 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl)phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)methyl propionate]methane, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,6 - hexamethylene bis [(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis [2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris[(3,5-di-tert-butyl -4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]- 2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol bis [(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] and the like. In addition, the content of the antioxidant described above is preferably in the range of 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the acrylic resin. It is within the range of part or less.

Among the above-mentioned processing stabilizers, phosphorus-based ones are preferably used. In the present embodiment, for example, trisnonylphenyl phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl]phosphite, tri Decylphosphite, octyldiphenylphosphite, di(decyl)monophenylphosphite, di(tridecyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) ) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis (2,4-dicumylphenyl)pentaerythritol diphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methyl phenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene Phosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2′-methylenebis(4,6-tert-butylphenyl)-2-ethylhexylphosphite, 2, 2′-methylenebis(4,6-tert-butylphenyl)-octadecylphosphite, 2,2′-ethylidenebis(4,6-ditert-butylphenyl)fluorophosphite, tris(2-[(2,4 ,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, 2-ethyl-2-butylpropylene glycol and 2, Phosphite of 4,6-tri-tert-butylphenol and the like. In addition, the content of the processing stabilizer described above is preferably in the range of 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.05 parts by mass or more and 5 parts by mass with respect to 100 parts by mass of the acrylic resin. It is within the range of part or less.

The film thickness of the transparent thermoplastic resin layer 4 is preferably in the range of 15 μm or more and 150 μm or less. The method for laminating the colored thermoplastic resin layer 1 and the transparent thermoplastic resin layer 4 includes a dry lamination method in which the adhesive resin layer 3 is interposed between them, and a colored thermoplastic resin layer 1 provided with the adhesive resin layer 3. An extrusion lamination method or the like can be used in which a transparent resin is melt-extruded from a T-die and laminated while being formed into a film.

[Adhesive resin layer]
The adhesive resin layer 3 is provided as necessary in order to bond the colored thermoplastic resin layer 1 provided with the pattern layer 2 and the transparent thermoplastic resin layer 4 together. If the target adhesive strength can be obtained without the adhesive resin layer 3, or if the transparent thermoplastic resin layer 4 is not provided, it may not be necessary.
The constituent material of the adhesive resin layer 3 is not particularly limited as long as it contributes to the improvement of the adhesive strength between arbitrary resins. material is available. As a constituent material of the adhesive resin layer 3, generally, a two-liquid curing type polyurethane adhesive having a high coating film cohesion is often used. Also, the coating method can be appropriately selected depending on the coating liquid viscosity and the like. The layer thickness of the adhesive resin layer 3 is preferably about 0.5 μm to 6 μm.

[Colored thermoplastic resin layer]
The colored thermoplastic resin layer 1 is preferably one on which the pattern layer 2 can be provided by gravure printing or the like. Examples of the colored thermoplastic resin layer 1 include thin paper, titanium paper, paper such as resin-impregnated paper, polyethylene, polypropylene, polybutylene, polystyrene, polycarbonate, polyester, polyamide, ethylene-vinyl acetate copolymer, polyvinyl alcohol, acrylic, and the like. or foams of these synthetic resins, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber, styrene-butadiene copolymer rubber, styrene-isoprene-styrene block copolymer rubber, styrene-butadiene-styrene It can be arbitrarily selected from block copolymer rubber, rubber such as polyurethane, organic or inorganic non-woven fabric, synthetic paper, metal foil such as aluminum, iron, gold, silver, and the like.

[Pattern layer]
The pattern layer 2 is a layer for imparting a concealing property or a design property, and can be provided by printing pattern ink all over or partially on the colored thermoplastic resin layer 1 .
Binders for design inks may be appropriately selected from, for example, nitrocellulose, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, polyester, and the like, either alone or modified. They may be aqueous, solvent-based, or emulsion-based, and the curing method may be arbitrarily selected from a one-liquid type and a two-liquid type using a curing agent. Furthermore, it is also possible to cure the ink by irradiation with active energy rays such as ultraviolet rays and electron beams.

