JP2023048896A - Decorative sheet, decorative material, and method for producing decorative sheet - Google Patents

Abstract

To provide a decorative sheet imparted with a texture closer to that of a natural material.SOLUTION: There is provided a decorative sheet comprising: a surface layer 50 that forms a surface; and a design layer 40 superimposed on the surface layer, and a 60° gloss value measured at the surface is 8 or less, and a 85° gloss value measured at the surface is less than the 60° gloss value measured at the surface.SELECTED DRAWING: Figure 2

Description

TECHNICAL FIELD The present invention relates to a decorative sheet, a decorative material, and a method for manufacturing a decorative sheet.

From the viewpoint of environmental conservation, decorative sheets as a substitute for natural materials are attracting more attention. Decorative sheets are required to express the texture of natural materials while eliminating artificial impressions. In order to reproduce the texture of a natural material, attempts have been made to provide an appropriate tactile sensation and reduce the 60° gloss value (for example, Patent Document 1).

JP 2021-054074 A

However, simply adjusting the tactile feel and the 60° gloss value cannot sufficiently express the complex texture of natural materials. These days, from the viewpoint of environmental conservation, it is becoming more difficult to obtain natural materials. Along with this trend, there is a growing demand for expressing the texture of natural materials with decorative sheets. An object of the present disclosure is to provide a decorative sheet with a texture that is closer to that of natural materials.

In one embodiment of the present disclosure, the first decorative sheet is
a surface layer that constitutes the surface;
and a design layer superimposed on the surface layer,
The 60° gloss value measured on the surface is 8 or less,
The 85° gloss value measured at the surface is less than the 60° gloss value measured at the surface.

In one embodiment of the present disclosure, the second decorative sheet is
a surface layer that constitutes the surface;
and a design layer superimposed on the surface layer,
The surface layer includes a first layer constituting the surface and a second layer positioned between the first layer and the design layer,
The first layer includes a binder resin containing a cured product of a curable resin composition containing an acrylic resin or an acrylic urethane resin, and particles held by the binder resin,
The second layer contains a thermoplastic resin containing urethane resin or acrylic urethane resin,
The average thickness of the surface layer is 5 μm or more and 20 μm or less,
The average particle diameter of the particles is 8 μm or more and 20 μm or less.

In one embodiment of the present disclosure, the third decorative sheet is
a surface layer that constitutes the surface;
and a design layer superimposed on the surface layer,
The surface layer contains a binder resin and particles,
The surface layer includes peaks having a thickness of 1.5 times or more the average thickness of the surface layer,
The mountain portion includes a plurality of particles,
The decorative sheet, wherein the peak angle is 165° or less.

In one embodiment of the present disclosure, a method for manufacturing a decorative sheet includes:
A step of forming a second layer containing a thermoplastic resin by applying a second layer resin composition containing a urethane resin or an acrylic urethane resin to a base material containing a design layer and drying the composition;
Applying a resin composition for the first layer containing a curable resin composition containing an acrylic resin or an acrylic urethane resin and particles having an average particle size of 8 μm to 20 μm onto the second layer and curing the composition. forming the first layer by
The average thickness of the surface layer including the first layer and the second layer is 5 μm or more and 20 μm or less.

According to the present invention, the decorative sheet can express a texture closer to that of a natural material.

FIG. 1 is a view for explaining an embodiment of the present disclosure, and is a longitudinal cross-sectional view showing an example of the layer structure of a decorative material and a decorative sheet. 2 is an enlarged sectional view of the decorative sheet shown in FIG. 1. FIG. FIG. 3 is a cross-sectional view similar to FIG. 2, showing a cross-section of the decorative sheet different from that of FIG. 4 is an enlarged plan view of the decorative sheet shown in FIG. 1. FIG. FIG. 5 is a diagram for explaining a method of manufacturing the surface layer shown in FIGS. 2 to 4. FIG. FIG. 6 is a view corresponding to FIG. 1 and a vertical cross-sectional view showing another example of the layer structure of the decorative material and the decorative sheet.

An embodiment will be described below with reference to specific examples shown in the drawings. In the drawings attached to this specification, for convenience of illustration and ease of understanding, the scale, length-to-width ratio, etc. are appropriately changed and exaggerated from those of the real thing.

