JP7726355B2 - Decorative sheets, decorative materials and fittings - Google Patents

Description

The present invention relates to decorative sheets, decorative members, and building materials.

Conventionally, decorative sheets made from vinyl chloride resin have been known for use in decorating residential interior materials, etc. (See, for example, Patent Document 1).

Japanese Patent Application Publication No. 5-278173

It has been pointed out that polyvinyl chloride resin may contain dioxins, which are considered to be harmful substances, in the gases it emits when burned. However, in recent years, improvements in incineration equipment and exhaust gas treatment technology have helped to reduce the generation of harmful substances, and the existence of polyvinyl chloride resin is being reconsidered.
Furthermore, with the growing awareness of zero-energy homes (ZEH), there is a high demand for highly insulated window frames (resin sashes) made of polyvinyl chloride resin, and it is also being considered to decorate the base material of these. When an olefin-based resin sheet is used as a decorative material for such window frames (resin sashes), there are problems such as the difficulty of recycling.

In contrast, polyvinyl chloride resin has the advantage of being highly adaptable to processing and easy to recycle, so using polyvinyl chloride resin as a decorative material in combination with base materials such as polyvinyl chloride window frames is expected to make a significant contribution to reducing environmental impact. However, polyvinyl chloride resin sheets can become discolored when used outdoors for long periods of time, and when attached to base materials such as window frames, the sheets are often bent during processing. Polyvinyl chloride resin sheets are prone to cracking when processed at low temperatures, so it is important to take this into consideration when designing.

The present invention was made in consideration of the above points, and aims to provide decorative sheets, decorative members, and fittings that are highly adaptable to processing.

As a result of extensive research, the present inventors have discovered that the above-mentioned objectives can be achieved in decorative sheets containing polyvinyl chloride resin by setting the composition of the decorative sheet, specifically the degree of polymerization and the content of plasticizer and weathering agent, to appropriate values.
In other words, a decorative sheet according to one embodiment of the present invention is a decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order, wherein the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less, and the transparent resin layer contains a high molecular weight polyester-based plasticizer in an amount of 20 PHR or more and 30 PHR or less.
In addition, a decorative sheet according to another aspect of the present invention is a decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order, wherein the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less, and the transparent resin layer contains 20 PHR or more and 30 PHR or less of a high molecular weight polyester-based plasticizer.

In addition, a decorative member according to another aspect of the present invention is characterized by comprising the decorative sheet of the above aspect and a substrate arranged on the outermost surface of the decorative sheet on the side of the pattern layer.
Furthermore, a fixture according to another aspect of the present invention is characterized by comprising the decorative sheet of the above aspect and a fixture component arranged on the outermost surface of the decorative sheet on the side of the pattern layer.

According to one aspect of the present invention, decorative sheets, decorative members, and fittings with excellent processability can be obtained.

1 is a cross-sectional view schematically illustrating an example of a decorative sheet according to one embodiment of the present invention. FIG. 10 is a cross-sectional view schematically illustrating an example of a decorative member according to another embodiment of the present invention.

Hereinafter, embodiments of the present technology will be described with reference to the drawings.
The drawings are schematic, and the relationship between thickness and planar dimensions, the thickness ratio of each layer, etc., differ from the actual ones. The layers do not necessarily have to be stacked in the order shown in the drawings, as long as they are within the scope of the present disclosure. Layers not shown in the drawings may also be added. Furthermore, the embodiments shown below are illustrative of configurations that embody the technical ideas of the present disclosure, and the materials, shapes, structures, etc. of the components of the present disclosure are not limited to those described below. The technical ideas of the present disclosure may be modified in various ways within the technical scope defined by the claims.
Furthermore, the directions of "left and right" and "up and down" in the following description are merely definitions for the sake of convenience and do not limit the technical idea of the present disclosure. Therefore, for example, if the page is rotated 90 degrees, "left and right" and "up and down" are read interchangeably, and if the page is rotated 180 degrees, "left" becomes "right" and "right" becomes "left" (first embodiment).
First, the first embodiment will be described.

(Configuration of decorative sheet)
FIG. 1 is a cross-sectional view that schematically shows an example of a decorative sheet 1 according to a first embodiment of the present invention.
As shown in Figure 1, the decorative sheet 1 comprises a colored polyvinyl chloride resin layer (colored substrate layer) 2, a design layer 4, a transparent polyvinyl chloride resin layer (transparent resin layer) 6, and a surface protective layer 8. The surface protective layer 8, which is the outermost layer of the decorative sheet 1, has an embossed portion 10 formed from the surface side to the transparent polyvinyl chloride resin layer 6.

(Colored polyvinyl chloride resin layer)
The colored polyvinyl chloride resin layer 2 functions as a support for the decorative sheet 1, and is colored opaquely to provide hiding properties, so that when the decorative sheet 1 is attached to an adherend such as a window frame, the colored polyvinyl chloride resin layer 2 can hide color variations and defects on the surface of the adherend.
The colored polyvinyl chloride resin layer 2 is formed from polyvinyl chloride resin, for example, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and is also suitable for printing. By forming the decorative sheet 1 using the colored polyvinyl chloride resin layer 2, scraps of the decorative sheet 1 produced when the decorative sheet 1 is attached to an adherend, or used decorative sheet 1, can be melted and extruded using an extruder or the like and reused as a recycled substrate. Furthermore, since PVC is easier to reuse by melting than olefin-based resins, the decorative sheet 1 according to this embodiment can have improved processability and recyclability.

Furthermore, the hue of the opaque colored polyvinyl chloride resin layer 2 can be appropriately selected as the base color of the pattern layer 4. Furthermore, when the texture of the surface of the adherend is to be utilized, the colored polyvinyl chloride resin layer 2 preferably has a transparency to the extent that the surface of the adherend can be seen through when viewed from the surface protective layer 8 side.
The colored polyvinyl chloride resin layer 2 can be obtained, for example, by mixing or kneading a colorant such as a pigment into polyvinyl chloride resin. While organic or inorganic pigments can be used as colorants, inorganic pigments are preferred. In other words, the colored polyvinyl chloride resin layer 2 preferably contains an inorganic substance as a colorant. For example, the colored polyvinyl chloride resin layer 2 preferably contains one or more inorganic substances selected from the group consisting of calcium carbonate, titanium oxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

Furthermore, the colored polyvinyl chloride resin layer 2 may contain, as needed, one or more additives selected from various additives such as colorants, fillers, ultraviolet absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, antifriction agents, light scattering agents, and gloss adjusters.
Although the colored polyvinyl chloride resin layer 2 made of polyvinyl chloride resin is described here as the colored substrate layer, the colored substrate layer is not limited to polyvinyl chloride resin. A colored thermoplastic resin layer made of a thermoplastic resin may be provided as the colored substrate layer, but from the viewpoint of recycling, it is preferable to use a polyvinyl chloride resin as the resin constituting the colored substrate layer, similar to the transparent polyvinyl chloride resin layer 6.

(Picture layer)
The pattern layer 4 is laminated on one side (the upper side in FIG. 1 ) of the colored polyvinyl chloride resin layer 2, and is a layer for adding a pattern to impart design features to the decorative sheet 1.
The design layer 4 is formed using printing ink, paint, etc. The printing ink, paint, etc. that forms the design layer 4 is formed by dissolving or dispersing a colorant such as a dye or pigment together with a suitable binder resin in a suitable diluent solvent. Examples of pigments include condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide, and pearl pigments such as mica.

The printing ink or paint that forms the design layer 4 is applied by using various printing methods such as gravure printing or offset printing, or various coating methods such as gravure coating or roll coating.
The binder resin contained in the design layer 4 is not particularly limited, but it is preferable to use a resin with good adhesiveness. That is, a resin that has thermal fusion properties with polyvinyl chloride resin, such as a vinyl chloride-vinyl acetate copolymer, an acrylic resin alone, or a mixture of a vinyl chloride-vinyl acetate copolymer and an acrylic resin, is preferable.
Any pattern can be used as the pattern formed by the pattern layer 4, such as a wood grain pattern, a stone pattern, a fabric pattern, an abstract pattern, a geometric pattern, letters, symbols, a solid color, or a combination thereof. In order to improve the hiding power of the decorative sheet 1, a hiding layer may be provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2. The hiding layer is formed, for example, using an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

The thickness of the design layer 4 is preferably in the range of 1 μm or more and 10 μm or less. This is because when the thickness of the design layer 4 is 1 μm or more, it is possible to make the printing clear. On the other hand, when the thickness of the design layer 4 is 10 μm or less, it is possible to improve the printing workability when producing the decorative sheet 1 and to reduce the production costs.
In addition, functional additives such as extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesive aids, drying agents, curing agents, curing accelerators, and curing retarders may be added to the pattern layer 4 to impart various functions.
In addition, the pattern layer 4 may be configured to have, for example, a solid colored base layer to conceal the color and pattern of the substrate to which the decorative sheet 1 is attached, and a pattern layer to add a pattern to impart design features.

(Transparent polyvinyl chloride resin layer)
The transparent polyvinyl chloride resin layer 6 is a layer for improving the weather resistance of the decorative sheet 1 .
The transparent polyvinyl chloride resin layer 6 is formed of polyvinyl chloride resin, for example, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, and has good moldability and processability, and is also suitable for printing. As described above, PVC can be used as a recycled substrate by melting and extruding it, and is easier to reuse by melting than olefin-based resins.
In other words, the decorative sheet 1 according to this embodiment can reliably improve processability and recyclability by using the colored polyvinyl chloride resin layer 2 and the transparent polyvinyl chloride resin layer 6, both of which contain polyvinyl chloride resin.

The transparent polyvinyl chloride resin layer 6 preferably has a transparency sufficient to allow the pattern layer 4, which is provided on the surface of the colored polyvinyl chloride resin layer 2 (the lower surface in FIG. 1 ), to be seen through when viewed from the surface protective layer 8. The transparent polyvinyl chloride resin layer 6 is preferably, for example, colorless and transparent, colored and transparent, or translucent.
The resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500. In terms of the K value calculated in accordance with JIS K7367-2:1999, the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having a K value of 60 to 75.

