Manufacturing method of decorative sheets

Abstract

The present invention provides a method for manufacturing decorative sheets that can suppress the occurrence of wrinkles during the printing process, even when the sheets are formed using polyvinyl chloride resin. [Solution] The method for manufacturing the decorative sheet 1 is a method for manufacturing a decorative sheet 1 in which at least a colored base layer 2, a pattern layer 3, a transparent resin layer 4, and a surface protection layer 5 are laminated in this order, wherein the colored base layer 2 is formed of colored polyvinyl chloride resin, the transparent resin layer 4 is formed of transparent polyvinyl chloride resin, the pattern layer 3 is printed on one side of the transparent resin layer 4, the surface protection layer 5 is formed on the other side of the transparent resin layer 4, and the residual solvent concentration per unit area in the transparent resin layer 4 on which the pattern layer 3 is printed is 3 mg / m² 2 The following applies:

Description

[Technical Field]

[0001] This disclosure relates to a method for manufacturing decorative sheets. [Background technology]

[0002] Conventionally, decorative sheets made of polyvinyl chloride resin have been known for use in decorating interior materials for houses (for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 5-278173 [Overview of the project] [Problems that the invention aims to solve]

[0004] As concern for environmental issues grew, the use of decorative sheets made from polyvinyl chloride resin was temporarily restricted, and the use of decorative sheets made from olefin resin as an alternative to polyvinyl chloride resin increased.

[0005] However, in recent years, improvements in incineration facilities and exhaust gas treatment technologies have suppressed the generation of harmful substances, and the role of polyvinyl chloride resin is being re-evaluated. Furthermore, more than half of the raw materials for polyvinyl chloride resin are made from salt, and the ethylene polymerization ratio derived from petrochemicals is lower compared to olefin resins, so it is also called a resource-saving resin. In addition, polyvinyl chloride resin has the advantage of being easy to process and recycle. For this reason, demand for decorative sheets made from polyvinyl chloride resin is increasing, also from the perspective of reducing environmental impact.

[0006] Furthermore, due to the growing awareness of zero-energy homes (ZEH), polyvinyl chloride (total sheet thickness) There is a growing demand for highly insulated resin sashes and window frames made from resin, and it is conceivable to decorate these base materials with decorative sheets, but there are problems such as the difficulty of recycling olefin-based resin sheets. Therefore, as mentioned above, using polyvinyl chloride resin for resin sashes and window frame base materials, along with decorative sheets made of polyvinyl chloride resin, is expected to make a significant contribution to reducing environmental impact.

[0007] Furthermore, there is a high demand for solid-color polyvinyl chloride sheets, particularly dark black ones, used as exterior materials. However, the darker the color, the higher the concentration and the larger the amount of ink used during printing. Also, when printing with high ink concentration, solid color printing is often performed. Consequently, wrinkles are more likely to occur on the sheet surface during the ink printing process. While extending the drying time after printing can suppress wrinkles, this increases manufacturing costs. For these reasons, there is a need to suppress the occurrence of wrinkles during the printing process on decorative sheets made of polyvinyl chloride resin.

[0008] In view of the problems described above, this disclosure aims to provide a method for manufacturing decorative sheets that can suppress the occurrence of wrinkles during the printing process, even when using polyvinyl chloride resin. [Means for solving the problem]

[0009] To solve the above problems, a method for manufacturing a decorative sheet according to one aspect of the present disclosure is a method for manufacturing a decorative sheet in which at least a colored base layer, a pattern layer, a transparent resin layer, and a surface protection layer are laminated in this order, wherein the colored base layer is formed of colored polyvinyl chloride resin, the transparent resin layer is formed of transparent polyvinyl chloride resin, the pattern layer is printed on one side of the transparent resin layer, the surface protection layer is formed on the other side of the transparent resin layer, and the residual solvent concentration per unit area in the transparent resin layer on which the pattern layer is printed is 3 mg / m². 2 The following applies: [Effects of the Invention]

[0010] According to one aspect of this disclosure, even when polyvinyl chloride resin is used, the occurrence of wrinkles due to the printing process can be suppressed. [Brief explanation of the drawing]

[0011] [Figure 1] This is a cross-sectional view showing a decorative material according to one embodiment of the present disclosure. [Modes for carrying out the invention]

[0012] The decorative sheets and decorative members according to the embodiments of this disclosure will be described below with reference to the drawings. Herein, the drawings are schematic, and the relationship between thickness and planar dimensions, the ratio of the thickness of each layer, etc., may differ from reality. Within the scope of this disclosure, it is not necessary for the layers to be laminated in the order shown in the drawings. Furthermore, additional layers not shown in these drawings may be added. In addition, the embodiments described below are illustrative of configurations for realizing the technical idea of ​​this disclosure, and the technical idea of ​​this disclosure is not limited to the materials, shapes, and structures of the components described below. The technical idea of ​​this disclosure can be modified in various ways within the technical scope defined by the claims described in the patent claims. Furthermore, the terms "left / right" and "up / down" in the following explanation are merely definitions for the sake of explanation and do not limit the technical concept of this disclosure. Therefore, for example, if the page is rotated 90 degrees, "left / right" and "up / down" will be swapped when read, and if the page is rotated 180 degrees, "left" will become "right" and "right" will become "left".

[0013] The composition of the decorative material 10 will be described below with reference to Figure 1. As shown in Figure 1, the decorative material 10 comprises a decorative sheet 1 and a base material 8 which is a base material for the decorative material and is the base material to which the decorative sheet 1 is attached. In this example, on one surface of the base material 8 (the upper surface in FIG. 1), the decorative sheet 1 is laminated. That is, the decorative material 10 includes the base material 8 and the decorative sheet 1 laminated on one surface of the base material 8. Specific configurations of the decorative sheet 1 and the base material 8 will be described later.

[0014] (Configuration of the decorative sheet) As shown in FIG. 1, the decorative sheet 1 includes a coloring original layer 2, a pattern layer 3, a transparent resin layer 4, a surface protection layer 5, and an embossed portion 7. Specifically, in the decorative sheet 1, the pattern layer 3, the transparent resin layer 4, and the surface protection layer 5 are laminated in this order on the coloring original layer 2 (one surface side of the coloring original layer 2). That is, the decorative sheet 1 has at least the coloring original layer 2, the pattern layer 3, the transparent resin layer 4, and the surface protection layer 5 laminated in this order. Also, an embossed portion 7 is formed on the surface of the surface protection layer 5 that is the outermost layer of the decorative sheet 1 (the surface opposite to the transparent resin layer 4).