In order to clarify the directional relationship between the drawings, some drawings show the common first direction D1, the second direction D2 and the third direction D3 by the arrows with the common reference numerals. The tip side of the arrow is the first side in each direction. For example, as shown in FIG. 1, a symbol with an X in a circle indicates an arrow pointing into the drawing along a direction perpendicular to the drawing. For example, as shown in FIG. 4, the dot-in-a-circle symbol indicates an arrow pointing forward from the plane of the drawing along a direction perpendicular to the plane of the drawing. In the illustrated example, the third direction D3 is the normal direction of the decorative sheet 20 . The illustrated flat decorative sheet 20 extends in a first direction D and a second direction D2. The first direction D and the second direction D2 are orthogonal to the third direction D3. The first direction D and the second direction D2 are orthogonal to each other.

As used herein, the terms "plate", "sheet", and "film" are not to be distinguished from one another based solely on their designation. For example, "sheet" is a concept that includes members that can be called films and plates. Therefore, the "decorative sheet" should not be distinguished from members called "decorative film" or "decorative board" only by the difference in name.

[Decorative sheet and decorative material]
The decorative material 10 includes a support material 15 and a decorative sheet 20. As shown in FIG. Decorative sheet 20 includes design layer 40 and surface layer 50 . The design layer 40 displays a design. The surface layer 50 forms one surface 21 of the decorative sheet 20 . The surface layer 50 covers the design layer 40 and protects the design layer 40 . The surface layer 50 is a transparent layer that allows the design of the design layer 40 to be observed through the surface 21 . The decorative sheet 20 including the design layer 40 can improve the designability of the decorative material 10 . The decorative sheet 20 including the design layer 40 can improve the design of the surrounding environment of the decorative material 10 .

The decorative sheet 20 according to one embodiment is a decorative sheet called "low gloss". The surface 21 of the decorative sheet 20 has a 60° gloss value of 8 or less. The decorative sheet 20 has a reduced luster in order to express the texture of natural materials. In the decorative sheet 20 according to the present embodiment, the 85° gloss value of the surface 21 is smaller than the 60° gloss value of the surface 21 . By adjusting the 60° gloss value and the 85° gloss value in this way, the texture of the natural material can be expressed more faithfully. As a result, according to the decorative sheet 20 according to the present embodiment, it is possible to achieve a remarkably superior design compared to conventional products.

In conventional decorative sheets, the 60° gloss value has been adjusted, but the 85° gloss value has not been sufficiently studied. In addition, unless special measures are taken, the 85° gloss value with a larger incident angle tends to be larger than the 60° gloss value with a smaller incident angle, according to natural phenomena. In view of these circumstances, the effect obtained by the feature that the 85° gloss value is smaller than the 60° gloss value is different and cannot be predicted from the state of the art.

The gloss value conforms to JIS Z 8741 and is measured by BYK-Gardner's micro-TRI-gloss Cat. No. 4563 shall be the value measured. A 60° gloss value is a value measured at an incident angle of 60°. The 85° gloss value is a value measured at an incident angle of 85°. A 20° gloss value is a value measured at an incident angle of 20°. The angle of incidence is the angle between the normal direction of the plane of incidence and the optical path of the incident light, and takes a value of 90° or less. The gloss value on the surface means the gloss value measured with the surface of the target member as the plane of incidence.

In the decorative material 10, the support material 15 and the decorative sheet 20 are stacked in the third direction D3. The decorative material 10 can be applied to interior walls, ceilings, floors, exterior walls, roofs, doors, and fittings of buildings. The decorative material 10 can be applied to home electric appliances, office equipment, and furniture. The decorative material 10 can be used as an interior material or an exterior material of a moving object. A mobile body to which the cosmetic material 10 can be applied is a mobile device. Examples of mobile objects include automobiles, railroad vehicles, ships, aircraft, and drones.

The support material 15 is an adherend of the decorative sheet 20 . The support material 15 may be the object to which the decorative sheet 20 is applied, or may be a part of the object. The support material 15 is given a design using the decorative sheet 20 . The support member 15 may be a member made of metal, wood, or resin. The metallic support member 15 may be, for example, an aluminum member, a steel member, a stainless member, or a composite panel. A composite panel may include a core and a cladding bonded to the core. The core material may be a resin plate. The coating material may be a plate material such as aluminum, galvalume, or stainless steel. The wood-based support material 15 may be MDF (medium density fiberboard), plywood, or particle board. Support 15 may be a molded article. The support material 15 as a molded product may be made of polyolefin, vinyl chloride resin, styrene resin, (meth)acrylic resin, polyester, polycarbonate, polyamide, polyimide, cellulose resin, phenol resin, rubber, or the like. The support material 15 as a molded product may be sheet-like or may have a three-dimensional shape.