The higher the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6, the stronger, more elongated, and less susceptible to cracking the decorative sheet 1, and the greater its durability. If the average degree of polymerization is too high, the gelation temperature increases, resulting in fisheyes and other defects, making film formation of the transparent polyvinyl chloride resin layer 6 difficult. Furthermore, the lower the average degree of polymerization, the more susceptible the decorative sheet 1 is to cracking, and its low viscosity results in poor calendering suitability and poor film formation stability. Therefore, it is preferable that the resin constituting the transparent polyvinyl chloride resin layer 6 be a polyvinyl chloride resin with an average degree of polymerization of 800 to 1500, as calculated in accordance with JIS K6720-2. Furthermore, when the average degree of polymerization of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6 is 800 to 1500, the decorative sheet 1 has a breaking elongation of 10% to 400% at 0°C, ensuring stable production during processing such as wrapping. If the breaking elongation at 0°C is less than 10%, the decorative sheet 1 is too hard, potentially causing whitening and cracking. If the breaking elongation at 0°C is greater than 400%, the decorative sheet 1 will be soft and have no stiffness, making it difficult to handle, resulting in poor productivity and poor scratch resistance.

Similarly, when the K value of the polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6 is within the range of 60 or more and 75 or less, the breaking elongation of the decorative sheet 1 at 0°C is 10% or more and 400% or less, and when the K value is less than 60 or greater than 75, the breaking elongation of the decorative sheet 1 at 0°C is less than 10% or greater than 400%.
A plasticizer may be added to the transparent polyvinyl chloride resin layer 6. A high molecular weight polyester resin is preferred as the plasticizer, and the content of the plasticizer is preferably 20 PHR or more and 30 PHR or less. In terms of viscosity, the viscosity of the plasticizer measured with a capillary viscometer in accordance with JIS K7367-5:2000 is preferably 500 MPa s or more and 3000 MPa s or less.

Among polyester resins, high molecular weight polyesters are preferred as plasticizers. Phthalic acid resins (dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more prone to bleed-out than high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance.
If the plasticizer content is less than 20 PHR, even if a phthalic acid resin is used, the cold resistance will be poor, so when a high molecular weight polyester resin is used as the plasticizer, the plasticizer content is preferably 20 PHR or more. If the plasticizer content is more than 30 PHR, the decorative sheet 1 becomes soft and loses its stiffness, making it difficult to handle and reducing productivity during processing. In addition, the scratch resistance of the decorative sheet 1 is also low.

Furthermore, if the viscosity of the plasticizer is less than 500 MPa·s, it has a low molecular weight, is prone to bleed-out, and has poor weather resistance. On the other hand, if the viscosity of the plasticizer is more than 3000 MPa·s, it is too high in molecular weight, making resin production difficult. It also has poor cold resistance.
When the plasticizer content is within the range of 20 PHR or more and 30 PHR or less, the breaking elongation of the decorative sheet 1 at 0°C is 10% or more and 400% or less, resulting in good production stability during processing such as wrapping. As mentioned above, if the breaking elongation at 0°C is less than 10%, the decorative sheet 1 will be hard and will whiten and crack, whereas if it is more than 400%, the decorative sheet 1 will be soft and have no stiffness, making it difficult to handle, resulting in poor productivity and poor scratch resistance.

[Weatherproofing agent]
The transparent polyvinyl chloride resin layer 6 may further contain a weather resistance agent, which can impart excellent weather resistance to the transparent polyvinyl chloride resin layer 6.
The transparent polyvinyl chloride resin layer 6 may contain a NOR-type hindered amine light stabilizer (HALS) as a weathering agent. The use of a NOR-type HALS with low basicity can suppress the dehydrochlorination reaction of the transparent polyvinyl chloride resin layer 6, making it effective against recent acid rain. Examples of NOR-type hindered amine light stabilizers (HALS) that can be used in the transparent polyvinyl chloride resin layer 6 include "ADEKA STAB LA-81" manufactured by ADEKA Corporation, "TINUVIN 123" (decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester) manufactured by BASF Japan Ltd., and "TINUVIN XT850FF" manufactured by BASF Japan Ltd.

Furthermore, the transparent polyvinyl chloride resin layer 6 may contain an ultraviolet absorber as a weather resistance agent, and preferably contains at least one of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber, and more preferably contains a cyanoacrylate-based ultraviolet absorber.
The amount of ultraviolet absorber added to the transparent polyvinyl chloride resin layer 6 may be determined depending on the desired weather resistance, but it is preferable that the amount of ultraviolet absorber be 0.5 parts by mass or more per 100 parts by mass of the transparent vinyl chloride resin that constitutes the transparent polyvinyl chloride resin layer 6. This ensures that the weather resistance of the decorative sheet 1 is improved.

(benzophenone-based ultraviolet absorber)
Examples of the "benzophenone-based" ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), and mixtures, modified products, polymers, and derivatives thereof.

(Benzotriazole-based ultraviolet absorber)
Examples of the "benzotriazole-based" ultraviolet absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and the like, as well as mixtures, modified products, polymers, and derivatives thereof.

(Triazine-based ultraviolet absorber)
Examples of the "triazine-based" ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and mixtures, modified products, polymers, and derivatives thereof.

(Cyanoacrylate UV absorber)
Examples of the "cyanoacrylate" ultraviolet absorber include ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, and the like.
The thickness of the transparent polyvinyl chloride resin layer 6 is preferably in the range of 50 μm to 150 μm, more preferably in the range of 50 μm to 100 μm, and even more preferably in the range of 60 μm to 80 μm. A thickness of 50 μm or more reliably improves the weather resistance of the decorative sheet 1 and can absorb unevenness of the adherend, such as a window frame, to improve the application finish of the decorative sheet 1. Furthermore, when the thickness of the transparent polyvinyl chloride resin layer 6 is 150 μm or less, the transparent polyvinyl chloride resin layer 6 is not formed thicker than necessary, improving processability (e.g., bending processability) and reducing the manufacturing cost of the decorative sheet 1.

[Heat stabilizer]
The transparent polyvinyl chloride resin layer 6 preferably contains a metal salt of a higher fatty acid as a heat stabilizer.

(Surface protective layer)
The surface protective layer 8 is a layer provided to impart functions such as weather resistance, scratch resistance, stain resistance, and designability to the decorative sheet 1. The material constituting the surface protective layer 8 is not particularly limited, and can be appropriately selected from, for example, urethane-based, acrylic-based, acrylic silicone-based, fluorine-based, and epoxy-based resin materials.
The surface protective layer 8 may contain various additives such as an ultraviolet absorber, a heat stabilizer, a light stabilizer, an antiblocking agent, a catalyst scavenger, a colorant, a light scattering agent, and a gloss adjuster, as needed, and preferably contains an ultraviolet absorber and a light stabilizer. The surface protective layer 8 is not necessarily provided, but is preferably provided.

Hereinafter, an example of the surface protection layer 8 according to this embodiment will be described with a specific example.
In this embodiment, the surface protection layer 8 may be primarily composed of an acrylic resin composition containing cyclohexyl(meth)acrylate as a monomer component. In this embodiment, cyclohexyl(meth)acrylate refers to cyclohexyl acrylate or cyclohexyl methacrylate. By including cyclohexyl(meth)acrylate as a monomer component, the surface protection layer 8 can have a lower affinity for water and can suppress deterioration due to hydrolysis or the like.

The content of cyclohexyl (meth)acrylate is preferably in the range of 5% to 50% by mass of all the monomer components of the acrylic resin composition, i.e., of the monomer components of the acrylic resin composition that is the main component of the surface protective layer 8. By setting the cyclohexyl (meth)acrylate content to 5% by mass or more, a sufficient deterioration suppression effect can be achieved. Furthermore, by setting the cyclohexyl (meth)acrylate content to 50% by mass or less, it is possible to impart high weather resistance over time without significantly changing the various performance properties of the surface protective layer 8 of the decorative sheet, such as improved surface hardness maintenance, improved stain resistance, and surface gloss adjustment. Here, the above-mentioned "main component" means that the content of the acrylic resin composition that constitutes the surface protective layer 8 is 50% by mass or more relative to the total mass of the surface protective layer 8.

In addition to cyclohexyl (meth)acrylate, examples of monomer components of the acrylic resin composition that can be used for the surface protection layer 8 in this embodiment include cyclohexylmethyl (meth)acrylate, cyclohexylethyl (meth)acrylate, cyclohexylpropyl (meth)acrylate, cyclohexylbutyl (meth)acrylate, dimethylcyclohexane mono(meth)acrylate, dimethylcyclohexane di(meth)acrylate, trimethylcyclohexane mono(meth)acrylate, trimethylcyclohexane di(meth)acrylate, trimethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane mono(meth)acrylate, tetramethylcyclohexane di(meth)acrylate, tetramethylcyclohexane tri(meth)acrylate, tetramethylcyclohexane tetra(meth)acrylate, dicyclohexylmethyl (meth)acrylate, dicyclohexylmethyl (meth)acrylate, phenoxycyclohexylmethyl (meth)acrylate, methoxycyclohexylmethyl (meth)acrylate, etc. Among these, those containing isomers may be each isomer alone and/or a mixture of each isomer.

Furthermore, in this embodiment, the surface protective layer 8 may be formed by applying a coating liquid containing the above-mentioned acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component and a weathering agent such as an ultraviolet absorber, which will be described later, to the outermost surface of the decorative sheet. As will be described in detail later, for example, a coating liquid containing the above-mentioned acrylic resin composition and a weathering agent may be applied to the transparent polyvinyl chloride resin layer 6 on which the embossed portions 10 have been formed, and then the coating liquid may be embedded in the embossed portions 10 by wiping, thereby forming the surface protective layer 8.
As a method for curing the coating liquid for forming the surface protective layer 8, for example, a one-component curing type, a two-component curing type that uses a curing agent, or an active energy ray curing type that is cured by irradiating with ultraviolet light or ionizing radiation or the like can be used. However, in consideration of weather resistance, the two-component curing type or the active energy ray curing type is preferred, and in consideration of post-processability after being bonded to various substrates to form a decorative member, a two-component curing type that is crosslinked by isocyanate curing is desirable.