[0015] (Coloring original layer) The coloring original layer 2 is configured to be a support of the decorative sheet 1. The coloring original layer 2 in the present embodiment is opaque and colored and has concealability. Thereby, when forming a decorative member by bonding, for example, the decorative sheet 1 and a predetermined substrate, the coloring original layer 2 can conceal color variations and defects on the substrate surface. <00L0099>

[0016] Also, as the material of the coloring original layer 2, a polyvinyl chloride (PVC) resin film having flexibility, being thermoplastic with good moldability and processing suitability, and further having printing suitability is used. That is, in the decorative sheet 1 according to the present embodiment, the coloring original layer 2 is a colored polyvinyl chloride resin layer formed of a colored polyvinyl chloride resin. By forming the original layer with PVC, the end material of the decorative sheet 1 during the production of the decorative material 10 and the used decorative sheet 1 can be melted and extruded by an extruder or the like and reused as a recycled base material. Also, PVC is easier to reuse by melting than olefin-based resins. In other words, the decorative sheet 1 according to this embodiment can improve processing suitability and recyclability by forming the colored raw material layer 2 with PVC.

[0017] Furthermore, the colored base layer 2, which is an opaque colored polyvinyl chloride colored sheet (colored film), can have its hue appropriately selected as the base color for the pattern layer 3. In addition, when it is necessary to make use of the surface texture of the base material 8, which is a base material for decorative materials, it is preferable that the colored base layer 2 is a colored polyvinyl chloride resin layer that has sufficient transparency to allow the surface of the base material 8 to be seen through.

[0018] For example, the colored base layer 2 can be colored by mixing or kneading a coloring agent such as a pigment into the resin material (polyvinyl chloride) that constitutes the colored base layer 2. Organic and inorganic pigments can be used as coloring agents, but inorganic pigments are preferred. In other words, it is preferable that the colored base layer 2 contains inorganic substances as coloring agents. For example, it is preferable that the colored base layer 2 contains one or more inorganic substances from among calcium carbonate, titanium dioxide, carbon black, silica, chromium, antimony, titanium composites, and other oxides.

[0019] Furthermore, the colored base layer 2 may contain, as needed, one or more additives selected from various additives such as colorants, fillers, UV absorbers, light stabilizers, heat stabilizers, antioxidants, antistatic agents, lubricants, flame retardants, antibacterial agents, antifungal agents, friction reducers, light scattering agents, and gloss adjusters. In particular, considering the durability and weather resistance when the decorative sheet 1 is used outdoors as an exterior material, it is preferable that the colored base layer 2 contains UV absorbers and light stabilizers. It is even more preferable that, in addition to UV absorbers and light stabilizers, it also contains plasticizers and heat stabilizers. Details of plasticizers will be described later. The UV absorber contained in the colored base layer 2 can be the same as that contained in the transparent resin layer 4. Furthermore, the light stabilizer contained in the colored base layer 2 can be the same as that contained in the surface protective layer 5.

[0020] (Picture layer) The pattern layer 3 is laminated on one side of the transparent resin layer 4 (the side facing the colored raw material layer 2 (the lower side) in Figure 1) and is a layer for adding a pattern to enhance the design. More specifically, the pattern layer 3 is located between the colored raw material layer 2 and the transparent resin layer 4. For example, the pattern layer 3 is formed by printing printing ink onto the transparent resin layer 4. Alternatively, the pattern layer 3 may be formed by printing printing ink onto the colored base layer 2.

[0021] Printing ink is a mixture of a solvent and solid components such as a colorant and binder resin. Examples of solvents include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ester-based organic solvents such as ethyl acetate, butyl acetate, 2-methoxyethyl acetate, and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, and propylene glycol; ketone-based organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine-based organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganic solvents such as water. A single solvent may be used alone, or two or more may be used in combination.

[0022] Examples of binder resins include chlorine-based resins, urethane resins, acrylic urethane resins, acrylic resins, polyester resins, polyamide resins, butyral resins, polystyrene resins, nitrocellulose resins (nitrated cotton), and cellulose acetate resins. Examples of chlorine-based resins include polyvinyl chloride resins such as polyvinyl chloride, chlorinated polyethylene, polyvinylidene chloride, ethylene-vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, and vinyl chloride-vinyl acetate-(meth)acrylic copolymers, as well as polypropylene chloride and chlorinated polypropylene. Here, (meth)acrylic means acrylic or methacrylic. The binder resin may be a single type or a combination of two or more types.

[0023] The printing ink that forms the pattern layer 3 is formed by dissolving or dispersing a coloring agent, 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, imidazolon, cobalt, phthalocyanine, carbon, titanium dioxide, iron oxide, mica, and other pearl pigments. The decorative sheet 1 may be a single-color sheet, for example, a dark black sheet. That is, the pattern layer 3 may be printed using black printing ink (black ink), or it may be printed using printing ink (dark color ink) that expresses a dark color close to black. The pattern layer 3 may be formed by solid printing of black ink (or dark color ink) onto the transparent resin layer 4. The black ink (or dark color ink) may contain a black coloring agent (for example, black pigment). The black pigment is not particularly limited, but may be, for example, azomethine azo pigment, perylene pigment, titanium black pigment, black iron oxide pigment, black composite oxide pigment, carbon black, etc. Furthermore, the black ink (or dark color ink) is not limited to black pigment, and may express black (or dark color) by a composition containing multiple coloring agents.

[0024] The solvents (e.g., organic solvents) contained in the printing ink ultimately volatilize due to heating during the sheet manufacturing process (e.g., heating after printing, such as thermal lamination). Therefore, in the decorative sheet 1, the pattern layer 3 is mainly formed from solid components such as colorants and binder resin. However, depending on the concentration of the solvent remaining in the transparent resin layer 4 after printing the pattern layer 3 (residual solvent), wrinkles may occur in the transparent resin layer 4. For this reason, in this disclosure, the upper limit of the concentration of the residual solvent after printing the pattern layer 3 is set to a predetermined value or less to suppress the occurrence of wrinkles caused by the printing process (printing of the pattern layer 3). The residual solvent will be described later.

[0025] The printing ink that forms the pattern layer 3 is applied using various printing methods, such as gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, inkjet printing, and transfer printing from a transfer sheet. A roll-to-roll printing apparatus may also be used. When printing the pattern layer 3 as a solid color, it is preferable to use gravure printing with a solid color plate. Any pattern can be used as the design, such as wood grain, stone pattern, fabric pattern, abstract pattern, geometric pattern, letters, symbols, solid color, or combinations thereof. In addition, to improve the opacity of the decorative sheet 1, an opacity layer may be provided between the pattern layer 3 and the colored base layer 2. The opacity layer is formed using, for example, an opaque printing ink or paint containing a large amount of opaque pigments such as titanium dioxide or iron oxide.

[0026] The thickness of the pattern layer 3 is preferably within the range of 1 μm to 10 μm. This is because when the thickness of the pattern layer 3 is 1 μm or more, it is possible to make the printing clearer. Also, when the thickness of the pattern layer 3 is 10 μm or less, the printability when manufacturing the decorative sheet 1 is improved and manufacturing costs can be reduced. Furthermore, the pattern layer 3 may contain functional additives such as stabilizers, catalysts, extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, drying agents, curing agents, curing accelerators, and curing retarders to impart various functions. These functional additives may be included in printing inks or paints. Furthermore, the pattern layer 3 may have a configuration that includes, for example, a solid-color base layer to conceal the color and pattern of the base to which the decorative sheet 1 is attached, and a pattern layer to add a design for aesthetic purposes.