FIG. 1 is a longitudinal sectional view showing an example of a decorative material 10 and a decorative sheet 20. FIG. 2 and 3 are enlarged sectional views showing the decorative sheet 20. FIG. FIG. 4 is a plan photograph showing the decorative sheet 20. As shown in FIG. As shown in FIG. 1, the decorative sheet 20 may further include a substrate 30. As shown in FIG. In the example shown in FIG. 1, the base material 30, the design layer 40, and the surface layer 50 are stacked in this order in the third direction D3. Each component will be described below.

<Base material>
The substrate 30 may be flat. Examples of materials for the base material 30 include fibrous materials, resins, metals, non-metallic inorganic materials, wood-based materials, and the like. The material for the base material can be appropriately selected depending on the application.

Substrate 30 may be a single layer. The base material 30 may include two or more layers made of the above materials. When the base material 30 is a laminate of two or more layers, two or more layers of different materials may be laminated so that the performances of the materials of each layer complement each other. The following A to J are exemplified as examples of the base material 30 formed by laminating two or more layers.
(A) Lamination of resin and wood material (B) Lamination of resin and metal (C) Lamination of resin and fibrous material (D) Lamination of resin and non-metallic inorganic material (E) Resin 1 and resin Lamination with 2 (F) Lamination of metal and wood material (G) Lamination of metal and non-metallic inorganic material (H) Lamination of metal and fibrous material (I) Lamination of metal 1 and metal 2 ( J) Lamination of non-metallic inorganic material and fibrous material

In E above, the resin 1 and the resin 2 may be different resins. For example, resin 1 may be an olefin resin and resin 2 may be an acrylic resin. In H above, metal 1 and metal 2 may be different metals. For example, metal 1 may be copper and metal 2 may be chromium.

When the base material 30 is a laminate such as A to J above, it may have a layer (adhesive layer, etc.) for enhancing adhesive strength between the constituent layers of the laminate.

Various synthetic resins and natural resins are exemplified as the resin used for the base material 30 . Examples of synthetic resins include cured products of thermoplastic resins and curable resin compositions.

Fibrous materials used for the base material 30 include thin paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, parchment paper, paraffin paper, parchment paper, glassine paper, backing paper for wallpaper, paperboard, and base paper for gypsum board. and the like are exemplified. The paper may further contain a resin such as an acrylic resin, a styrene-butadiene rubber, a melamine resin, or a urethane resin in order to increase the interfiber strength of the paper base material or prevent the paper base material from fluffing. . Examples of resin-added paper include inter-paper reinforced paper and resin-impregnated paper. Examples of fibrous materials used for the base material 30 include woven fabrics or non-woven fabrics containing fibers such as silk, cotton, hemp, polyester resin fibers, acrylic resin fibers, glass fibers, and carbon fibers. As the substrate 30 in which a resin layer is laminated on a fibrous material layer, there is exemplified a wallpaper raw roll obtained by laminating a resin layer such as a vinyl chloride resin layer, an olefin resin layer, an acrylic resin layer on the surface of a backing paper for wallpaper. be.

Thermoplastic resins include polyethylene, polypropylene, polymethylpentene, ionomer, olefin resins such as various olefin thermoplastic elastomers, vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, and polyethylene terephthalate. , polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester resins such as polyester thermoplastic elastomers, polymethyl (meth)acrylate, polyethyl (meth)acrylate, poly (meth) ) Acrylic resins such as butyl acrylate, methyl (meth)acrylate-butyl (meth)acrylate copolymer, polyamide resins such as nylon 6 or nylon 66, cellulose triacetate, cellophane, celluloid, etc. Resins, styrene resins such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS), polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate Examples include resins and polyimide resins. Examples of the curable resin composition include a thermosetting resin composition and an ionizing radiation curable resin composition exemplified for the first layer 51 of the surface layer 50 to be described later. Examples of natural resins include natural rubber, rosin, and amber.

Examples of the metal used for the base material 30 include aluminum or alloys containing aluminum such as duralumin, alloys containing iron such as iron or carbon steel, stainless steel, alloys containing copper such as copper or brass, bronze, gold, and silver. , chromium, nickel, cobalt, tin, titanium and the like. The metal substrate may include a plating layer plated with these metals.

Examples of non-metallic inorganic materials used for the base material 30 include non-ceramic ceramic materials such as cement, ALC (lightweight cellular concrete), gypsum, calcium silicate, and wood chip cement; and ceramic materials such as ceramics, earthenware, glass, and enamel. Examples include ceramic materials, limestone, marble, granite, andesite and other natural stones.