A preferred example of a two-component curing acrylic resin composition is a composition containing 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 in one molecule that can react with the functional groups. Particularly preferred is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

Acrylic polyols containing two or more hydroxyl groups per molecule include, in addition to the aforementioned cyclohexyl (meth)acrylate, (meth)acrylic acid ester copolymers containing hydroxyethyl (meth)acrylate as a monomer component. Meanwhile, polyisocyanate compounds containing two or more isocyanate groups per molecule include, 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, biuret types, and the like, synthesized using known techniques from one or more compounds selected from these. Furthermore, compositions containing a mixture of one or more of these different types of polyisocyanates can also be used. Among these, HDI, HDI trimer type, TMP adduct type, and biuret type are preferred from the standpoint of weather resistance. The amount of isocyanate compound relative to the resin components described above can be set at will, but it is desirable to set it so that the hydroxyl group/isocyanate group equivalent ratio is approximately 1/1 to 1/3. In particular, if the hydroxyl group equivalent exceeds the isocyanate group equivalent, crosslinking may not proceed sufficiently, failing to impart the desired performance to the surface protective layer 8, which is undesirable.

When the coating liquid for forming the surface protective layer 8 is cured by active energy ray curing, known monomers, oligomers, etc. having a (meth)acryloyl group can be used as the active energy ray curable acrylic resin composition, and the above-mentioned cyclohexyl (meth)acrylate can be blended in addition to these monomers and oligomers.
In order to further improve the weather resistance of the decorative sheet 1, in this embodiment, an ultraviolet absorber and a light stabilizer are added to the surface protective layer 8 as weather resistance agents.

(ultraviolet absorber)
As the ultraviolet absorber, for example, known ones such as benzotriazole-based, triazine-based (e.g., hydroxyphenyltriazine-based), and benzophenone-based ones can be used. Among these, if a hydroxyphenyltriazine-based ultraviolet absorber is selected, the triazine skeleton suppresses bleeding, and the triazine skeleton is more chemically stable than the skeletons of benzotriazole-based and benzophenone-based ultraviolet absorbers, making it possible to maintain ultraviolet absorption performance for a long period of time. In other words, it is preferable that the surface protective layer 8 contains a triazine-based ultraviolet absorber as the ultraviolet absorber.

Examples of hydroxyphenyltriazine-based ultraviolet absorbers include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethylhexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl) 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazin-2-yl)-3-hydroxy-phenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-iso-octyloxyphenyl)-s-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, and the like. In this embodiment, the surface protective layer 8 may contain 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (hereinafter referred to as "ultraviolet absorber A" for convenience). 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, which is used as the ultraviolet absorber A, is commonly known as the main component of "Tinuvin 479: manufactured by BASF Japan, Ltd."

In the surface protective layer 8 of this embodiment, the amount of the triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber added is preferably in the range of 1 part by mass or more and 30 parts by mass or less relative to 100 parts by mass of the resin composition (e.g., acrylic resin composition) that forms the surface protective layer 8. By adding the ultraviolet absorber in an amount of 1 part by mass or more, an effect of improving weather resistance is exerted, and by adding the ultraviolet absorber in an amount of 30 parts by mass or less, the effects on physical properties of the surface protective layer 8 other than weather resistance can be suppressed to a level that does not pose a practical problem.
In particular, when the above-mentioned ultraviolet absorber A is used as the ultraviolet absorber added to the surface protective layer 8, the amount added is preferably in the range of 1 part by mass to 20 parts by mass, more preferably in the range of 5 parts by mass to 15 parts by mass, and even more preferably in the range of 8 parts by mass to 12 parts by mass, relative to 100 parts by mass of the acrylic resin composition. By setting the amount of ultraviolet absorber A to 1 part by mass or more, an effect of improving weather resistance is exerted, and by setting it to 20 parts by mass or less, the effects on physical properties other than the weather resistance of the surface protective layer 8 can be suppressed to a level that does not cause practical problems.

In addition, in this embodiment, the triazine-based (hydroxyphenyltriazine-based) UV absorber in the surface protective layer 8 is a combination of UV absorber A and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter referred to as "UV absorber B" for convenience), providing even better weather resistance. This is because UV absorber B has a high ability to absorb UV light in the relatively high-energy short-wavelength range and is chemically more stable than other UV absorbers that absorb light in roughly the same wavelength range. Therefore, using these two UV absorbers in combination broadens the UV absorption wavelength range. UV absorber B, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, is commonly known as the main component of "ADK STAB LA-46 (manufactured by ADEKA Corporation)."

In this embodiment, the amount of UV absorber A added to surface protective layer 8 is preferably in the range of 10 to 200 parts by weight, more preferably in the range of 20 to 100 parts by weight, and even more preferably in the range of 40 to 80 parts by weight, per 100 parts by weight of UV absorber B. By adding UV absorber A in the above range, even better weather resistance can be achieved.

(Light stabilizer)
For example, a radical scavenger can be used as the light stabilizer added to the surface protective layer 8. By using the above-mentioned triazine-based ultraviolet absorber in combination with the radical scavenger, the weather resistance of the decorative sheet 1 can be further improved. Examples of hindered amine radical scavengers that can be used in this embodiment include bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, 1-oxy-2,2,6,6-tetramethyl-4-hydroxypiperidine, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis( 1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol/diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidyl) 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate cyclohexane and N-butyl 2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide, and a reaction product of 2-aminoethanol.

In this embodiment, the amount of light stabilizer (e.g., a hindered amine-based radical scavenger) added to surface protective layer 8 is preferably in the range of 1 part by mass or more and 30 parts by mass or less relative to 100 parts by mass of the resin composition (e.g., an acrylic resin composition) that forms surface protective layer 8. By adding 1 part by mass or more of the light stabilizer, it is possible to obtain the desired weather resistance, and by adding 30 parts by mass or less, it is possible to suppress bleed-out of the weather resistance agent and also to suppress the effect on other physical properties of surface protective layer 8.
In the present embodiment, the surface protective layer 8 contains an ultraviolet absorber and a light stabilizer, but the present disclosure is not limited to this. The surface protective layer 8 may be configured to contain at least one of an ultraviolet absorber and a light stabilizer, as long as it has the desired weather resistance depending on the application.

(Amount of application)
The coating amount of the surface protective layer 8, i.e., the coating amount of the material of the surface protective layer 8 on the transparent polyvinyl chloride resin layer 6, is preferably in the range of 3 g/ ^m2 or more and less than 10 g/ ^m2 . If the coating amount is less than 3 g/ ^m2 , good weather resistance cannot be obtained, and if it is 10 g/m2 or ^more , recyclability may be impaired. Therefore, by setting the coating amount within this range, good weather resistance and recyclability can both be achieved. Furthermore, by setting the coating amount within this range, productivity and processability (e.g., bending processability) can be improved.

(Embossed part)
As shown in Figure 1, an embossed portion 10 is provided on the outermost surface of the decorative sheet 1. By providing the embossed portion 10 on the outermost surface, it is possible to improve fingerprint resistance while maintaining the matte feel of the surface of the decorative sheet 1. Furthermore, the embossed portion 10 can be formed into various uneven shapes, such as wood grain vessel grooves, stone slab surface unevenness (granite cleavage planes, etc.), cloth surface texture, matte finish, sand grain, hairline, and linear grooves, thereby imparting a given design to the surface of the decorative sheet 1. The embossed portion 10 can be formed into various uneven shapes, for example, depending on the design of the picture layer 4 or the desired design.
The embossed portions 10 are formed on the surface (outermost surface) side of the surface protective layer 8, which is the outermost layer of the decorative sheet 1, and form a concave-convex pattern. In this embodiment, the above-mentioned surface protective layer 8 is embedded in the embossed portions 10 that form this concave-convex pattern. This point will be described below.

In the decorative sheet 1 according to this embodiment, the embossed portions 10 are provided in the transparent polyvinyl chloride resin layer 6. In other words, the transparent polyvinyl chloride resin layer 6 is the layer on which the embossed portions 10 are formed. The shape of the uneven pattern provided on the surface of the transparent polyvinyl chloride resin layer 6 is not particularly limited, but it is preferable that the shape of the embossed portions 10 that make up the uneven pattern be such that the opening diameter increases from the design layer 4 side of the transparent polyvinyl chloride resin layer 6 toward the surface protection layer 8. This shape makes it easier to embed the surface protection layer composition (coating liquid) into the embossed portions 10 by wiping.

Furthermore, the side surface on which the embossed portion 10 is formed is preferably an inclined surface. If the side surface on which the embossed portion 10 is formed is an inclined surface, the surface protective layer composition (coating liquid) can be easily embedded in the embossed portion 10 by wiping.
In addition, the entire side surface forming the embossed portion 10 may be covered with the surface protection layer 8 .
The depth of the embossed portion 10 is preferably within a range of 1 μm to 50 μm in the thickness direction of the transparent polyvinyl chloride resin layer 6. When the depth of the embossed portion 10 is within the above-mentioned range, the surface protective layer composition (coating liquid) can be easily embedded into the embossed portion 10 by wiping, and peeling of the surface protective layer can be prevented.

The width of the embossed portion 10 in the cross section shown in Figure 1 is preferably in the range of 1 µm to 20 µm. If the width of the embossed portion 10 is in this range, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portion 10 by wiping, and peeling of the surface protective layer embedded in the embossed portion 10 can be prevented.

Furthermore, it is preferable that the embossed portion 10 is completely filled (packed) with the surface protective layer composition (coating liquid), and a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 10% or more is preferred. A filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 10% or more can improve the weather resistance of the embossed portion 10. In other words, a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 10% or more can reduce the occurrence of whitening or breakage in the conduit portion, for example. As mentioned above, a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 100% is preferred, but a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 80% or less is more preferred, and a filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 60% or less is even more preferred. A filling rate of the surface protective layer 8 relative to the volume of the embossed portion 10 of 80% or less can provide a satisfactory tactile feel in the embossed portion 10.