[0027] (Transparent resin layer) The transparent resin layer 4 is a layer for improving the weather resistance of the decorative sheet 1. In the decorative sheet 1 according to this embodiment, the material for the transparent resin layer 4 is a polyvinyl chloride (PVC) resin film that is flexible, thermoplastic, has good moldability and processability, and is printable. In other words, in the decorative sheet 1 according to this embodiment, the transparent resin layer 4 is a transparent polyvinyl chloride resin layer formed from transparent polyvinyl chloride resin (transparent polyvinyl chloride resin). As described above, PVC can be used as a recycled base material by melting and extruding, and it is easier to reuse by melting compared to olefin resins. In other words, the decorative sheet 1 according to this embodiment can reliably improve processing suitability and recyclability by forming the colored raw material layer 2 and the transparent resin layer 4 with PVC. Furthermore, the transparent resin layer 4 is preferably transparent enough to allow the pattern layer 3, which is provided on the side facing the colored raw material layer 2 (the lower side in Figure 1), to be seen through. For example, it may be colorless, colored, or semi-transparent.

[0028] Furthermore, the transparent resin layer 4 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, friction reducers, light scattering agents, and gloss adjusters. In particular, considering the durability and weather resistance when the decorative sheet 1 is used outdoors as an exterior material, it is preferable that the transparent resin layer 4 contains an ultraviolet absorber and a light stabilizer. It is even more preferable that it contains a plasticizer and a heat stabilizer in addition to the ultraviolet absorber and light stabilizer. The ultraviolet absorber contained in the transparent resin layer 4 will be described in detail below. Note that the light stabilizer contained in the transparent resin layer 4 can be the same as that of the surface protection layer 5.

[0029] [UV absorber] Furthermore, in this embodiment, the transparent resin layer 4 contains an ultraviolet absorber. In other words, in the decorative sheet 1 according to this embodiment, the transparent resin layer 4 is formed of transparent polyvinyl chloride resin and contains an ultraviolet absorber. This provides the transparent resin layer 4 with excellent weather resistance. More specifically, it is preferable that the transparent resin layer 4 contains at least one of the following ultraviolet absorbers: a benzotriazole-based ultraviolet absorber or a triazine-based ultraviolet absorber. This provides excellent weather resistance to the transparent vinyl chloride resin forming the transparent resin layer 4, thereby improving the weather resistance of the decorative sheet 1. The amount of UV absorber added to the transparent resin layer 4 should be adjusted according to the desired weather resistance, but it is preferable to add at least 0.5 parts by mass per 100 parts by mass of the transparent vinyl chloride resin constituting the transparent resin layer 4. This ensures that the weather resistance of the decorative sheet 1 is reliably improved.

[0030] (Benzotriazole-based UV absorbers) Examples of "benzotriazole-based" UV 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 mixtures, modified products, polymers, and derivatives thereof.

[0031] (Triazine-based UV absorber) Examples of "triazine-based" UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-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.

[0032] The thickness of the transparent resin layer 4 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. When the thickness is 50 μm or more, the weather resistance of the decorative sheet 1 is reliably improved, and the unevenness of the substrate to which it is adhered (in this example, the substrate 8) can be absorbed, resulting in a good finish when the decorative sheet 1 is applied. Furthermore, when the thickness of the transparent resin layer 4 is 150 μm or less, the transparent resin layer 4 does not need to be formed to be unnecessarily thick, improving the workability (e.g., bendability) and reducing the manufacturing cost of the decorative sheet 1.

[0033] (Surface protective layer) The surface protection layer 5 of the decorative sheet 1 according to this embodiment is a layer provided to the decorative sheet 1 to impart functions such as weather resistance, scratch resistance, stain resistance, and design properties. The material constituting the surface protection layer 5 is not particularly limited, and can be appropriately selected and used from resin materials such as urethane-based, acrylic-based, acrylic-silicone-based, fluorine-based, and epoxy-based materials. The surface protective layer 5 may contain various additives as needed, such as ultraviolet absorbers, heat stabilizers, light stabilizers, anti-blocking agents, catalyst scavengers, colorants, light scattering agents, and gloss modifiers. An example of the surface protective layer 5 according to this embodiment will be described below with specific examples.

[0034] In this embodiment, the surface protective layer 5 may mainly consist of an acrylic resin composition containing cyclohexyl (meth)acrylate as a monomer component. In this embodiment, cyclohexyl (meth)acrylate means cyclohexyl acrylate or cyclohexyl methacrylate. By including cyclohexyl (meth)acrylate as a monomer component, the affinity for water can be reduced, and degradation due to hydrolysis and other factors can be suppressed.

[0035] Regarding the cyclohexyl (meth)acrylate content, it is desirable that the cyclohexyl (meth)acrylate content be within the range of 5% by mass or more and 50% by mass or less among the monomer components of all acrylic resin compositions, that is, among the monomer components of the acrylic resin composition that is the main component of the surface protection layer 5. By setting the cyclohexyl (meth)acrylate content to 5% by mass or more, a sufficient degradation suppression effect can be obtained. Furthermore, by setting the cyclohexyl (meth)acrylate content to 50% by mass or less, it becomes possible to impart high weather resistance over time without significantly changing the various properties of the surface protection layer 5 of the decorative sheet, such as improved surface hardness maintenance, improved stain resistance, and adjustment of surface gloss. Here, the "main component" mentioned above means that the content of the acrylic resin composition constituting the surface protection layer 5 is 50% by mass or more of the total mass of the surface protection layer 5.

[0036] In addition to cyclohexyl (meth)acrylate, examples of monomer components of the acrylic resin composition that can be used in the surface protective layer 5 according to 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, and methoxycyclohexylmethyl (meth)acrylate. Among these, those containing isomers may be each isomer individually and / or a mixture of each isomer.

[0037] Furthermore, in this embodiment, the surface protection layer 5 may be formed by coating the outermost surface of the decorative sheet with a coating liquid containing an acrylic resin composition containing the above-mentioned cyclohexyl (meth)acrylate as a monomer component and a weather-resistant agent such as an ultraviolet absorber, which will be described later. As will be described in detail later, for example, the coating liquid containing the above-mentioned acrylic resin composition and weather-resistant agent may be coated onto the transparent resin layer 4 on which the embossed portion 7 is formed, and then wiped to embed the coating liquid into the embossed portion 7 and form the surface protection layer 5. As for the curing method of the coating liquid for forming the surface protective layer 5, any of the following can be used: a one-component curing type, a two-component curing type using a curing agent, or an active energy ray curing type cured by irradiation with ultraviolet light or ionizing radiation. However, considering weather resistance, the two-component curing type or the active energy ray curing type is preferable, and if post-processing after bonding to various substrates to become decorative components is considered, the two-component curing type that is crosslinked by isocyanate curing is desirable.