Examples of the base material 30 of wood-based material include wood base materials made of wood such as cedar, cypress, pine, zelkova, oak, oak, walnut, lauan, teak, and rubber trees. The wood substrate may be plate-shaped. The wood substrate may be veneer, veneer, plywood, laminated lumber, particle board, fiberboard, or the like.

The base material 30 may contain additives as needed. When the material constituting the base material 30 is a resin, additives include inorganic fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. etc. are exemplified. The content of the additive is not particularly limited as long as it does not impair the processing characteristics, etc. The content of the additive is appropriately set according to the required characteristics, etc.

The shape and dimensions of the base material 30 are not particularly limited. The shape and dimensions of the substrate can be appropriately selected depending on the application, desired properties and processability. When the base material 30 is flat, the thickness of the base material 30 is not particularly limited. The thickness may generally be about 10 μm or more and 10 cm or less from the viewpoints of manufacturing suitability, mechanical strength, ease of use and economy. The thickness of the base material 30 may be about 20 μm or more and 300 μm or less, or about 1 mm or more and 2 cm or less.

In order to improve the adhesion between the base material and other layers that make up the decorative sheet or material, one or both sides of the base material are subjected to physical surface treatment such as an oxidation method or roughening method, or chemical surface treatment. surface treatment may be applied. Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, and the like. A sandblasting method, a solvent treatment method, and the like are exemplified as the roughening method. These surface treatments are appropriately selected according to the type of substrate. In general, the corona discharge treatment method is preferable from the viewpoint of surface treatment effect and operability.

<Design layer>
The decorative sheet 20 includes a design layer 40 to improve design. The design layer 40 is positioned between the base material 30 and the surface layer 50 in the third direction D3. The illustrated design layer 40 is adjacent to the substrate 30 . The illustrated design layer 40 is adjacent to the surface layer 50 . The design layer 40 may be positioned over the entire area of the decorative sheet 20 or may be positioned only over a partial area of the decorative sheet 20 .

Examples of the design layer 40 include a colored layer formed by printing ink uniformly, a pattern layer formed by printing ink as a pattern, a metal thin film, and the like. The pattern represented by the design layer 40 is not particularly limited. The pattern represented by the design layer 40 may represent natural materials such as wood and stone.

As a specific example, the pattern represented by the design layer 40 may be a pattern on the surface of wood. The tree represented by the design layer 40 is not particularly limited, and may be cedar, cypress, walnut, pine, cherry, or the like. The pattern on the surface of the tree may be the pattern of the surface of the tree, that is, the pattern of the bark. The pattern on the surface of the wood may be a pattern on the cross section of the wood, that is, a wood grain pattern. The wood grain pattern may include annual rings and duct grooves. The wood grain pattern may include earlywood (springwood) and latewood (summer or autumnwood).

The pattern represented by the design layer 40 may be a stone grain pattern on the surface of a stone plate such as marble or granite. The pattern represented by the design layer 40 may be a grain pattern on the surface of the leather. The pattern represented by the design layer 40 may be a grain pattern. The pattern represented by the design layer 40 may be a satin pattern. The pattern represented by the design layer 40 may be a pattern formed by arranging a plurality of concave lines and convex lines extending in directions parallel to each other. The pattern represented by the design layer 40 may be a geometric pattern. The pattern represented by the design layer 40 may be abstract patterns such as characters, graphics, polka dots, and floral patterns. The pattern represented by the design layer 40 may be a texture pattern on the surface of the fabric. The pattern represented by the design layer 40 may be a tiling pattern including joint grooves. The pattern represented by the design layer 40 may be a brickwork pattern including joint grooves.

The ink used for the colored layer and pattern layer is obtained by appropriately mixing a binder resin with coloring materials such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers, and the like. Ink may be used. The binder resin for the colored layer and pattern layer is not particularly limited. Binder resins for colored layers and pattern layers include, for example, urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and vinyl chloride-vinyl acetate copolymer resins. , vinyl chloride-vinyl acetate-acrylic copolymer resin, chlorinated propylene resin, nitrocellulose resin, cellulose acetate resin, and the like. Moreover, various types of resins such as a one-liquid curable resin and a two-liquid curable resin with a curing agent such as an isocyanate compound may be used.

Colorants are not particularly limited. Inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine, cobalt blue; quinacridone red, isoindolinone yellow, nickel azo complex , phthalocyanine blue, and azomethine azo black. The coloring material may be a dye. The coloring material may be a metal pigment composed of scale-like foil pieces of aluminum, brass, or the like. The coloring material may be a pearlescent (pearl) pigment composed of scale-like foil pieces such as titanium dioxide-coated mica and basic lead carbonate.