Furthermore, by setting the filling rate of the surface protection layer 8 to 100% of the volume of the embossed portion 10, the surface of the surface protection layer 8 filled in the embossed portion 10 and the surface of the transparent polyvinyl chloride resin layer 6 in the area not having the embossed portion 10 can be made flush, so to speak.
The embossed portion 10 is not necessarily provided, but is preferably provided.

(Total thickness of decorative sheet)
The total thickness of the decorative sheet 1, i.e., the sum of the thicknesses of the colored polyvinyl chloride resin layer 2, the design layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8, is preferably in the range of 100 μm to 300 μm, more preferably 120 μm to 200 μm. If the total thickness of the decorative sheet 1 is thinner than 100 μm, the hiding power and scratch resistance are reduced, and further, the decorative sheet 1 loses rigidity during processing, resulting in reduced productivity. If the total thickness of the decorative sheet 1 is thicker than 300 μm, the processability, such as bending, is reduced. This allows for the formation of a decorative sheet 1 that has the same level of hiding power as decorative sheets formed using conventional olefin-based resins and good processability. Note that the total thickness of the decorative sheet 1 here refers, in the case of the decorative sheet 1 shown in FIG. 1 , to the sum of the thicknesses of the colored polyvinyl chloride resin layer 2, the design layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8, i.e., the sum of the thicknesses of all layers that make up the decorative sheet 1. For example, in the decorative sheet 1 shown in Figure 1, if a concealing layer is provided between the pattern layer 4 and the colored polyvinyl chloride resin layer 2, the thickness refers to the total thickness of the decorative sheet 1, which is the sum of the thickness of the colored polyvinyl chloride resin layer 2, the thickness of the pattern layer 4, the thickness of the transparent polyvinyl chloride resin layer 6, the thickness of the surface protective layer 8, and the thickness of the concealing layer; in other words, it refers to the total thickness of the decorative sheet 1 formed including a laminate in which the colored polyvinyl chloride resin layer 2, the pattern layer 4, the transparent polyvinyl chloride resin layer 6, and the surface protective layer 8 are laminated in this order.

(Modification)
In the decorative sheet 1, a gloss-adjusting layer (not shown) may be provided on the surface protective layer 8 so that the gloss-adjusting layer and the pattern of the pattern layer 4 are in harmony with each other.
In addition, in the decorative sheet 1, the pattern of the pattern layer 4 and the embossed portion 10 may be synchronized.
Furthermore, although the decorative sheet 1 has a colored polyvinyl chloride resin layer 2 as a colored substrate layer, the colored polyvinyl chloride resin layer (colored substrate layer) 2 is not necessarily provided, that is, the decorative sheet 1 may have a single layer specification. When the decorative sheet 1 has a single layer specification, it is preferable to provide a concealing layer (not shown) on the surface of the design layer 4 opposite the transparent polyvinyl chloride resin layer 6.

(Decorative material)
The decorative sheet 1 shown in FIG. 1 may be laminated to a substrate 20 as shown in FIG. 2 to form a decorative member 100.

(Base material)
The substrate 20 can be a wood substrate or a metal substrate. Examples of wood substrates include wood veneer, wood plywood, laminated lumber, particle board, medium-density fiberboard, and hard fiberboard. Examples of metal substrates include steel and aluminum plates. The substrate 20 can be made of a resin such as plastic, or a composite material thereof. When the substrate 20 is a resin substrate, for example, vinyl chloride resin can be used. Vinyl chloride resin substrates 20 have high insulating properties and are increasingly in demand as window frame fixtures (sashes). Furthermore, a decorative member 100 in which a vinyl chloride resin substrate 20 is decorated with a decorative sheet 1 can be reused by dissolving both the substrate 20 and the decorative sheet 1, thereby improving recyclability.

The substrate 20 may be made of, for example, a non-combustible steel plate or a non-combustible material as specified in Ministry of Construction Notification No. 1400. The substrate 20 may have a bent structure or a three-dimensional structure.
By laminating the decorative sheet 1 according to this embodiment to the substrate 20, a decorative member having excellent processability and recyclability can be obtained, even when the substrate 20 is formed using polyvinyl chloride resin.
The configuration of the decorative member 100 is not limited to the example shown in Fig. 2. That is, the decorative member 100 may be configured to include a decorative sheet 1 laminated on one surface of the substrate 20, as well as on the other surface of the substrate 20 (the lower surface in Fig. 1).

When laminating the decorative sheet 1 to the substrate 20, an adhesive layer 12 may be provided by laminating the sheet via an adhesive selected as necessary, or the sheet may be laminated directly without an adhesive or the like.
The adhesive may be selected depending on the material of the substrate 20, and may be a two-component curing or hot melt adhesive.
Methods for laminating and adhering the decorative sheet 1 to the substrate 20 include a method of pressing with a metal plate in contact with the substrate using flat pressure, and a continuous lamination method using a circular pressure method. In particular, the continuous lamination method using an endless metal belt allows for the high-quality decorative member 100 to be produced continuously at high speed without warping or waviness on the surface, with good adhesion between the layers and densely cured and integrated.

The substrate 20 is effective when applied to window frames and other fixtures, particularly exterior fixtures. In other words, with the growing awareness of zero-energy homes (ZEHs), there is a high demand for highly insulated window frames and other fixtures made of polyvinyl chloride resin. Because the decorative sheet 1 is made of polyvinyl chloride, by attaching it to a fixture or fixture component, particularly a window frame made of polyvinyl chloride resin, and combining the substrate 20 and the decorative sheet 1 into a monomaterial, it is possible to obtain fixtures, particularly exterior fixtures, that are highly recyclable compared to fixtures made of olefin-based resin sheets, etc.
It is also possible to use building materials made of other materials, such as aluminum, as the base material 20. In this case, although recyclability will be somewhat reduced compared to when the material is made mono-material, by laminating a decorative sheet 1 made of polyvinyl chloride resin, it is possible to obtain building materials that are highly suitable for processing.

(Method for manufacturing decorative sheet and decorative member)
An example of a method for producing the decorative sheet 1 according to this embodiment will now be briefly described.
For example, the design layer 4 is printed on the colored polyvinyl chloride resin layer 2 made of a colored polyvinyl chloride resin sheet.
Next, a transparent polyvinyl chloride resin layer 6 is formed by thermal lamination on the colored polyvinyl chloride resin layer 2 on which the pattern layer 4 has been formed, and at the same time, an embossed portion 10 is formed by providing a concave-convex pattern on the surface of the transparent polyvinyl chloride resin layer 6 opposite to the colored polyvinyl chloride resin layer 2 by embossing.
Next, a coating liquid for forming a surface protection layer 8 is applied to the surface of the transparent polyvinyl chloride resin layer 6 on which the uneven pattern (embossed portion 10) has been formed.
Finally, the coating liquid is wiped so as to fill the embossed portions 10 that form the uneven pattern, and the coating liquid is cured to form a surface protection layer 8 on the transparent polyvinyl chloride resin layer 6.
In this way, the decorative sheet 1 according to this embodiment is formed.

An adhesive is applied to the surface of the decorative sheet 1 formed in this manner on the side of the colored polyvinyl chloride resin layer 2, and a substrate 20 is attached to it, thereby forming a decorative member 100 in which the decorative sheet 1 and the substrate 20 are bonded together via the adhesive layer 12.
The above-described embodiment is an example of the present invention, and the present invention is not limited to the above-described embodiment. Various modifications can be made depending on the design, etc., even in forms other than this embodiment, as long as they do not deviate from the technical idea of the present invention.

(effect)
(1) The decorative sheet 1 according to the first embodiment of the present invention is formed by laminating at least a design layer 4 and a transparent polyvinyl chloride resin layer 6 in this order, and the resin constituting the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500, and the transparent polyvinyl chloride resin layer 6 further contains 20 to 30 PHR of a high-molecular-weight polyester plasticizer. Therefore, even when a transparent polyvinyl chloride resin sheet is formed into a film, film formation stability can be ensured, and good wrapping suitability of the decorative sheet 1 and good bending condition of the decorative sheet 1 during wrapping can be obtained.
Furthermore, the decorative sheet 1 is composed of at least a design layer 4 and a transparent polyvinyl chloride resin layer 6 laminated in this order, and the resin constituting the transparent polyvinyl chloride resin layer 6 is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 to 75, and the transparent polyvinyl chloride resin layer 6 further contains 20 to 30 PHR of a high-molecular-weight polyester plasticizer. Therefore, even in this case, even when a transparent polyvinyl chloride resin sheet is formed into a film, film formation stability can be ensured, and good wrapping suitability of the decorative sheet 1 and good bending condition of the decorative sheet 1 during wrapping can be obtained.

(2) The decorative sheet 1 has a breaking elongation of 10% or more and 400% or less at 0°C, so it has a moderate softness, which prevents whitening and cracking during wrapping, and prevents a decrease in productivity and a decrease in scratch resistance.
(3) The viscosity of the plasticizer added to the transparent polyvinyl chloride resin layer 6, as measured by a capillary viscometer in accordance with JIS K7367-5:2000, satisfies the range of 500 MPa·s to 3000 MPa·s, ensuring good weather resistance. Furthermore, by adjusting the viscosity to 500 MPa·s to 3000 MPa·s, the breaking elongation of the decorative sheet 1 at 0°C can be easily adjusted to within the range of 10% to 400%.
(4) By using a NOR type HALS as the HALS added to the transparent polyvinyl chloride resin layer 6, the de-HCl reaction can be suppressed.