[0038] As a two-component curing type acrylic resin composition, a composition containing, for example, an acrylic resin having two or more functional groups selected from hydroxyl groups, amino groups, and carboxyl groups in one molecule, and a polyisocyanate compound having two or more isocyanate groups that can react with the functional groups in one molecule is preferred. Particularly preferred is a composition containing an acrylic polyol having two or more hydroxyl groups in one molecule and a polyisocyanate compound.

[0039] As acrylic polyols having two or more hydroxyl groups in one molecule, in addition to the cyclohexyl (meth)acrylate mentioned above, for example, (meth)acrylic acid ester copolymers containing hydroxyethyl (meth)acrylate as a monomer component can be used. On the other hand, as polyisocyanate compounds having two or more isocyanate groups in one molecule, for example, tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) and their hydrogenated compounds, isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), and trimer types, TMP adduct types, and burette types synthesized by known techniques from one or more compounds selected from these. Furthermore, compositions by mixing one or more of these different types of polyisocyanates can be used. Among these, HDI, or the trimer type, TMP adduct type, and burette type of HDI are preferred from the viewpoint of weather resistance. The content of the isocyanate compound relative to the resin component described above can be set arbitrarily, but it is desirable to set it so that the hydroxyl group / isocyanate group equivalent ratio is about 1 / 1 to 1 / 3. In particular, if the equivalent amount of hydroxyl groups is greater than the equivalent amount of isocyanate groups, crosslinking may not proceed sufficiently, and the desired performance may not be added to the surface protective layer 5, which is undesirable.

[0040] In this embodiment, the surface protective layer 5 is preferably formed of a hydrophobic acrylic polyol. The hydrophobic acrylic polyol may be a hydrophobic acrylic polyol (hydrophobic group-modified acrylic polyol) as an acrylic polyol having hydroxyl groups. This improves the moisture and heat resistance of the decorative sheet 1 and imparts excellent moisture and heat resistance to the surface protective layer 5, thereby improving the moisture and heat resistance of the decorative sheet 1.

[0041] When the curing method for the coating solution used to form the surface protective layer 5 is active energy ray curing, known monomers, oligomers, etc. having (meth)acryloyl groups can be used as the active energy ray curing type acrylic resin composition, and in addition to these monomers and oligomers, the above-mentioned cyclohexyl (meth)acrylate may be added.

[0042] In order to further improve the weather resistance of the decorative sheet 1, in this embodiment, it is preferable that the surface protective layer 5 contains an ultraviolet absorber and a light stabilizer as weathering agents. In other words, it is preferable that the surface protective layer 5 is formed of the above-mentioned hydrophobic group-introduced acrylic polyol and contains an ultraviolet absorber and a light stabilizer.

[0043] <UV absorber> As UV absorbers, known types such as benzotriazole-based, triazine-based (e.g., hydroxyphenyltriazine-based), and benzophenone-based UV absorbers can be used. Among these, selecting a hydroxyphenyltriazine-based UV absorber allows for long-term UV absorption performance because the triazine skeleton suppresses bleeding, and the triazine skeleton is chemically more stable than the skeletons of benzotriazole-based and benzophenone-based UV absorbers. In other words, it is preferable that the surface protective layer 5 contains a triazine-based UV absorber as the UV absorber.

[0044] Examples of hydroxyphenyltriazine-based UV absorbers include 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol, 2-[4-[(2-hydroxy-3-tridecyloxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-ethyl-hexanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazine-2-yl) Examples include -3-hydroxyphenoxy]-ethyl ester, octanoic acid, 2-[4-(4,6-diphenyl-[1,3,5]triazine-2-yl)-3-hydroxyphenoxy]-ethyl ester, 2,4,6-tris{2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)}-1,3,5-triazine, 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-isooctyloxyphenyl)-s-triazine, and 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-bis-butyloxyphenyl)-1,3,5-triazine. In this embodiment, the surface protective layer 5 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). Note that 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine, which is used as ultraviolet absorber A, is generally known as the main component of "Tinuvin 479: manufactured by BASF Japan Ltd."

[0045] In the surface protection layer 5 of this embodiment, the amount of the above-mentioned triazine-based (hydroxyphenyltriazine-based) ultraviolet absorber added is preferably within the range of 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of the resin composition (e.g., acrylic resin composition) forming the surface protection layer 5. By adding 1 part by mass or more of the above-mentioned ultraviolet absorber, a weather resistance improvement effect is achieved, and by adding 30 parts by mass or less, the influence on physical properties other than weather resistance of the surface protection layer 5 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 5, the amount added is preferably in the range of 1 part by mass or more and 20 parts by mass or less per 100 parts by mass of the acrylic resin composition, more preferably in the range of 5 parts by mass or more and 15 parts by mass or less, and even more preferably in the range of 8 parts by mass or more and 12 parts by mass or less. By adding 1 part by mass or more of ultraviolet absorber A, a weather resistance improvement effect is achieved, and by adding 20 parts by mass or less, the influence on physical properties other than weather resistance of the surface protective layer 5 can be suppressed to a level that does not pose a practical problem.

[0046] Furthermore, in this embodiment, by using both UV absorber A and 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol (hereinafter referred to as "UV absorber B" for convenience) as triazine-based (hydroxyphenyltriazine-based) UV absorbers in the surface protective layer 5, even better weather resistance is provided. This is because UV absorber B has a high UV absorption capacity in the short-wavelength region, which is relatively high energy among UV rays, and is chemically stable compared to other UV absorbers that absorb in almost the same wavelength region, so the wavelength region over which UV rays are absorbed is broadened when used in combination. Note that 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, which is used as UV absorber B, is generally known as the main component of "ADEKA Stab LA-46: manufactured by ADEKA Corporation".

[0047] In this embodiment, the amount of ultraviolet absorber A added to the surface protective layer 5 is preferably within the range of 10 parts by mass to 200 parts by mass, more preferably within the range of 20 parts by mass to 100 parts by mass, and even more preferably within the range of 40 parts by mass to 80 parts by mass, relative to 100 parts by mass of ultraviolet absorber B. By setting the amount of ultraviolet absorber A within the above numerical range, even better weather resistance can be provided.

[0048] <Light stabilizer> In this embodiment, the surface protective layer 5 contains a light stabilizer in addition to an ultraviolet absorber as a weather-resistant agent. This improves the weather resistance of the decorative sheet 1.

[0049] As a light stabilizer added to the surface protective layer 5, for example, a radical scavenger can be used. In other words, the surface protective layer 5 may contain a triazine-based ultraviolet absorber and a light stabilizer. By using the above-mentioned triazine-based ultraviolet absorber and the radical scavenger in combination, the weather resistance of the decorative sheet 1 can be further improved. Examples of hindered amine-based 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, bi Su(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-diter-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino) Hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tertiaryoctylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2,4-Bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino Examples include, but are not limited to, the reaction products of )-s-triazine-6-yl]aminoundecane, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatecyclohexane and N-butyl peroxide 2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro1,3,5-triazine and 2-aminoethanol.