The content of the coloring material is not particularly limited. The content of the coloring material may be adjusted according to the pattern, shade and density of the decoration layer, and the material of the coloring material. As an example, the content of the coloring material may be 20 parts by mass or more and 500 parts by mass or less, or may be 50 parts by mass or more and 300 parts by mass or less with respect to 100 parts by mass of the resin constituting the colored layer and the pattern layer. It may be more than 200 parts by mass and less than 200 parts by mass.

The colored layer and pattern layer may contain additives such as ultraviolet absorbers, light stabilizers and coloring agents. The thicknesses of the colored layer and the pattern layer can be appropriately selected according to the desired pattern. The thickness of the colored layer and the pattern layer may be selected from the viewpoint of concealing the ground color of the support material 15 and improving the design. The thickness of the colored layer and pattern layer may be 0.5 μm or more and 20 μm or less, 1 μm or more and 10 μm or less, or 2 μm or more and 5 μm or less.

Examples of metal thin films include thin films of single metal elements such as gold, silver, copper, tin, iron, nickel, chromium, and cobalt; thin films of alloys containing two or more of the above metal elements; Examples of alloys include brass, bronze, stainless steel, and the like. The film thickness of the metal thin film can be about 0.1 μm to 1 μm.

<Surface layer>
The surface layer 50 constitutes one surface 21 of the decorative sheet 20 . The surface layer 50 is overlaid on the design layer 40 . The surface layer 50 may have the function of protecting the design layer 40 . For example, the abrasion resistance of the surface layer 50 may be superior to that of the design layer 40 .

In the present embodiment, surface layer 50 is configured to reduce luster on surface 21 of decorative sheet 20 . By suppressing the luster on the surface 21, the texture of the decorative sheet 20 approaches the texture of the natural material. The 60° gloss value measured at surface 21 may be 8 or less, 6 or less, or 4 or less.

The 85° gloss value measured on the surface 21 may be smaller than the 60° gloss value measured on the surface 21 in order to more faithfully represent the texture of the natural material. According to this decorative sheet 20, complex luster characteristics of natural materials can be expressed more faithfully.

The inventors of the present invention have extensively studied the gloss characteristics of natural materials and conventional decorative sheets. According to the studies by the inventors of the present invention, the natural materials have gloss characteristics different from those of conventional decorative sheets. Conventionally, the glossiness of decorative sheets has been evaluated using a 60° gloss value. However, even the decorative sheet whose 60° gloss value was suppressed to the same level as that of the natural material exhibited gloss characteristics different from those of the natural material. More specifically, when the decorative sheet was observed at a very large viewing angle, the glossy luster of the decorative sheet was conspicuous.

As a result of repeated studies by the inventors of the present invention, the 85° gloss value increased to about 10 for the decorative sheet with the 60° gloss value suppressed to 8 or less. Considering the natural phenomenon that the regular reflectance of light incident at 85 degrees is higher than the regular reflectance of light incident at 60 degrees, it is natural that the 85 degrees gloss value is larger than the 60 degrees gloss value. It's about. That is, normally, the 20° gloss value is smaller than the 60° gloss value, and the 60° gloss value is smaller than the 85° gloss value.

On the other hand, with the natural material, the gloss value at angles wider than 60°, for example, was lower than the 60° gloss value. For example, as demonstrated in the experiments described later, the 85° gloss value was 3.2 for the cross section of the tree whose 60° gloss value was 3.7. On the other hand, the 20° gloss value for the same tree section was 0.7. In other words, natural materials have complex gloss characteristics, and due to differences in these gloss characteristics, conventional decorative sheets could not sufficiently express the texture of natural materials.

As described above, by making the 85° gloss value measured on the surface 21 smaller than the 60° gloss value measured on the surface 21, the decorative sheet 20 can faithfully express the gloss characteristics of natural materials. As a result, the texture of the decorative sheet 20 becomes similar to that of the natural material. In this decorative sheet 20, the 20° gloss value may be smaller than the 60° gloss value, like natural materials. This also allows the decorative sheet 20 to faithfully express the texture of the natural material.

The 85° gloss value may be 4 or less, 3 or less, 2 or less, or 1 or less. By setting the 85° gloss value in this manner, the gloss value at a wide angle is sufficiently lowered, so that the gloss characteristics of natural materials can be expressed more faithfully.

2 and 3 are cross-sectional views showing an example of the surface layer 50 of the decorative sheet 20 according to this embodiment. 2 and 3 show cross sections of the decorative sheet 20 along the third direction D3. 2 and 3 show cross sections of the decorative sheet 20 along the normal direction.