As pigments for pattern inks, for example, various known pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica are used. can do. These ink materials need to be selected in consideration of adhesion to the colored thermoplastic resin layer 1 under the pattern layer 2 and the resin laminated on the pattern layer 2 .
Various additives such as an ultraviolet absorber, a radical scavenger, and a dispersant may be added to the pattern layer 2 as necessary. The pattern layer 2 may be provided directly on the colored thermoplastic resin layer 1 by a known printing technique such as gravure printing, offset printing, screen printing, flexographic printing, silk printing, electrostatic printing, or inkjet printing. can be done. In addition to the application of ink, it is also possible to impart a metallic design by vapor deposition or sputtering of various metals.

[Base material]
In this embodiment, the decorative sheet 10 described above may be attached to the base material 7 to form the decorative member 11 . Specifically, by laminating the decorative sheet 10 on a metal base such as a steel plate or an aluminum plate, a wood base such as MDF, or a resin base such as PET, the decorative sheet 10 has high weather resistance. It is possible to obtain the member 11, and even when it is used for outdoor purposes, the deterioration of the design property over time is hardly observed.

[Adhesive layer]
The adhesive layer 6 is a layer made of an adhesive, and is a layer for bonding the base material 7 and the colored thermoplastic resin layer 1 together.
As the adhesive constituting the adhesive layer 6, for example, a urethane-based adhesive, an acrylic adhesive, an ethylene-vinyl acetate copolymer, a vinyl chloride-vinyl acetate copolymer, a polyester-based adhesive, or the like can be used. In particular, in the present embodiment, a two-liquid curable urethane adhesive or the like obtained by blending polyester polyol and polyisocyanate is preferable. In addition, adding an inorganic powder such as silica, barium sulfate, or calcium carbonate to these materials to form the adhesive layer 6 is effective in preventing blocking during winding and storage, and in improving the adhesive force due to the anchoring effect. .
The layer thickness of the adhesive layer 6 is preferably about 0.5 μm to 6 μm.
As the constituent material of the adhesive layer 6, the same constituent material as that of the adhesive resin layer 3 described above may be used.

(Manufacturing method of decorative sheet and decorative member)
An example of a method for manufacturing the decorative sheet 10 according to this embodiment will be briefly described below.
The colored thermoplastic resin layer 1, pattern layer 2 and adhesive resin layer 3 described above are laminated in this order.
Next, a transparent thermoplastic resin layer 4 is formed on the adhesive resin layer 3, and at the same time, an uneven pattern is formed on the surface of the transparent thermoplastic resin layer 4 by embossing.
Next, a coating liquid for forming the surface protective layer 5 is applied to the surface of the transparent thermoplastic resin layer 4 on which the uneven pattern is formed.
Finally, the surface protective layer 5 is formed on the transparent thermoplastic resin layer 4 by wiping the coating liquid so as to fill the recesses 8 forming the uneven pattern and curing the coating liquid.
Thus, the decorative sheet 10 according to this embodiment is formed.

An example of a method for manufacturing the decorative member 11 according to this embodiment will be briefly described below.
The above-described decorative sheet 10 and the base material 7 are bonded together with the above-described adhesive layer 6 interposed therebetween.
Finally, the adhesive layer 6 is cured to form the decorative member 11 .

[Example]
(Example 1)
A pattern layer (thickness: 3 μm) was provided by gravure-printing a wood grain pattern on a masking polyethylene raw material (thickness: 70 μm) using a two-part urethane ink (V180: manufactured by Toyo Ink Co., Ltd.).
Next, the following transparent thermoplastic resin layer composition was applied to a thickness of 80 μm on the polyethylene raw fabric provided with the pattern layer via a dry lamination adhesive (Takelac A540: manufactured by Mitsui Chemicals, Inc.) (thickness: 2 μm). A transparent thermoplastic resin layer was formed by extrusion lamination, and at the same time, the surface was embossed with a wood grain pattern (conduit portion).
Next, the following surface protective layer composition was applied to the outermost surface of the transparent thermoplastic resin layer by gravure coating and dried. At this time, the recessed portions of the transparent thermoplastic resin layer were filled with the surface protective layer composition by wiping, and cured at 25° C. for 3 days to obtain the decorative sheet of Example 1.