[0050] In this embodiment, the amount of light stabilizer (e.g., hindered amine-based radical scavenger) added to the surface protective layer 5 is preferably within the range of 1 part by mass to 30 parts by mass per 100 parts by mass of the resin composition (e.g., acrylic resin composition) forming the surface protective layer 5. Adding 1 part by mass or more of the light stabilizer allows for the desired weather resistance to be obtained, while adding 30 parts by mass or less suppresses the bleed-out of the weather stabilizer and minimizes its influence on other physical properties of the surface protective layer 5.

[0051] <Application amount> The amount of surface protective layer 5 applied, that is, the amount of material for the surface protective layer 5 applied on the transparent resin layer 4, is 3 g / m². 2 More than 10g / m 2 A range of less than 3 g / m² is preferable. 2 If the amount is less than 10g / m², good weather resistance cannot be obtained. 2If the coating amount exceeds this range, it may hinder recyclability. By keeping the coating amount within this range, it is possible to achieve both good weather resistance and recyclability. Furthermore, keeping the coating amount within this range improves productivity and processability (e.g., bendability).

[0052] In this embodiment, the surface protection layer 5 includes an ultraviolet absorber and a light stabilizer, but the disclosure is not limited thereto. The surface protection layer 5 may be provided with the desired weather resistance according to the application, and the surface protection layer 5 may be configured to include at least one of the ultraviolet absorber and the light stabilizer.

[0053] In this embodiment, various known coating methods can be used to provide the surface protection layer 5, such as gravure coating, reverse coating, gravure reverse coating, die coating, and flow coating. Furthermore, various additives such as anti-friction agents, anti-blocking agents, and antistatic agents may be added to the surface protection layer 5 in this embodiment as needed.

[0054] (Embossed area) As shown in Figure 1, an embossed portion 7 is provided on the outermost surface of the decorative sheet 1 according to this embodiment. By providing an embossed portion 7 on the outermost surface, it is possible to improve fingerprint resistance while maintaining the matte finish of the decorative sheet 1 surface. Furthermore, the embossed portion 7 can be made into various uneven shapes, such as wood grain grooves, stone slab surface irregularities (granite cleavage surfaces, etc.), fabric surface textures, pearlescent, sandy, hairline, or fine-line grooves, thereby imparting a given design to the surface of the decorative sheet 1. The embossed portion 7 can be made into various uneven shapes, for example, according to the design of the pattern layer 3 or according to the desired design. The embossed portion 7 is formed on the surface (outermost surface) side of the surface protection layer 5, which is the outermost layer of the decorative sheet 1, and constitutes an uneven pattern. In this embodiment, the surface protection layer 5 described above is embedded in the embossed portion 7 that constitutes this uneven pattern. This point will be explained below.

[0055] In the decorative sheet 1 according to this embodiment, the embossed portion 7 is provided on the transparent resin layer 4. That is, the transparent resin layer 4 is the layer on which the embossed portion 7 is formed. The shape of the uneven pattern provided on the surface of the transparent resin layer 4 is not particularly limited, but it is preferable that the shape of the embossed portion 7 constituting the uneven pattern is such that the opening diameter increases from the back side (pattern layer 3 in this example) to the front side (surface protection layer 5) of the transparent resin layer 4. With such a shape, it is easier to embed the surface protection layer composition (coating liquid) into the embossed portion 7 by wiping.

[0056] Furthermore, it is preferable that the side surface forming the embossed portion 7 is an inclined surface. If the side surface forming the embossed portion 7 is an inclined surface, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portion 7 by wiping. Furthermore, all sides forming the embossed portion 7 may be covered with the surface protective layer 5. Furthermore, the depth of the embossed portion 7 is preferably within the range of 1 μm to 50 μm in the thickness direction of the transparent resin layer 4. If the depth of the embossed portion 7 is within the above numerical range, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portion 7 by wiping, and peeling of the surface protective layer can be prevented.

[0057] Furthermore, the width of the embossed portion 7 is preferably within the range of 1 μm to 20 μm. If the width of the embossed portion 7 is within the above numerical range, it becomes easier to embed the surface protective layer composition (coating liquid) into the embossed portion 7 by wiping, and it is possible to prevent the surface protective layer embedded in the embossed portion 7 from peeling off.

[0058] Furthermore, it is preferable that the embossed portion 7 is completely filled with the surface protective layer composition (coating liquid), but it is preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 is 10% or more. If the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 is 10% or more, the weather resistance of the embossed portion 7 can be improved. That is, if the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 is 10% or more, the occurrence of whitening and breakage in the conduit portion can be reduced. Also, as mentioned above, it is preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 is 100%, but it is more preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 is 80% or less, and it is even more preferable that the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 is 60% or less. If the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 is 80% or less, a sufficient tactile feel can be obtained in the embossed portion 7. Alternatively, by making the filling rate of the surface protective layer 5 relative to the volume of the embossed portion 7 100%, the surface of the surface protective layer 5 filling the embossed portion 7 and the surface of the transparent resin layer 4 in the area without the embossed portion 7 may be made flush.

[0059] (Vinyl chloride resin layer) As described above, in this embodiment, the decorative sheet 1 comprises two layers of polyvinyl chloride resin: a colored raw material layer 2 and a transparent resin layer 4. Furthermore, as described above, it is preferable that at least one of the two polyvinyl chloride resin layers contains an ultraviolet absorber and a light stabilizer. This further improves the weather resistance of the decorative sheet 1. The ultraviolet absorber and light stabilizer may be contained in one of the two polyvinyl chloride resin layers, or in both layers. By containing ultraviolet absorbers and light stabilizers in multiple layers, weather resistance can be more reliably improved.

[0060] [Plasticizer] Furthermore, as described above, it is preferable that the two polyvinyl chloride resin layers (colored raw material layer 2, transparent resin layer 4) contain a plasticizer in addition to the ultraviolet absorber and light stabilizer. This improves the weather resistance of the decorative sheet 1 and improves its mechanical properties. The plasticizer may be contained in one of the two polyvinyl chloride resin layers, or in both layers. By containing plasticizers in multiple layers, it is possible to more reliably improve the mechanical properties.

[0061] The plasticizer is not particularly limited as long as it is compatible with the vinyl chloride resin. Examples include phthalate-based plasticizers such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP), and diundecyl phthalate (DUP); adipic acid-based plasticizers such as dibutyl adipate; phosphate-based plasticizers such as tributyl phosphate, tricresyl phosphate, and triphenyl phosphate; trimellitic acid-based plasticizers such as tributyl trimellitic acid and trioctyl trimellitic acid; various known polyester-based plasticizers such as adipic acid-based polyesters; and citrate esters such as acetyl tributyl citrate and acetyl trioctyl citrate. Among these, phthalate-based plasticizers, adipic acid-based plasticizers, and polyester-based plasticizers are preferred from the viewpoint of improving both processability and long-term adhesion, and from the viewpoint of improving processability, phthalate-based plasticizers and polyester-based plasticizers are more preferred. Furthermore, considering solvent resistance, oil resistance, weather resistance, and durability, it is even more preferable to use polymer polyester-based plasticizers. These plasticizers may be used individually or in combination of multiple types. For example, it is preferable that at least one of the two polyvinyl chloride resin layers (colored raw material layer 2, transparent resin layer 4) contains at least one of polyester-based plasticizers and phthalate-based plasticizers as a plasticizer.