The decorative sheet 20 shown in FIGS. 2 and 3 has the gloss characteristics described above. That is, the configuration of the decorative sheet 20 shown in FIGS. 2 and 3 is an example of a decorative sheet in which the 85° gloss value is smaller than the 60° gloss value.

In the decorative sheet 20 shown in FIGS. 2 and 3, the surface layer 50 contains binder resin 61 and particles 62 . The surface layer 50 includes peaks 71M with increased thickness. The peak portion 71M has a thickness that is 1.5 times or more the average thickness of the surface layer 50 . The peak portion 71M contains a plurality of particles. The apex angle θt of the peak portion 71M is 165° or less.

The thickness T50 (μm) of the surface layer 50 is the length (μm) of the surface layer 50 along the normal direction of the decorative sheet 20, as shown in FIG. The average thickness (μm) of the surface layer 50 is the average thickness at 50 locations measured every 100 μm in the direction orthogonal to the normal direction in the vertical cross section of the decorative sheet, that is, the cross section along the normal direction of the decorative sheet. value (μm). In FIGS. 2 and 3, the height position at which the surface layer 50 has an average thickness is indicated by a dotted line DL50.

The height T71 (μm) of the peak portion 71M is the length along the normal direction of the decorative sheet 20 to the top portion 71t of the peak portion 71M, as shown in FIG. As shown in FIG. 2, the apex angle θt (°) of the peak portion 71M is the angle between the first straight line 71L1 and the second straight line 71L2 in the longitudinal section of the decorative sheet, that is, the cross section along the normal direction of the decorative sheet. is the magnitude of the angle. The first straight line 71L1 passes through the first average thickness position 71m1 on the outer contour of the mountain portion 71M at the same height position DL50 as the average thickness of the surface layer 50 and the top portion 71t of the mountain portion 71M. The second straight line 71L2 passes through a second average thickness position 71m2 on the outer contour of the mountain portion 71M at the same height position DL50 as the average thickness of the surface layer 50, and the top portion 71t of the mountain portion 71M. The angle (°) of the apex angle θt is 180° or less.

The apex angle θt is relatively large due to the peak portion 71M formed so as to include a plurality of particles. By setting the apex angle θt to 165° or less and having a thickness of 1.5 times or more the average thickness of the surface layer 50, the peaks 71M diffuse light rather than cause large undulations on the surface 21. Acts as a protrusion to generate. According to the peak portion 71M having the relatively large apex angle θt, wide-angle gloss can be reduced. This makes it possible to obtain the decorative sheet 20 in which the 85° gloss value is lower than the 60° gloss value. As a result, as described above, the decorative sheet 20 can express the gloss characteristics of natural materials.

The apex angle θt of the peak portion 71M may be larger than 120°. By making the apex angle θt larger than 120°, light incident at a large incident angle can be selectively diffused by the peak portion 71M. More specifically, when the apex angle θt is made larger than 120°, light incident at an incident angle larger than 60° can be selectively reflected and selectively diffused by the peaks 71M. When the apex angle θt is set to 165° or less, light incident at 85° can be stably diffused. As a result, light incident at a wide angle of incidence can be diffused at a high rate by the peaks 71M. This decorative sheet 20 can more faithfully express the luster characteristics of natural materials. As a result, it becomes easier to reduce the 85° gloss value and the 60° gloss value.

The average thickness (μm) of the surface layer 50 may be 5 μm or more, 6 μm or more, or 7 μm or more. The average thickness (μm) of the surface layer 50 may be 20 μm or less, 17 μm or less, or 15 μm or less. The upper and lower limits of the average thickness of the surface layer 50 may be arbitrarily combined with each preferable range. By setting the average thickness of the surface layer 50 in this manner, it becomes easier to achieve the gloss characteristics according to the above-described present embodiment. By setting the average thickness of the surface layer 50 in this manner, the surface layer 50 can be provided with a sufficient protective function. By setting the average thickness of the surface layer 50 in this way, the particles 62 can be held stably.

The average particle size of particles 62 may be larger than the average thickness of surface layer 50 . As in the illustrated example, in an example in which the surface layer 50 includes a first layer 51 containing particles 62 and a layer separate from the first layer 51, the average particle diameter of the particles 62 is It may be larger than the average thickness of the first layer 51 . With this configuration, it becomes easier to achieve the above-described gloss characteristics of the present embodiment. According to this configuration, excellent tactile sensation can be imparted. The average thickness (μm) of the first layer 51 is the average of 50 measured values extracted in the same manner as the average thickness of the surface layer 50 .