(Transparent thermoplastic resin layer composition)
・Transparent homopolypropylene resin (Prime PP; manufactured by Prime Polymer Co., Ltd.)
... 99 parts by mass Ultraviolet absorber (TINUVIN 326; manufactured by BASF Japan Ltd.) ... 0.5 parts by mass Light stabilizer (TINUVIN XT55; manufactured by BASF Japan Ltd.) ... 0.5 part by mass

(Surface protective layer composition)
・Main agent (methyl methacrylate/cyclohexyl methacrylate = 80/20)
... 90 parts by mass Ultraviolet absorber (TINUVIN 479; manufactured by BASF Japan Ltd.) ... 9 parts by mass Light stabilizer (TINUVIN 123; manufactured by BASF Japan Ltd.) ... 1 part by mass Curing agent (Takenate D170; Mitsui Chemicals, Inc.): 10 parts by mass Solvent (ethyl acetate): 240 parts by mass The following formula (7) shows the molecular structure of "tinuvin 479".

(Comparative example 1)
A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1 except that Tinuvin 400 was used as the ultraviolet absorber added to the surface protective layer of Example 1.
The molecular structure of "tinuvin 400" is shown in the following formula (8).

(Comparative example 2)
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1, except that ADEKA STAB LA-F70 was used as the UV absorbent added to the surface protective layer of Example 1.
The following formula (9) shows the molecular structure of “ADEKA STAB LA-F70”.

(Comparative Example 3)
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Example 1, except that the step of embedding the surface protective layer composition in the concave portions of the transparent thermoplastic resin layer was omitted.

<Evaluation>
The decorative sheets obtained in the above examples and comparative examples were evaluated for design and weather resistance by the following methods. The evaluation results are shown in Table 1 below.

a) Designability The appearance of the decorative sheet was visually evaluated according to the following criteria. However, the reference sheet was prepared separately from a sheet containing no ultraviolet absorber in Example 1.
⊚: Visual observation shows no difference in appearance from the reference sheet.
◯: A very slight difference in appearance from the reference sheet is observed by visual observation.
x: By visual observation, a feeling of white turbidity is observed with respect to the reference sheet.
It should be noted that, if the evaluation of the designability is "⊚" or "○", there is no problem in use, so it was judged as acceptable.

b) Weather resistance Discoloration of the pattern after the accelerated weather resistance test of the decorative sheet was visually observed and evaluated as 3, 2, and 1 in descending order of occurrence of discoloration, whitening, and cracking (rupture) of the pattern. In the accelerated weather resistance test, a metal weather tester (KU-R5DCI-A) manufactured by Daipla Wintes Co., Ltd. was used, with a black panel temperature of 63 ° C and an illumination of 65 mW / cm ² (20 hours of UV irradiation + 4 hours of condensation) for one cycle. 30 cycles were performed.
Regarding the presence or absence of discoloration of the pattern, visual observation was carried out separately for the area where the wood grain pattern was formed (conduit portion) and the area where the wood grain pattern was not formed (flat portion).
If the evaluation of weather resistance is "1", there is no problem in use, so it was judged as acceptable.

As shown in Table 1, the decorative sheet according to the present embodiment exemplified in Example 1 has less white turbidity and good designability by adding a hydroxyphenyltriazine-based ultraviolet absorber having a specific structure to the surface protective layer. and has excellent weather resistance.