[0062] The plasticizer content in each of the two polyvinyl chloride resin layers described above is, for example, within the range of 20% (20 parts) to 30% (30 parts) relative to 100% polyvinyl chloride resin (100 parts colored polyvinyl chloride resin or 100 parts transparent polyvinyl chloride resin). In other words, the amount of plasticizer added is, for example, within the range of 20 PHR to 30 PHR. This allows for good and stable control of the mechanical properties (in this example, elastic modulus, yield strength, and elongation at break) of the decorative sheet 1 throughout the year (for example, in a temperature environment of 0 to 40°C) even when formed using polyvinyl chloride resin. In short, a decorative sheet with good processability and productivity can be obtained. On the other hand, if the plasticizer content in each layer is less than 20 PHR, the cold resistance may be poor. Also, if the plasticizer content is more than 30 PHR, the decorative sheet 1 becomes soft and loses its rigidity, making it difficult to handle and potentially reducing productivity during processing. Furthermore, the scratch resistance of decorative sheet 1 may also be reduced.

[0063] (Total sheet thickness) The overall thickness (total thickness) of the decorative sheet 1 according to this embodiment is preferably in the range of 200 μm to 300 μm, and more preferably in the range of 230 μm to 270 μm. This makes it possible to form a decorative sheet 1 that has opacity comparable to that of a conventional decorative sheet formed using olefin resin, and also has good durability, weather resistance, and processability. In this example, the total thickness of the decorative sheet 1 is the sum of the thicknesses of the two polyvinyl chloride resin layers, the colored raw material layer 2 and the transparent resin layer 4.

[0064] (Decorative material) In this embodiment, the decorative sheet 1 described above may be bonded to a base material 8, which is a base material for decorative materials, to form a decorative material 10.

[0065] (base material) The base material 8 can be a wood-based or metal-based material. Examples of wood-based materials include wood veneer, wood plywood, laminated wood, particleboard, medium-density fiberboard, and rigid fiberboard. Examples of metal-based materials include steel plates and aluminum plates. The base material 8 may also be a resin such as plastic, or a composite material thereof. When the base material 8 is a resin-based material, for example, polyvinyl chloride resin can be used. Base material 8 made of polyvinyl chloride resin has high thermal insulation properties and is in high demand as a window frame (sash). Furthermore, decorative material 10, which is a polyvinyl chloride resin base material 8 decorated with a decorative sheet 1, allows for the melting and reuse of both the base material 8 and the decorative sheet 1, thus improving recyclability. The base material 8 may also be made of, for example, a non-combustible steel plate or a non-combustible material as specified in Ministry of Construction Notification No. 1400.

[0066] As shown in Figure 1, a decorative sheet 1 is laminated to one side of the base material 8 (the upper side in Figure 1). In other words, the decorative material 10 according to this embodiment comprises a base material 8, which is a base material for decorative materials, and a decorative sheet 1 that is bonded to the base material 8. By laminating the decorative sheet 1 according to this embodiment onto the base material 8, a decorative material can be obtained that has excellent weather resistance even when formed using polyvinyl chloride resin, and furthermore, has excellent processability and recyclability. More specifically, the decorative material 10 comprises a base material 8 and a decorative sheet 1 laminated on one surface of the base material 8. Note that the configuration of the decorative material 10 is not limited to the example shown in Figure 1. That is, the decorative material 10 may also be configured to include a decorative sheet 1 laminated on the other surface of the base material 8 (the lower surface in Figure 1) in addition to the one surface of the base material 8.

[0067] (Method of manufacturing decorative sheets and decorative materials) The following describes an example of a manufacturing method for the decorative sheet 1 according to this embodiment. The manufacturing method for the decorative sheet 1 according to this embodiment is a method for manufacturing a decorative sheet in which at least a colored raw material layer, a pattern layer, a transparent resin layer, and a surface protection layer are laminated in this order. The aforementioned colored raw material layer 2 is formed from colored polyvinyl chloride resin, and the transparent resin layer 4 is formed from transparent polyvinyl chloride resin.

[0068] Furthermore, a pattern layer 3 is printed on one side of the transparent resin layer 4, and a surface protection layer 5 is formed on the other side of the transparent resin layer 4 (the side opposite to the pattern layer 3). At this time, for example, a coating liquid for forming the surface protection layer 5 may be applied to the other side, and then an embossed portion 7 may be formed by creating a raised and recessed pattern on the surface protection layer 5. Alternatively, an embossed portion 7 may be formed on the other side of the transparent resin layer 4, and then a coating liquid for forming the surface protection layer 5 may be applied to the side on which the embossed portion 7 is formed. In this case, the surface protection layer 5 can be formed on the transparent resin layer 4 by wiping so as to embed the coating liquid into the embossed portion 7 that constitutes the raised and recessed pattern, and then curing the coating liquid. As a result, the pattern layer 3, surface protection layer 5, and embossed portion 7 are formed on the transparent resin layer 4. These are collectively called the upper layer. Alternatively, the embossed portion 7 may be formed after the surface protection layer 5 has been applied to the transparent resin layer 4. Alternatively, the pattern layer 3 may be solid printed on one side of the transparent resin layer 4 using black ink, making the decorative sheet 1 a single-color sheet in dark black. This improves the aesthetic appeal of the decorative sheet 1. Next, the colored raw material layer 2 is placed on one side of the transparent resin layer 4 (upper layer) (the side with the pattern layer 3 printed on it) and laminated (heat laminated) is performed.

[0069] [Concentration of residual solvent] In the manufacturing method of the decorative sheet 1 according to this embodiment, the concentration of solvent (e.g., organic solvent) remaining in the transparent resin layer 4 when the pattern layer 3 is printed (residual solvent concentration) is kept below a predetermined value. Here, the solvent is assumed to be an organic solvent contained in the printing ink that forms the pattern layer 3. Specifically, in the manufacturing method of the decorative sheet 1 according to this embodiment, the residual solvent concentration per unit area in the transparent resin layer 4 on which the pattern layer 3 is printed is 3 mg / m². 2 The following applies: In other words, the upper limit of the residual solvent concentration per unit area in the transparent resin layer 4 after printing the pattern layer 3 is set to 3 mg / m². 2Let's assume this. As a result, in the decorative sheet using polyvinyl chloride resin, the generation of wrinkles due to the printing process can be suppressed. When the upper limit value of the residual solvent concentration exceeds the above upper limit value (3 mg / m 2 ), when the above-mentioned thermal lamination is carried out after printing the pattern layer 3, wrinkles may occur in the transparent resin layer 4 due to the residual solvent, and as a result, wrinkles may be formed on the surface of the decorative sheet 1. In particular, as described above, when the pattern layer 3 is printed using a dark-colored (e.g., black) printing ink to make the decorative sheet 1 a single-color sheet with a dark black color, wrinkles are more likely to occur due to an increase in the ink amount.