(5) By forming the decorative member 100 from a base material 20 and a decorative sheet 1 bonded to this base material 20, a decorative member 100 with excellent processability can be provided even if the decorative sheet 1 is formed using polyvinyl chloride resin.
(6) Because the fitting is formed by laminating the decorative sheet 1 to the fitting component as the base material 20, it is possible to provide a fitting with excellent workability, even when the decorative sheet 1 is formed using polyvinyl chloride resin. In particular, by laminating the decorative sheet 1 to an exterior fitting component (base material 20) made of a vinyl chloride material, both the decorative sheet 1 and the fitting component are made into a mono-material made of a vinyl chloride material, which further enhances recyclability.
Example 1

The first embodiment of the present invention will be described in detail below with reference to examples and comparative examples. Note that the present invention is not limited to the following examples.

(Example 1-1)
A colored polyvinyl chloride resin sheet was used as the colored polyvinyl chloride resin layer (colored substrate layer). A design layer was formed on one side of the colored polyvinyl chloride resin sheet by gravure printing using a printing ink for vinyl chloride. Then, a transparent polyvinyl chloride resin sheet serving as a transparent polyvinyl chloride resin layer (transparent resin layer) was thermally laminated onto the colored polyvinyl chloride resin sheet including the design layer. Then, a resin composition mainly composed of an acrylic resin composition was laminated onto the transparent polyvinyl chloride sheet as a surface protective layer.
This resulted in the production of the decorative sheet of Example 1-1. The resulting decorative sheet had a breaking elongation of 40% at 0°C.
The composition of each layer is as follows:

(Colored polyvinyl chloride resin sheet)
Material: Polyvinyl chloride resin (PVC)
Thickness: 80 μm

(Transparent polyvinyl chloride resin sheet)
Material: Polyvinyl chloride resin (PVC)
Degree of polymerization: 820
K value: 62.1
Thickness: 80 μm
Plasticizer: High molecular weight polyester
Viscosity: 510
Additives: 20PHR
UV absorber: 0.5 parts by mass of cyanoacrylate UV absorber HALS: 0.5 parts by mass of NOR type (ADK STAB LA81, manufactured by ADEKA Corporation)

(Picture layer)
Binder resin: A mixture of vinyl chloride resin-vinyl acetate resin copolymer and acrylic resin

(Surface protective layer)
Base: methyl methacrylate/2-hydroxyethyl methacrylate (95/5 copolymer) 90 parts by weight Ultraviolet absorber: Tinuvin 479 (manufactured by BASF Japan Ltd.) 9 parts by weight Light stabilizer: Tinuvin 123 (manufactured by BASF Japan Ltd.) 1 part by weight Curing agent: Takenate D170 (manufactured by Mitsui Chemicals, Inc.) 10 parts by weight Solvent: ethyl acetate 240 parts by weight Coating amount: 3 g/ ^m2

(Example 1-2)
A decorative sheet of Example 1-2 was obtained in the same manner as in Example 1-1, except that a transparent polyvinyl chloride resin (PVC) with a degree of polymerization of 1440 and a K value of 73.6 was used and the amount of plasticizer added was 28 PHR. The resulting decorative sheet had a breaking elongation of 320% at 0°C.
(Examples 1-3)
A decorative sheet of Example 1-3 was obtained in the same manner as in Example 1-1, except that a high molecular weight polyester plasticizer with a viscosity of 2500 was used as the plasticizer in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 110% at 0°C.

(Examples 1 to 4)
A decorative sheet of Example 1-4 was obtained in the same manner as in Example 1-3, except that a benzophenone-based ultraviolet absorber was used as the ultraviolet absorber in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 120% at 0°C.
(Examples 1-5)
The decorative sheet of Example 1-5 was obtained in the same manner as in Example 1-1, except that the transparent polyvinyl chloride resin sheet used was a polyvinyl chloride resin (PVC) with a degree of polymerization of 1020 and a K value of 66.5, the plasticizer used was a high-molecular-weight polyester-based plasticizer with a viscosity of 1200, and the additive amount of this plasticizer was 24 PHR. The resulting decorative sheet had a breaking elongation of 260% at 0°C.

(Examples 1-6)
The decorative sheet of Example 1-6 was obtained in the same manner as in Example 1-5, except that the transparent polyvinyl chloride resin sheet used was a polyvinyl chloride resin (PVC) with a degree of polymerization of 1320 and a K value of 71.7, and the plasticizer used was a high molecular weight polyester-based plasticizer with a viscosity of 2000. The resulting decorative sheet had a breaking elongation of 300% at 0°C.
(Examples 1-7)
The decorative sheet of Example 1-7 was obtained in the same manner as in Example 1-1, except that a phthalic acid-based plasticizer with a viscosity of 400 was used as the plasticizer in the transparent polyvinyl chloride resin sheet, and a benzophenone-based ultraviolet absorber was used as the ultraviolet absorber. The resulting decorative sheet had a breaking elongation of 170% at 0°C.

(Examples 1-8)
A decorative sheet of Example 1-8 was obtained in the same manner as in Example 1-1, except that an NH type HALS was used as the HALS in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 40% at 0°C.
(Examples 1 to 9)
The decorative sheet of Example 1-9 was obtained in the same manner as in Example 1-5, except that no ultraviolet absorber was added to the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 250% at 0°C.

(Comparative Example 1-1)
A decorative sheet of Comparative Example 1 was obtained in the same manner as in Example 1-1, except that a polyvinyl chloride resin (PVC) with a degree of polymerization of 690 and a K value of 58.6 was used for the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 30% at 0°C.
(Comparative Example 1-2)
A decorative sheet of Comparative Example 2 was obtained in the same manner as in Example 1-1, except that a transparent polyvinyl chloride resin (PVC) with a degree of polymerization of 1740 and a K value of 77.4 was used in the transparent polyvinyl chloride resin sheet. The resulting decorative sheet had a breaking elongation of 520% at 0°C.

(Comparative Examples 1-3)
A decorative sheet of Comparative Example 3 was obtained in the same manner as in Examples 1-5, except that the amount of plasticizer added to the transparent polyvinyl chloride resin sheet was 35 PHR. The resulting decorative sheet had a breaking elongation of 460% at 0°C.
(Comparative Examples 1-4)
A decorative sheet of Comparative Example 4 was obtained in the same manner as in Examples 1-3, except that the amount of plasticizer added to the transparent polyvinyl chloride resin sheet was 15 PHR. The resulting decorative sheet had a breaking elongation of 5% at 0°C.

〔evaluation〕
The decorative sheets of the Examples and Comparative Examples were each evaluated for film formation stability of the transparent polyvinyl chloride resin sheet, suitability for wrapping, state of bent portions during wrapping, and light resistance. The evaluation criteria were as follows:

(Film formation stability of transparent polyvinyl chloride resin sheet)
The film-forming stability during film-forming of a polyvinyl chloride resin sheet was evaluated.
◯ (pass): No fish eyes or the like occurred, the calendering suitability was good, and sheets could be stably produced.
× (fail): Fish eyes or the like are observed, or the calendering suitability is poor, and a sheet cannot be stably produced.

(suitability for wrapping processing)
The ease of handling when wrapping the decorative sheet was evaluated.
◎ (Pass): Possible under a wide range of production conditions 〇 (Pass): Possible under limited production conditions × (Fail): Difficult to produce (weak and difficult to handle, or prone to breaking and cracking)

(Bent part condition during wrapping process)
The state of the bent portion during wrapping of the decorative sheet was evaluated.
⊚ (pass): No whitening or cracking occurs at the bent portion during processing at 0°C.
Good (pass): When processed at 0°C, slight whitening occurs at the bent portion, but it is at an acceptable level. No cracks occur.
× (fail): Whitening or cracking occurs at the bent portion during processing at 0°C.

(weather resistance)
Metal weather testing machine (KU-R5DCI-A, manufactured by Daipla Wintes Co., Ltd.)
A 504-hour accelerated weather resistance test was carried out under the following test conditions.
Test conditions: BPT (black panel temperature): 63°C, illuminance: 65mW/cm ² , 21 cycles of "20 hours of UV irradiation + 4 hours of condensation" were performed. The color difference ΔE before and after the accelerated weathering test was evaluated.
◎(Pass): ΔE<2.0
〇 (Pass): ΔE = 2.0 or more and 4.0 or less × (Fail): ΔE > 4.0
A grade of "○" or higher was considered a pass.

The evaluation results for each of the above evaluation items are shown in Table 1.

As shown in Table 1, Examples 1-1 to 1-9, in which the resin constituting the transparent polyvinyl chloride resin sheet (transparent polyvinyl chloride resin layer 6) satisfies at least one of the following criteria: polyvinyl chloride resin with an average degree of polymerization of 800 to 1500 as calculated in accordance with JIS K6720-2, or polyvinyl chloride resin with a K value of 60 to 75 as calculated in accordance with JIS K7367-2:1999, and which contains 20 to 30 PHR of a high-molecular-weight polyester plasticizer, had a breaking elongation of 10 to 400% at 0°C, and were confirmed to have good film-forming stability for the transparent polyvinyl chloride resin sheet, good wrapping suitability for the decorative sheet, and good bending condition during wrapping of the decorative sheet.

The decorative sheets of Examples 1-1 to 1-6 also had good weather resistance, but it was confirmed that better weather resistance was obtained when a cyanoacrylate-based UV absorber was used (Example 1-3) than when a benzophenone-based UV absorber was used (Example 1-4). Furthermore, it was confirmed that insufficient weather resistance was achieved in Example 1-7, which used a phthalic acid-based plasticizer with a viscosity of 400 MPa·s for the transparent polyvinyl chloride resin sheet and a benzophenone-based UV absorber; Example 1-8, which used an NH-type HALS for the transparent polyvinyl chloride resin sheet; and Example 1-9, in which the transparent polyvinyl chloride resin sheet did not contain a UV absorber.