The decorative sheet of the present invention relates to a decorative sheet used for construction materials such as interior and exterior construction materials, surfaces and frame materials for fittings, surface materials for home electric appliances, flooring materials, and the like, and includes wooden boards and inorganic boards. , a metal plate or the like to be used as a decorative member.

DESCRIPTION OF SYMBOLS 1... Colored thermoplastic resin layer 2... Pattern layer 3... Adhesive resin layer 4... Transparent thermoplastic resin layer 5... Surface protective layer 6... Adhesive layer 7... Substrate 8... Concave portion 10... Decorative sheet 11... Decorative member

Claims (12)

A decorative sheet comprising an olefin resin layer having an uneven pattern formed on its surface and a surface protective layer formed on the surface of the olefin resin layer,
The surface protective layer is mainly composed of an acrylic resin composition containing only methyl (meth)acrylate and cyclohexyl (meth)acrylate as monomer components, and has a structure represented by the following formula (1). Contains one or more agents,
The surface protective layer is embedded in the recesses forming the uneven pattern of the olefin resin layer,
The filling rate of the surface protective layer in the recess is in the range of 10% or more and 80% or less ,
The recess has a depth in the range of 10 μm or more and 50 μm or less and a width in the range of 1 μm or more and 10 μm or less,
The olefin resin layer comprises a benzotriazole-based ultraviolet absorber and a homopolypropylene resin composition,
The content of the benzotriazole-based ultraviolet absorber contained in the olefin resin layer is in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the homopolypropylene resin composition. makeup sheet.

2. The surface protective layer is characterized in that the hydroxyphenyltriazine-based ultraviolet absorber is contained within a range of 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. 1. The cosmetic sheet according to 1. 3. The decorative sheet according to claim 1, wherein all surfaces forming the recesses are covered with a resin forming the surface protective layer. 4. The decorative sheet according to any one of claims 1 to 3 , wherein the surface protective layer further contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by formula (2) below.

The content of the hydroxyphenyltriazine-based UV absorber having the structure represented by the formula (1) is 40 parts by mass or more with respect to 100 parts by mass of the hydroxyphenyltriazine-based UV absorber having the structure represented by the formula (2). 5. The decorative sheet according to claim 4 , wherein the content is in the range of 80 parts by mass or less. 6. The decorative sheet according to any one of claims 1 to 5 , wherein the surface protective layer further contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by formula (3) below.

6. The decorative sheet according to any one of claims 1 to 5 , wherein the surface protective layer further contains a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by formula (4) below.

The surface protective layer comprises the hydroxyphenyltriazine-based UV absorber, the benzotriazole-based UV absorber, and an acrylic resin composition,
The content of the benzotriazole-based ultraviolet absorber contained in the surface protective layer is in the range of 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the acrylic resin composition. The decorative sheet according to any one of claims 1 to 7 . A substrate, and the decorative sheet according to any one of claims 1 to 8 provided on at least one side of the substrate,
A decorative member, wherein the substrate is a metal-based substrate, a wood-based substrate, or a resin-based substrate. The base material and the decorative sheet are bonded via an adhesive layer,
The decorative sheet includes, in order from the adhesive layer side, a colored thermoplastic resin layer, a pattern layer, an adhesive resin layer, the olefin resin layer, and the surface protective layer,
10. The decorative member according to claim 9 , wherein the base material is a woody base material. A method for manufacturing the decorative sheet according to any one of claims 1 to 8 ,
forming the uneven pattern on the surface of the olefin resin layer by embossing;
forming the surface protective layer on the surface of the olefin resin layer on which the uneven pattern is formed;
A method for producing a decorative sheet, wherein in the step of forming the surface protective layer, the surface protective layer is embedded in the recesses forming the uneven pattern of the olefin resin layer. 12. The method for producing a decorative sheet according to claim 11 , wherein in the step of forming the surface protective layer, the surface protective layer is embedded in the concave portions forming the uneven pattern of the olefin resin layer by wiping. .

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