[0070] In the transparent resin layer 4 after printing the pattern layer 3, by setting the upper limit value of the residual solvent concentration to 3 mg / m 2 or less, regardless of the coating amount of the printing ink on the transparent resin layer 4, the generation of wrinkles (the generation of wrinkles in the transparent resin layer 4 due to the residual solvent) due to the printing process (printing of the pattern layer 3) in the decorative sheet 1 can be suppressed, and the design property of the decorative sheet 1 can be improved. Therefore, even when the decorative sheet 1 is a single-color sheet with a dark black color as described above (when the coating amount of the printing ink increases), the generation of wrinkles due to the printing process (printing of the pattern layer 3) can be suppressed. Also, by setting the above residual solvent concentration to 3 mg / m 2 or less, even when the coating amount of the printing ink increases, thermal lamination can be carried out without significantly extending the drying time after printing. For this reason, an increase in manufacturing cost can be suppressed.

[0071] The residual solvent concentration can be measured by performing gas chromatography (analysis of vaporized components) on the transparent resin layer 4 printed with the pattern layer 3. That is, in the present embodiment, the residual solvent concentration is measured using a gas chromatograph (GC: Gas Chromatograph). The above residual solvent concentration may be adjusted, for example, according to the composition of the printing ink of the pattern layer 3. For example, it may be adjusted by a functional additive or the like contained in the printing ink of the pattern layer 3. Also, the residual solvent concentration may be adjusted, for example, according to the composition of the transparent resin layer 4 on which the pattern layer 3 is printed. For example, it may be adjusted by an additive (e.g., weathering agent) or the like contained in the transparent resin layer 4.

[0072] In this way, the decorative sheet 1 according to this embodiment is formed. Furthermore, it is preferable that the decorative sheet 1 be manufactured so that the total thickness of the sheet is within the range of 200 μm to 300 μm. This makes it possible to form a decorative sheet 1 that has the same level of opacity as a decorative sheet formed using conventional olefin resins, and also has good durability, weather resistance, and processability.

[0073] Furthermore, it is preferable that at least one of the two polyvinyl chloride resin layers (transparent resin layer 4, colored raw material layer 2) contains an ultraviolet absorber, a light stabilizer, and a plasticizer. This improves the weather resistance of the decorative sheet 1 and enhances its mechanical properties. Furthermore, it is preferable that at least one of the two layers of polyvinyl chloride resin contains a heat stabilizer in addition to an ultraviolet absorber, light stabilizer, and plasticizer. This further improves weather resistance and durability. Furthermore, it is preferable that the plasticizer is at least one of polyester-based plasticizers and phthalate-based plasticizers. By using polyester-based plasticizers (especially polymer polyester-based plasticizers), solvent resistance, oil resistance, weather resistance, and durability can be improved. By using phthalate-based plasticizers, processability can be improved. Furthermore, it is preferable that the surface protective layer 5 is formed of a hydrophobic group-introduced acrylic polyol and contains an ultraviolet absorber and a light stabilizer. This makes it possible to improve the moisture and heat resistance of the decorative sheet 1 and to enhance its weather resistance.

[0074] Below, an example of a method for manufacturing the cosmetic material 10 according to this embodiment will be briefly described. The decorative sheet 1 and the base material 8 described above can be bonded together to form the decorative material 10.

[0075] <Variation> While hydroxyphenyltriazine-based ultraviolet absorbers that can be added to the surface protective layer 5 have been described, the hydroxyphenyltriazine-based ultraviolet absorbers that can be used in this embodiment are not limited to these. The surface protective layer 5 according to this embodiment may contain, for example, a hydroxyphenyltriazine-based ultraviolet absorber having a structure represented by the following general formula (1). Alternatively, the surface protective layer 5 may contain an ultraviolet absorber having a structure represented by the following general formula (2). Specifically, it may contain 2,4-bis[2-hydroxy-4-(2-ethylhexyloxy)phenyl)]-6-(4-methoxyphenyl)-s-triazine shown in the following formula (3), or it may contain a hydroxyphenyltriazine-based ultraviolet absorber shown in the following formula (4).

[0076] [ka]

[0077] In general formula (1), R1 to R3 each independently represent a hydrogen atom, a methyl group, a phenyl group, or an alkoxy group, and at least two of them are alkoxy groups having 8 to 18 carbon atoms that do not contain a carbonyl group; R4 and R5 each independently represent a hydroxyl group, a methyl group, or a hydrogen atom; and R6 to R8 each independently represent a methyl group or a hydrogen atom.

[0078] [ka]

[0079] In general formula (2), R1 and R2 represent alkoxy groups having 8 to 18 carbon atoms, R3 represents an alkoxy group having 1 to 4 carbon atoms, R4 represents a hydroxyl group, and R5 to R8 represent hydrogen atoms.

[0080] [ka]

[0081] [ka]

[0082] Furthermore, by using both hydroxyphenyltriazine and benzotriazole UV absorbers in combination, even better weather resistance can be imparted due to their interaction. This is because benzotriazole UV absorbers have an absorption peak at longer wavelengths than hydroxyphenyltriazine UV absorbers, thus broadening the wavelength range over which ultraviolet light is absorbed when used in combination. The amount of benzotriazole UV absorber to be added is preferably in the range of 1 to 30 parts by mass per 100 parts by mass of the acrylic resin composition. Adding 1 part by mass or more will yield the desired effect, while adding 30 parts by mass or less will suppress the bleed-out of the weather-resistant agent. However, because benzotriazole UV absorbers have an absorption peak at longer wavelengths, they may have a yellowish tint. If color is a concern, the amount added should be reduced.

[0083] Examples of benzotriazole-based ultraviolet absorbers include, but are not limited to, 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-diter-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-ter-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-ter-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumylphenyl)benzotriazole, 2,2'-methylenebis(4-ter-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-ter-butyl-5'-carboxyphenyl)benzotriazole.

[0084] <Examples> The present disclosure will be described in detail below with reference to examples and comparative examples, but the present disclosure is not limited to the examples below.

[0085] (Example 1) Transparent polyvinyl chloride resin (hereinafter referred to as PVC: Poly Vinyl Cloride) A pattern layer was created on one side of a transparent resin layer formed by gravure printing a PVC printing ink (containing an organic solvent) using a solid plate, and a surface protective layer mainly composed of an acrylic resin composition was formed on the other side to form the upper layer. Furthermore, a colored raw material layer formed from colored polyvinyl chloride resin was laminated to the pattern layer side of the transparent resin layer and heat-laminated to obtain the decorative sheet according to Example 1. The composition of each layer in this example is shown below. [Colored original fabric layer] Material: PVC, Thickness: 80μm Additives: Yes (colorants, weather stabilizers (UV absorbers, light stabilizers), plasticizers, etc.) [Transparent resin layer] Material: PVC, Thickness: 80μm Additives: Yes (colorants, weather stabilizers (UV absorbers, light stabilizers), plasticizers, etc.) [Surface protective layer] • Main component: Hydrophobic group-introduced acrylic polyol • Additives: Yes (weather stabilizers (UV absorbers, light stabilizers), etc.) [Total sheet thickness] 240 μm (= base material layer thickness: 80 μm + colored base material layer thickness: 80 μm + transparent resin layer thickness: 80 μm) [Residual solvent concentration] The transparent resin layer, after the image layer has been printed and before heat lamination, was used as a sample, and the residual solvent concentration per unit area (mg / m²) was determined using a gas chromatograph "(Shimadzu Corporation) GC-2010". 2 The following measurements were taken: The sample was 10cm x 10cm in size, folded into quarters, and had seven cuts made in it. In Example 1, the residual solvent concentration was 0.6 mg / m³. 2 That was the case.