Furthermore, in Example 1-1, Comparative Example 1-1, in which the resin constituting the transparent polyvinyl chloride resin sheet (transparent polyvinyl chloride resin layer 6) was a polyvinyl chloride resin with an average degree of polymerization of less than 800, had a low breaking elongation viscosity at 0°C, and it was confirmed that the film-forming stability of the transparent polyvinyl chloride resin sheet was reduced. Conversely, in Example 1-1, Comparative Example 1-2, in which the resin constituting the polyvinyl chloride resin sheet with an average degree of polymerization of 1500 or more was a polyvinyl chloride resin sheet with an average degree of polymerization higher than 1500, was easy to stretch and less likely to crack, but had a large breaking elongation at 0°C and was soft and lacking in stiffness, resulting in poor film-forming stability of the transparent polyvinyl chloride resin sheet. Furthermore, it was confirmed that the decorative sheet's suitability for wrapping processing was poor, and the condition of bent parts during wrapping was also poor.

Furthermore, in Examples 1-5, Comparative Example 3, in which the amount of plasticizer added to the transparent polyvinyl chloride resin sheet exceeded 30 PHR, had a breaking elongation of more than 400% at 0°C, and was soft and had no stiffness, so it was confirmed that the suitability for wrapping processing and the state of the bent part during wrapping processing were poor.
In addition, in Example 1-1, Comparative Example 1-4, in which the amount of plasticizer added to the transparent polyvinyl chloride resin sheet was less than 20 PHR, had a breaking elongation of less than 10% at 0°C and was hard, and it was confirmed that the suitability for wrapping processing and the condition of the bent part during wrapping processing were poor.

Second Embodiment
Next, a second embodiment of the present invention will be described.
The decorative sheet of the second embodiment is the same as the decorative sheet of the first embodiment except for the configuration of the transparent polyvinyl chloride resin layer 6, so the same parts are given the same reference numerals and detailed description thereof is omitted.

(Transparent polyvinyl chloride resin layer)
The transparent polyvinyl chloride resin layer (transparent resin layer) 6 a in the second embodiment is a layer for improving the weather resistance of the decorative sheet 1 .
The transparent polyvinyl chloride resin layer 6 a is formed of polyvinyl chloride resin, for example, a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, and has good moldability and processability, and is also suitable for printing. As described above, PVC can be used as a recycled substrate by melting and extruding it, and is easier to reuse by melting than olefin-based resins.
In other words, the decorative sheet 1 according to the second embodiment can reliably improve processability and recyclability by using a colored polyvinyl chloride resin layer 2 and a transparent polyvinyl chloride resin layer 6a containing polyvinyl chloride resin.

The transparent polyvinyl chloride resin layer 6a preferably has a transparency sufficient to allow the pattern layer 4, which is provided on the surface of the colored polyvinyl chloride resin layer 2 (the lower surface in FIG. 1 ), to be seen through when viewed from the surface protective layer 8. The transparent polyvinyl chloride resin layer 6a is preferably, for example, colorless and transparent, colored and transparent, or translucent.
The resin constituting the transparent polyvinyl chloride resin layer 6a is preferably a polyvinyl chloride resin containing a NOR-type hindered amine light stabilizer (HALS). The hindered amine light stabilizer is preferably one with low basicity, preferably with a base dissociation constant pkb of 5 to 12, more preferably with a base dissociation constant pkb of 8 to 10. A low basicity with a base dissociation constant pkb of 5 or more can suppress the base- _{induced dehydrochlorination} reaction of the transparent polyvinyl chloride resin layer 6a, which is effective against recent acid rain. On the other hand, since the higher the basicity, the lower the weather resistance, so the base dissociation constant pkb is preferably 12 or less.

The content of the hindered amine light stabilizer in the transparent polyvinyl chloride resin layer 6a is preferably 0.05% to 5% of the resin solid content, and more preferably 0.1% to 1%.
The polyvinyl chloride resin constituting the transparent polyvinyl chloride resin layer 6a is preferably a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500. Alternatively, the resin constituting the transparent polyvinyl chloride resin layer 6 is preferably a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 to 75.

The higher the average degree of polymerization of the polyvinyl chloride resin that makes up the transparent polyvinyl chloride resin layer 6a, the stronger, more stretchable, and less likely to crack the decorative sheet 1 will be, and the greater its durability will be. If the average degree of polymerization is too high, the gelation temperature will increase, resulting in fish eyes and other problems, making it difficult to form the transparent polyvinyl chloride resin layer 6a. Furthermore, the lower the average degree of polymerization, the more likely the decorative sheet 1 will crack, and the lower the viscosity will result in poor calendering suitability and poor film formation stability. Therefore, it is preferable that the resin that makes up the transparent polyvinyl chloride resin layer 6a be a polyvinyl chloride resin with an average degree of polymerization of 800 or more and 1500 or less, calculated in accordance with JIS K6720-2.

The transparent polyvinyl chloride resin layer 6a preferably has an ultraviolet transmittance of 0.05% T or less at a wavelength of 320 nm and 0.4% T or less at a wavelength of 360 nm.
Here, in decorative sheets (polyvinyl chloride (PVC) sheets) formed using polyvinyl chloride resin, the C-C bonds in the PVC main chain are broken by absorbing ultraviolet light around 320 nm, causing the sheet to become embrittled and initiate a dehydrochlorination reaction. Furthermore, at around 360 nm, the C-Cl bonds of the PVC are broken, producing polyenes with C=C double bonds, resulting in the sheet turning brown (a phenomenon known as brown spots).
In this embodiment, the ultraviolet transmittance of the transparent polyvinyl chloride resin layer 6a is 0.05%T or less at a wavelength of 320 nm and 0.4%T or less at a wavelength of 360 nm. By keeping the ultraviolet transmittance at a wavelength of 320 nm to 0.05%T or less, embrittlement and dehydrochlorination of the decorative sheet can be suppressed. Furthermore, by keeping the ultraviolet transmittance at a wavelength of 360 nm to 0.4%T or less, the formation of C═C double-bond polyenes can be suppressed, thereby suppressing the occurrence of discoloration (brown spots). In other words, by controlling the ultraviolet transmittance at wavelengths of 320 nm and 360 nm in the transparent polyvinyl chloride resin layer 6a to the above-mentioned upper limit values, the weather resistance of the decorative sheet 1 can be improved. Therefore, a decorative sheet 1 having excellent weather resistance can be obtained, capable of withstanding long-term outdoor use, for example, as a decorative sheet for decorating the surface of decorative materials for exterior and semi-exterior applications.
A plasticizer may be added to the transparent polyvinyl chloride resin layer 6a. A high-molecular-weight polyester resin is preferred as the plasticizer, and the content of the plasticizer is preferably 20 PHR or more and 30 PHR or less. Furthermore, in terms of viscosity, the viscosity of the plasticizer measured with a capillary viscometer in accordance with JIS K7367-5:2000 is preferably 500 MPa s or more and 3000 MPa s or less.

Among polyester resins, high molecular weight polyesters are preferred as plasticizers. Phthalic acid resins (dioctyl phthalate (DOP), diisononyl phthalate (DINP), dioctyl adipate (DOA), etc.) and epoxy resins have good plasticizing efficiency, but are more prone to bleed-out than high molecular weight polyesters, and high molecular weight polyesters are superior in terms of solvent resistance, oil resistance, and weather resistance.
If the plasticizer content is less than 20 PHR, even if a phthalic acid resin is used, the cold resistance will be poor, so when a high molecular weight polyester resin is used as the plasticizer, the plasticizer content is preferably 20 PHR or more. If the plasticizer content is more than 30 PHR, the decorative sheet 1 becomes soft and loses its stiffness, making it difficult to handle and reducing productivity during processing. In addition, the scratch resistance of the decorative sheet 1 is also low.

Furthermore, if the viscosity of the plasticizer is less than 500 MPa·s, it has a low molecular weight, is prone to bleed-out, and has poor weather resistance. On the other hand, if the viscosity of the plasticizer is more than 3000 MPa·s, it is too high a molecular weight, making resin production difficult. It also has poor cold resistance.

[Weatherproofing agent]
The transparent polyvinyl chloride resin layer 6a may further contain a weather resistance agent, which can impart excellent weather resistance to the transparent polyvinyl chloride resin layer 6a.

The transparent polyvinyl chloride resin layer 6a preferably contains an ultraviolet absorber to effectively control the ultraviolet transmittance described above. That is, in the decorative sheet 1 according to the second embodiment, the transparent polyvinyl chloride resin layer 6a is preferably formed from a transparent polyvinyl chloride resin and contains an ultraviolet absorber. This allows the ultraviolet transmittance of the transparent polyvinyl chloride resin layer 6a to be effectively controlled as described above, and provides the decorative sheet 1 with excellent weather resistance.
More specifically, the transparent polyvinyl chloride resin layer 6 a preferably contains at least one ultraviolet absorber selected from the group consisting of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber.
This improves the ultraviolet absorption ability of the transparent polyvinyl chloride resin layer 6a over a wide range of wavelengths, from 320 nm to 360 nm, and effectively controls the ultraviolet transmittance, imparting excellent weather resistance to the transparent polyvinyl chloride resin layer 6a and improving the weather resistance of the decorative sheet 1.

Some benzophenone-based UV absorbers can absorb light in the wavelength range of 320 to 340 nm. Benzotriazole-based UV absorbers can absorb light in the wavelength ranges of 300 to 320 nm and 340 to 360 nm. Triazine-based UV absorbers absorb light in the wavelength range of 270 to 360 nm, and cyanoacrylate-based UV absorbers have a maximum absorption around 310 nm and are suitable for use with PVC.
The content of the ultraviolet absorber in the transparent polyvinyl chloride resin layer 6a may be adjusted depending on the desired weather resistance, but for example, it is preferably in the range of more than 0.3 parts by mass and not more than 1.0 part by mass, and more preferably in the range of 0.5 parts by mass to 0.8 parts by mass, per 100 parts by mass of the transparent vinyl chloride resin that constitutes the transparent polyvinyl chloride resin layer 6a. This ensures improved weather resistance of the decorative sheet 1.

(benzophenone-based ultraviolet absorber)
Benzophenone-based ultraviolet absorbers that can be used include, for example, octabenzone and its modified products, polymers, and derivatives. Other examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone). Examples of known products include "ADEKA STAB (registered trademark) LA-1413 manufactured by ADEKA Corporation" and "Chimassorb 81 manufactured by BASF Japan Ltd."