The average particle diameter of the particles 62 may be smaller than the average thickness of the peak portion 71M. According to this configuration, as shown in FIG. 2, the particles 62 gather to form a high mountain portion 71M. This makes it easier to achieve the gloss characteristics according to the present embodiment described above. With this configuration, it is possible to prevent the particles 62 from falling off from the binder resin 61 .

The average particle diameter (μm) of the particles 62 may be 8 μm or more, 10 μm or more, or 13 μm or more. The average particle diameter (μm) of the particles 62 may be 20 μm or less, 19 μm or less, or 17 μm or less. The upper limit and the lower limit of the average particle size of the particles 62 may be combined arbitrarily with each preferable range. By setting the average particle diameter of the particles 62 in this manner, it becomes easier to achieve the above-described gloss characteristics according to the present embodiment. By setting the average particle diameter of the particles 62 in this manner, excellent tactile sensation can be obtained. By setting the average particle diameter of the particles 62 in this manner, desired gloss characteristics can be imparted. By setting the average particle diameter of the particles 62 in this manner, the particles 62 can be prevented from falling off from the binder resin 61 .

The particle diameter (μm) of the particles 62 is defined as the maximum width, that is, the maximum length of the particles in the longitudinal section of the decorative sheet. The average particle diameter (μm) of the particles 62 is obtained by observing a cross-sectional area in which five or more particles 62 are observed along the direction orthogonal to the normal direction of the decorative sheet, and observing the largest particle 62 in each cross-sectional area. , and specified as the average value (μm) of the particle diameters of the 30 particles 62 measured.

The average thickness (μm) of the peak portions 71M is specified as an average value of thicknesses T71 (see FIG. 2) of the peak portions 71M measured for 30 peak portions 71M.

A plurality of particles 62 included in the peak portion 71M may be in contact with each other within the peak portion 71M. As shown in FIG. 2, the plurality of particles 62 included in the peak 71M may be separated from each other. In the example shown in FIG. 2, the particles 62 are densely packed in the peak portion 71M, but the particles 62 do not form secondary particles by so-called agglomeration. A binder resin 61 exists between a plurality of particles 62 .

Also, the average particle diameter of the particles 62 is smaller than the average thickness of the peak portion 71M. Therefore, the particles 62 do not protrude greatly from the surface of the peak portion 71M. Thereby, the surface roughness of the peak portion 71M is suppressed. Diffusion at the peak portion 71M mainly depends on the overall shape and the overall projecting shape of the peak portion 71M. As a result, unlike conventional gloss characteristics that depend on diffusion by the particles 62 themselves, more complicated gloss characteristics of natural materials can be reproduced, and the 85° gloss value is likely to be lower than the 60° gloss value.

As shown in FIG. 3, the surface layer 50 includes a bulging portion 71 that does not satisfy the condition of the peak portion 71M described above but has a large thickness. The thickness of the bulging portion 71 other than the peak portion 71M may be less than 1.5 times the average thickness of the surface layer 50 at its top. The apex angle θt of the bulging portion 71 other than the peak portion 71M may be larger than 165°. The thickness of the bulging portion 71 is specified in the same manner as the thickness of the peak portion 71M described above. The apex angle θt of the bulging portion 71 is specified in the same manner as the apex angle θt of the peak portion 71M described above.

In the decorative sheet 20 shown in FIGS. 2 and 3 , regions other than the bulging portion 71 are trough portions 72 . In this example, valleys 72 have a thickness less than the average thickness of surface layer 50 . The density of the particles 62 in the valley portion 72 is lower than the density of the particles 62 in the swelling portion 71 . The mass ratio of the particles 62 in the valley portion 72 is smaller than the mass ratio of the particles 62 in the bulging portion 71 . As a result, the particles 62 protrude greatly from the binder resin 61 in the troughs 72 . The particles 62 can impart a tactile sensation and adjust gloss characteristics even in the valleys 72 . The particles 62 may be exposed from the binder resin 61 or may be covered with the binder resin 61 .

FIG. 4 is an enlarged photograph of the decorative sheet 20 having the cross section of FIGS. 2 and 3 taken from the normal direction. In FIG. 4, the pattern of the design layer 40 is observed in black. In FIG. 4 , the region observed in white is the valley portion 72 region. In FIG. 4, the area observed in brown is the area of the bulging portion 71 including the peak portion 71M. In the illustrated example, bulging portions 71 with a length of about 100 μm to 200 μm and valley portions 72 with a length of about 100 μm to 200 μm are dispersed in a plane. Particles 62 exposed in valleys 72 are also observed.