[0086] (Example 2) A decorative sheet according to Example 2 was obtained in the same manner as in Example 1, except that the contents of the transparent resin layer were different from those in Example 1. In Example 2, the residual solvent concentration was 1.2 mg / m². 2 That was the case. (Example 3) A decorative sheet according to Example 3 was obtained in the same manner as in Example 1, except that the contents of the transparent resin layer differed from those in Examples 1 and 2. In Example 3, the residual solvent concentration was 1.8 mg / m². 2 That was the case. (Example 4) A decorative sheet according to Example 4 was obtained in the same manner as in Example 1, except that the contents of the transparent resin layer differed from those in Examples 1-3. In Example 4, the residual solvent concentration was 2.1 mg / m². 2 That was the case.

[0087] (Comparative Example 1) A decorative sheet according to Comparative Example 1 was obtained in the same manner as in Example 1, except that the contents of the transparent resin layer differed from those in Examples 1-4. In Comparative Example 1, the residual solvent concentration was 8.4 mg / m². 2 That was the case.

[0088] <Rating> The decorative sheets obtained in the above examples and comparative examples were evaluated for their performance (design) using the following method. The evaluation results are shown in Table 1.

[0089] (Design evaluation) For the decorative sheets of the examples and comparative examples, the presence or absence of wrinkles after heat lamination was visually determined. If no wrinkles were observed visually, the design was good, and there were no problems with using it as a product, it was marked as "○". If wrinkles were observed visually, the design was poor, and it was unusable as a product, it was marked as "×".

[0090] [Table 1]

[0091] As can be seen from Table 1, in the decorative sheets of Examples 1-4, the residual solvent concentration per unit area of ​​the transparent resin layer after printing the pattern layer (before heat lamination) was 3 mg / m². 2The results were as follows. Therefore, no wrinkles occurred in the transparent resin layer due to the printing of the pattern layer, and no wrinkles were visible to the naked eye from the sheet surface, so the evaluation was passed ("○"). In other words, the above residual solvent was set to the upper limit (3 mg / m²). 2 It was found that by doing the following, the occurrence of wrinkles caused by printing the pattern layer (printing process) in the decorative sheet can be suppressed, and the design quality of the decorative sheet 1 can be improved. On the other hand, in the decorative sheet of Comparative Example 1, the residual solvent concentration per unit area of ​​the transparent resin layer after printing the pattern layer (before heat lamination) was 3 mg / m². 2 The limit was exceeded, resulting in wrinkles in the transparent resin layer and a failing grade ("×").

[0092] Furthermore, the decorative sheet and method for manufacturing the decorative sheet described herein are not limited to the embodiments and examples described above, and various modifications are possible as long as they do not impair the features of the invention.

[0093] Furthermore, for example, this disclosure can take the following configuration. (1) A method for manufacturing a decorative sheet in which at least a colored base layer, a pattern layer, a transparent resin layer, and a surface protection layer are laminated in this order, The aforementioned colored base layer is formed from colored polyvinyl chloride resin. The transparent resin layer is formed from transparent polyvinyl chloride resin. The pattern layer is printed on one side of the transparent resin layer, and the surface protective layer is formed on the other side of the transparent resin layer. The residual solvent concentration per unit area in the transparent resin layer on which the pattern layer is printed is 3 mg / m². 2 The following is a method for manufacturing decorative sheets. (2) The method for manufacturing a decorative sheet according to (1) above, characterized in that at least one of the colored raw material layer and the transparent resin layer is formed by including an ultraviolet absorber, a light stabilizer and a plasticizer. (3) The method for manufacturing a decorative sheet according to (2) above, characterized in that at least one of the colored raw material layer and the transparent resin layer is formed to further contain a heat stabilizer in addition to an ultraviolet absorber, a light stabilizer and a plasticizer. (4) The method for producing a decorative sheet according to (2) or (3) above, characterized in that the plasticizer is at least one of a polyester-based plasticizer and a phthalate-based plasticizer. (5) The method for producing a decorative sheet according to any one of (1) to (4) above, characterized in that the surface protective layer is formed of a hydrophobic group-introduced acrylic polyol and contains an ultraviolet absorber and a light stabilizer. (6) A method for manufacturing a decorative sheet according to any one of (1) to (5) above, characterized in that the pattern layer is solid printed on one side of the transparent resin layer using black ink. [Industrial applicability]

[0094] This disclosure is a technology suitable for building exteriors and semi-exterior building materials, such as entrance doors, their frames, window frames, and bay window counters. [Explanation of Symbols]

[0095] 1 Decorative sheet 2 Colored original fabric layer 3 Pattern Layers 4 Transparent resin layer 5 Surface protective layer 7 Embossed area 8 Base material 10 Decorative materials

Claims

1. A method for manufacturing a decorative sheet in which at least a colored base layer, a pattern layer, a transparent resin layer, and a surface protection layer are laminated in this order, The aforementioned colored base layer is formed from colored polyvinyl chloride resin. The transparent resin layer is formed from transparent polyvinyl chloride resin. The pattern layer is printed on one side of the transparent resin layer, and the surface protective layer is formed on the other side of the transparent resin layer. The residual solvent concentration per unit area in the transparent resin layer on which the pattern layer is printed is 3 mg / m². ２ The following is a method for manufacturing decorative sheets.

2. At least one of the colored raw material layer and the transparent resin layer is formed containing an ultraviolet absorber, a light stabilizer and a plasticizer. A method for manufacturing a decorative sheet according to feature 1.

3. At least one of the colored raw material layer and the transparent resin layer is formed by further containing a heat stabilizer in addition to an ultraviolet absorber, a light stabilizer, and a plasticizer. The method for manufacturing a decorative sheet according to feature 2.

4. The method for producing a decorative sheet according to claim 2 or 3, characterized in that the plasticizer is at least one of a polyester-based plasticizer and a phthalate-based plasticizer.

5. The method for producing a decorative sheet according to claim 4, characterized in that the surface protective layer is formed of a hydrophobic group-introduced acrylic polyol and contains an ultraviolet absorber and a light stabilizer.

6. The pattern layer is solid-printed onto one of the transparent resin layers using black ink. A method for manufacturing a decorative sheet according to any one of claims 1 to 3.

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