(Benzotriazole-based ultraviolet absorber)
Examples of the "benzotriazole-based" ultraviolet absorbers include 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and the like, as well as mixtures, modified products, polymers, and derivatives thereof.

(Triazine-based ultraviolet absorber)
As the triazine-based ultraviolet absorber, for example, a hydroxyphenyltriazine-based one is used. By using a hydroxyphenyltriazine-based ultraviolet absorber, the triazine skeleton suppresses bleeding, and the triazine skeleton is more chemically stable than the skeletons of benzotriazole-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers, making it possible to maintain ultraviolet absorption performance for a long period of time.

Examples of the triazine-based ultraviolet absorber used in the transparent polyvinyl chloride resin layer 6a include 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-dodecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-
hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and the like, as well as mixtures, modified products, polymers, and derivatives thereof.

(Cyanoacrylate UV absorber)
Examples of cyanoacrylate-based ultraviolet absorbers include ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, etc. Known products include cyanoacrylate-based ultraviolet absorbers "Uvinal (registered trademark) 3035 (product number)" (molecular weight 277), "Uvinal 3039" (molecular weight 361), and "Uvinal 3030FF" (molecular weight 1060) manufactured by BASF Japan Ltd.

The thickness of the transparent polyvinyl chloride resin layer 6a is preferably in the range of 50 μm to 150 μm, more preferably in the range of 50 μm to 100 μm, and even more preferably in the range of 60 μm to 80 μm. A thickness of 50 μm or more reliably improves the weather resistance of the decorative sheet 1 and can absorb unevenness in the adherend, such as window frames, resulting in a good application finish for the decorative sheet 1. Furthermore, if the thickness of the transparent polyvinyl chloride resin layer 6a is 150 μm or less, the transparent polyvinyl chloride resin layer 6a is not formed thicker than necessary, improving processability (e.g., wrapping processability) and reducing the manufacturing cost of the decorative sheet 1.

[Heat stabilizer]
The transparent polyvinyl chloride resin layer 6a preferably contains a metal salt of a higher fatty acid as a heat stabilizer.

(effect)
(1) The decorative sheet 1 according to the second embodiment of the present invention is composed of at least a design layer 4 and a transparent polyvinyl chloride resin layer 6a laminated in this order, and the resin constituting the transparent polyvinyl chloride resin layer 6a is a polyvinyl chloride resin that satisfies at least one of the following conditions: an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 to 1500, or a K value calculated in accordance with JIS K7367-2:1999 of 60 to 75, and further the transparent polyvinyl chloride resin layer 6 contains 20 to 30 PHR of a high-molecular-weight polyester plasticizer. Therefore, even when a transparent polyvinyl chloride resin sheet is formed into a film, film formation stability can be ensured, and good wrapping suitability of the decorative sheet 1 and good bending condition of the decorative sheet 1 during wrapping can be obtained.

(2) The viscosity of the plasticizer added to the transparent polyvinyl chloride resin layer 6a, as measured by a capillary viscometer in accordance with JIS K7367-5:2000, satisfies the range of 500 MPa·s to 3000 MPa·s, thereby ensuring good weather resistance.
(3) By including a light stabilizer and an ultraviolet absorber (UVA) in the transparent polyvinyl chloride resin layer 6a, the weather resistance of the decorative sheet can be improved.
In particular, the de-HCl reaction can be suppressed by using a NOR-type HALS as a light stabilizer added to the transparent polyvinyl chloride resin layer 6. Furthermore, the use of a NOR-type HALS with low basicity can suppress the de-HCl reaction even more than a highly basic one. In particular, the use of a NOR-type HALS with a base dissociation constant pkb of 5 to 12 is effective in suppressing _{the de-HCl} reaction caused by a base while ensuring weather resistance.
(4) The transparent polyvinyl chloride resin layer 6a has an ultraviolet transmittance of 0.05% T or less at a wavelength of 320 nm and 0.4% T or less at a wavelength of 360 nm. Therefore, even when formed using polyvinyl chloride resin, a decorative sheet with excellent weather resistance can be provided, and a decorative sheet 1 with excellent weather resistance that can withstand long periods of use, for example, outdoors, can be obtained. In other words, a decorative sheet 1 with excellent processability and weather resistance can be obtained.

(5) By forming the decorative member 100 from a base material 20 and a decorative sheet 1 bonded to this base material 20, a decorative member 100 with excellent processability can be provided even if the decorative sheet 1 is formed using polyvinyl chloride resin.
(6) Because the fitting is formed by laminating the decorative sheet 1 to the fitting component as the base material 20, it is possible to provide a fitting with excellent workability, even when the decorative sheet 1 is formed using polyvinyl chloride resin. In particular, by laminating the decorative sheet 1 to an exterior fitting component (base material 20) made of a vinyl chloride material, both the decorative sheet 1 and the fitting component are made into a mono-material made of a vinyl chloride material, which further enhances recyclability.
Example 2

The second embodiment of the present invention will be described in detail below using examples and comparative examples. Note that the present invention is not limited to the following examples.

(Example 2-1)
A colored polyvinyl chloride resin sheet was used as the colored polyvinyl chloride resin layer (colored substrate layer). A design layer was formed on one side of the colored polyvinyl chloride resin sheet by gravure printing using a printing ink for vinyl chloride. Then, a transparent polyvinyl chloride resin sheet serving as a transparent polyvinyl chloride resin layer (transparent resin layer) was thermally laminated onto the colored polyvinyl chloride resin sheet including the design layer. Then, a resin composition mainly composed of an acrylic resin composition was laminated onto the transparent polyvinyl chloride sheet as a surface protective layer.
The composition of each layer is as follows:

(Colored polyvinyl chloride resin sheet)
Material: Polyvinyl chloride resin (PVC)
Thickness: 80 μm

(Transparent polyvinyl chloride resin sheet)
Material: Polyvinyl chloride resin (PVC)
Degree of polymerization: 820
K value: 62.1
Thickness: 80 μm
Plasticizer: High molecular weight polyester
Additives: 20PHR
HALS: NOR type pkb=10
0.2% (ADEKA STAB LA81 manufactured by ADEKA Corporation)
Ultraviolet absorber: triazine-based 0.5 parts by mass

(Picture layer)
Binder resin: A mixture of vinyl chloride resin-vinyl acetate resin copolymer and acrylic resin

(Surface protective layer)
Base: methyl methacrylate/2-hydroxyethyl methacrylate (95/5 copolymer) 90 parts by weight Ultraviolet absorber: Tinuvin 479 (manufactured by BASF Japan Ltd.) 9 parts by weight Light stabilizer: Tinuvin 123 (manufactured by BASF Japan Ltd.) 1 part by weight Curing agent: Takenate D170 (manufactured by Mitsui Chemicals, Inc.) 10 parts by weight Solvent: ethyl acetate 240 parts by weight Coating amount: 3 g/ ^m2

(Example 2-2)
In the decorative sheet of Example 2-1, the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8, and the decorative sheet of Example 2-2 was obtained in the same manner as in Example 1.
(Example 2-3)
In the decorative sheet of Example 2-1, the amount of HALS added to the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 1%, except that the decorative sheet of Example 2-3 was obtained in the same manner as in Example 2-1.

(Example 2-4)
In the decorative sheet of Example 2-1, the amount of HALS added in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3%, the degree of polymerization of the transparent polyvinyl chloride resin sheet was 1440, and the K value was 73.6. The decorative sheet of Example 2-4 was obtained in the same manner as in Example 2-1.
(Example 2-5)
The decorative sheet of Example 2-5 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the amount of HALS added in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3% and the amount of plasticizer added was 28 PHR.

(Example 2-6)
In the decorative sheet of Example 2-1, the amount of HALS added in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3%, and the amount of ultraviolet absorber added was 0.8 parts by mass, except that the decorative sheet of Example 2-6 was obtained in the same manner as in Example 2-1.
(Example 2-7)
The decorative sheet of Example 2-7 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the amount of HALS added in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 0.3%, and the ultraviolet absorber was a cyanoacrylate-based ultraviolet absorber.

(Comparative Example 2-1)
In the decorative sheet of Example 2-1, a decorative sheet of Comparative Example 2-1 was obtained by the same procedure as in Example 2-1, except that in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer), an NH type HALS with a base dissociation constant pkb=4 was used as the HALS, and the amount of this HALS added was 0.3%.
(Comparative Example 2-2)
A decorative sheet of Comparative Example 2-2 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) did not contain HALS, and the degree of polymerization of the transparent polyvinyl chloride resin sheet was 1440 and the K value was 73.6.

(Comparative Example 2-3)
A decorative sheet of Comparative Example 2-3 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the degree of polymerization of the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) was 690 and the K value was 58.6.
(Comparative Example 2-4)
A decorative sheet of Comparative Example 2-4 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the degree of polymerization of the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was 1740 and the K value was 77.4.
(Comparative Example 2-5)
The decorative sheet of Comparative Example 2-5 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8, the amount of HALS added was 0.3%, the amount of plasticizer added was 35 PHR, and the ultraviolet absorber was a cyanoacrylate-based ultraviolet absorber.
(Comparative Example 2-6)
A decorative sheet of Comparative Example 2-6 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8, the amount of HALS added was 0.3%, and the amount of ultraviolet absorber added was 0.1 parts by mass.
(Comparative Example 2-7)
The decorative sheet of Comparative Example 2-7 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=8, the amount of HALS added was 0.3%, and no ultraviolet absorber was added.
(Comparative Example 2-8)
The decorative sheet of Comparative Example 2-8 was obtained in the same manner as in Example 2-1, except that in the decorative sheet of Example 2-1, the base dissociation constant of the HALS contained in the transparent polyvinyl chloride resin sheet serving as the transparent polyvinyl chloride resin layer (transparent resin layer) was pkb=9, the amount of HALS added was 0.3%, the amount of plasticizer added was 15 PHR, and the ultraviolet absorber was a cyanoacrylate-based ultraviolet absorber.

〔evaluation〕
The decorative sheets of the Examples and Comparative Examples were measured for UV transmittance (320 nm) and UV transmittance (360 nm). Each decorative sheet was also evaluated for weather resistance, film-forming stability of the transparent polyvinyl chloride resin sheet, and wrapping processability. The evaluation criteria were as follows:

(weather resistance)
A 504-hour accelerated weather resistance test was carried out under the following test conditions using a metal weather tester (KU-R5DCI-A, manufactured by Daipla Wintes Co., Ltd.).
Test conditions: BPT (black panel temperature): 63°C, illuminance: 65mW/ ^cm2 , 21 cycles (504 hours) of "20 hours of UV irradiation + 4 hours of condensation" were performed. The color difference ΔE before and after the accelerated weathering test was evaluated. The evaluation criteria were as follows:
◎(Pass): ΔE<2.0
◯ (pass): ΔE=2.0 or more and less than 4.0 × (fail): ΔE≧4.0
(Film formation stability of transparent polyvinyl chloride resin sheet)
The film-forming stability during film-forming of a polyvinyl chloride resin sheet was evaluated.
◯ (pass): No fish eyes or the like occurred, the calendering suitability was good, and sheets could be stably produced.
× (fail): Fish eyes or the like are observed, or the calendering suitability is poor, and a sheet cannot be stably produced.

(suitability for wrapping processing)
The ease of handling when wrapping the decorative sheet was evaluated.
◎ (Pass): Possible under a wide range of production conditions 〇 (Pass): Possible under limited production conditions × (Fail): Difficult to produce (weak and difficult to handle, or prone to breaking or cracking, or whitening or cracking occurs at the bent part)

The above measurement results and the evaluation results for each evaluation item are shown in Tables 2 and 3.

As shown in Tables 2 and 3, the decorative sheets of Examples 2-1 to 2-7, in which the resin constituting the transparent polyvinyl chloride resin sheet (transparent polyvinyl chloride resin layer 6) satisfies at least one of the following criteria: polyvinyl chloride resin with an average degree of polymerization of 800 to 1500 as calculated in accordance with JIS K6720-2, or polyvinyl chloride resin with a K value of 60 to 75 as calculated in accordance with JIS K7367-2:1999; contain 20 to 30 PHR of a high-molecular-weight polyester plasticizer; and have an ultraviolet transmittance of 0.05%T or less at a wavelength of 320 nm and an ultraviolet transmittance of 0.4%T or less at a wavelength of 360 nm, were all rated as "◎" (pass) for weather resistance, confirming that even when formed using polyvinyl chloride resin (PVC), they have excellent weather resistance and can withstand long-term use in exterior and semi-exterior applications.

The decorative sheets of Examples 2-1 to 2-7 were also confirmed to have good film-forming stability for the transparent polyvinyl chloride resin sheet and good wrapping processability for the decorative sheets. It was also confirmed that when a cyanoacrylate-based UV absorber was used as the UV absorber (Example 2-7), good properties could be obtained, similar to when a triazine-based UV absorber was used. Furthermore, of the decorative sheets of Examples 2-1 to 2-7, the decorative sheet of Example 2-5, which contains a higher amount of plasticizer than the other decorative sheets, was confirmed to have acceptable wrapping processability, although it was somewhat difficult to handle.

On the other hand, the decorative sheet of Comparative Example 2-1 in Example 2-1, in which 0.3% of NH-type HALS was added, and the decorative sheet of Comparative Example 2-2 in Example 2-4, in which no HALS was added, had good film-forming stability of the transparent polyvinyl chloride resin sheet and good wrapping processability of the decorative sheet, but were unable to obtain sufficient weather resistance. Furthermore, the decorative sheets of Comparative Examples 2-3 and 2-4, in which the average degree of polymerization was outside the range of 800 to 1500 and the K value was outside the range of 60 to 75, were able to obtain good weather resistance, but the film-forming stability of the transparent polyvinyl chloride resin sheet was unacceptable, and the decorative sheet of Comparative Example 2-4, in which the average degree of polymerization exceeded 1500 and the K value exceeded 75, also failed to obtain satisfactory wrapping processability of the decorative sheet.
Furthermore, the decorative sheet of Comparative Example 2-5, in which the amount of plasticizer added was more than 30 PHR, and the decorative sheet of Comparative Example 2-8, in which the amount of plasticizer added was less than 20 PHR, failed in terms of wrapping processability. Furthermore, the decorative sheet of Comparative Example 2-6, in which the UV transmittance at a wavelength of 320 nm was more than 0.05%T and the UV transmittance at a wavelength of 360 nm was more than 0.4%T, and the decorative sheet of Comparative Example 2-7, which did not contain an UV absorber, were unable to achieve sufficient weather resistance.

The present invention can have the following configurations, for example.
(1)
A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order,
the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less,
The decorative sheet is characterized in that the transparent resin layer contains a high molecular weight polyester plasticizer in an amount of 20 PHR or more and 30 PHR or less.
(2)
A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order,
the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less;
The decorative sheet is characterized in that the transparent resin layer contains a high molecular weight polyester plasticizer in an amount of 20 PHR or more and 30 PHR or less.
(3)
The decorative sheet according to (1) or (2) above, characterized in that the elongation at break at 0°C is 10% or more and 400% or less.
(4)
The decorative sheet according to any one of (1) to (3) above, wherein the plasticizer has a viscosity of 500 MPa·s or more and 3000 MPa·s or less, as measured with a capillary viscometer in accordance with JIS K7367-5:2000.
(5)
The decorative sheet according to any one of (1) to (4) above, wherein the transparent resin layer contains a NOR-type hindered amine light stabilizer (HALS).
(6)
The decorative sheet according to (5) above, wherein the hindered amine light stabilizer has a base dissociation constant pkb of 5 or more and 12 or less.
(7)
The decorative sheet according to any one of (1) to (6) above, characterized in that the transparent resin layer contains at least one of a benzophenone-based ultraviolet absorber, a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber.
(8)
The decorative sheet according to any one of (1) to (7) above, wherein the transparent resin layer contains a metal salt of a higher fatty acid as a heat stabilizer.
(9)
The decorative sheet according to any one of (1) to (8) above, further comprising a surface protection layer on the outermost surface on the transparent resin layer side.
(10)
A decorative sheet according to any one of (1) to (9) above, characterized in that a colored substrate layer is provided on the side of the design layer opposite the transparent resin layer.
(11)
The decorative sheet according to any one of (1) to (10) above,
A decorative member comprising: a substrate disposed on the outermost surface of the decorative sheet on the side of the pattern layer.
(12)
The decorative sheet according to any one of (1) to (10) above,
A fitting comprising a fitting component arranged on the outermost surface of the decorative sheet on the side of the pattern layer.
(13)
The fixture described in (12) above is characterized in that the fixture component is an exterior fixture component made of a vinyl chloride material.

DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Colored polyvinyl chloride resin layer 4 Design layer 6, 6a Transparent polyvinyl chloride resin layer 8 Surface protective layer 10 Embossed portion 20 Base material 100 Decorative member

Claims (14)

A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order,
the resin constituting the transparent resin layer is a polyvinyl chloride resin having an average degree of polymerization calculated in accordance with JIS K6720-2 of 800 or more and 1500 or less,
the transparent resin layer contains a high-molecular-weight polyester plasticizer in an amount of 20 PHR or more and 30 PHR or less;
the transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber;
The decorative sheet is characterized in that the transparent resin layer contains a NOR-type hindered amine light stabilizer (HALS) . A decorative sheet comprising at least a pattern layer and a transparent resin layer laminated in this order,
the resin constituting the transparent resin layer is a polyvinyl chloride resin having a K value calculated in accordance with JIS K7367-2:1999 of 60 or more and 75 or less;
the transparent resin layer contains a high-molecular-weight polyester plasticizer in an amount of 20 PHR or more and 30 PHR or less;
the transparent resin layer contains at least one of a benzotriazole-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a cyanoacrylate-based ultraviolet absorber;
The decorative sheet is characterized in that the transparent resin layer contains a NOR-type hindered amine light stabilizer (HALS) . The decorative sheet according to claim 1 or 2, characterized in that the breaking elongation at 0°C is 10% or more and 400% or less. The decorative sheet according to claim 1 or 2, characterized in that the viscosity of the plasticizer, measured using a capillary viscometer in accordance with JIS K7367-5:2000, is 500 MPa·s or more and 3000 MPa·s or less. 3. The decorative sheet according to claim 1, wherein the hindered amine light stabilizer has a base dissociation constant pkb of 5 or more and 12 or less. The decorative sheet according to claim 1 or 2, characterized in that the transparent resin layer contains at least one of a triazine-based ultraviolet absorber and a cyanoacrylate-based ultraviolet absorber. The decorative sheet according to claim 1 or 2, characterized in that the transparent resin layer contains a metal salt of a higher fatty acid as a heat stabilizer. The decorative sheet according to claim 1 or 2, characterized in that it comprises a surface protection layer on the outermost surface on the side of the transparent resin layer. The decorative sheet according to claim 1 or 2, characterized in that a colored substrate layer is provided on the side of the design layer opposite the transparent resin layer. The decorative sheet according to claim 1 or 2, characterized in that the design layer contains a mixture of vinyl chloride resin-vinyl acetate resin copolymer resin and acrylic resin as a binder resin. The decorative sheet according to claim 1 or 2, characterized in that the transparent resin layer does not contain a barium-zinc-based heat stabilizer or a magnesium-zinc-based heat stabilizer. The decorative sheet according to claim 1 or 2;
A decorative member comprising: a substrate disposed on the outermost surface of the decorative sheet on the side of the pattern layer. The decorative sheet according to claim 1 or claim 2;
A fitting comprising a fitting component arranged on the outermost surface of the decorative sheet on the side of the pattern layer. The fixture according to claim 13 , characterized in that the fixture component is an exterior fixture component made of a vinyl chloride material.