The area ratio of the region thinner than the average thickness of the surface layer 50, that is, the region of the valley portion 72, in the entire decorative sheet 20 may be 5% or more and 70% or less, or may be 10% or more and 60% or less. % or more and 50% or less. By setting such a ratio, desired gloss characteristics can be achieved.

The area ratio of the peak portion 71M to the entire decorative sheet 20 may be 5% or more and 40% or less, 10% or more and 35% or less, or 15% or more and 30% or less. By setting such a ratio, desired gloss characteristics can be achieved.

The average interval between peaks 71M may be 500 μm or less, 450 μm or less, or 400 μm or less. The average interval between peaks 71M may be 50 μm or more, 100 μm or more, or 150 μm or more. The upper limit and the lower limit of the average spacing of the peaks 71M may be arbitrarily combined with each preferable range. By setting the average interval of the peak portions 71M in this way, it becomes easier to achieve the above-described gloss characteristics according to the present embodiment. In addition, a suitable tactile sensation can be imparted.

The interval D71 (μm) between the peaks 71M is the interval between the tops 71t of two adjacent peaks 71M in the longitudinal section of the decorative sheet 20, as shown in FIG. The average interval (μm) of the peaks 71M is specified as the average value of the intervals of the peaks 71M measured at 30 locations. The interval (μm) and average interval (μm) for the bulging portion 71, which will be described later, are specified in the same manner as the interval (μm) and average interval (μm) for the peak portion 71M.

When the surface layer 50 contains particles 62, it is also assumed that the particles 62 fall off during use of the decorative sheet 20. If the particles 62 fall off, the decorative sheet 20 will not have a good tactile feel. As the particles 62 fall off, the gloss characteristics change. If the particles 62 fall off, the decorative sheet 20 cannot express the texture of natural materials. In order to suppress this problem, the rate of change in the 60° gloss value before and after the abrasion resistance test may be 30% or less, 25% or less, 20% or less, or 16% or less.

The rate of change in the 60° gloss value before and after the rub resistance test is the amount of change in the 60° gloss value after the rub resistance test from the 60° gloss value before the rub resistance test to the 60° gloss value before the rub resistance test. It is a ratio (%). That is, "change rate of 60 ° gloss value before and after rub resistance test" = (| "60 ° gloss value before rub resistance test" - "60 ° gloss value after rub resistance test" |) / "rubbing resistance test Previous 60° gloss value") x 100 (%). The abrasion resistance test is a rubbing test in which steel wool is rubbed against the surface of the decorative sheet to be evaluated. The steel wool is Bonster #0000 manufactured by Nippon Steel Wool Co., Ltd. In the abrasion resistance test, steel wool is pressed against the surface of the decorative sheet with a load of 300 g/cm ² . Steel wool is reciprocated on the surface of the decorative sheet (with a stroke of 120 mm 20 times).

As described above, the peak portion 71M and the bulging portion 71 contain multiple particles 62 . A plurality of particles 62 are fixed together by a binder resin 61 . In other words, according to the peak portion 71M and the bulging portion 71, the tactile sensation is imparted by the entire shape of the peak portion 71M and the bulging portion 71, and the tactile sensation is imparted by the overall shape of the ridge portion 71M and the bulging portion 71, without relying only on the tactile sensation imparted by the particles 62 projecting from the binder resin 61 and the light diffusion. Diffusion of light makes it possible to express the texture of natural materials. Therefore, it is not necessary to make the particles 62 protrude greatly from the binder resin 61 . According to such a configuration, it is possible to realize a preferable range of the rate of change of the 60° gloss value before and after the abrasion resistance test. Thereby, falling off of the particles 62 during use of the decorative sheet 20 can be suppressed. In addition, by making the average particle diameter of the particles 62 smaller than the average thickness of the ridges 71M, it is possible to further prevent the particles 62 from coming off.

It is also assumed that the particles 62 protrude greatly from the binder resin 61 in the troughs 72 . However, since the peaks 71M protrude more than the particles 62 in the valleys 72, falling off of the particles 62 in the valleys 72 can be suppressed.

The particles 62 contained in the surface layer 50 may be resin particles or inorganic particles. Examples of materials for the resin particles include acrylic resins, urethane resins, silicone resins, and polyamide resins such as nylon. Examples of inorganic particle materials include silica, alumina, zirconia, titania (titanium dioxide), kaolinite, calcium carbonate, barium sulfate, and the like. The particles 62 may be used alone or in combination of two or more. The particles 62 may be inorganic particles from the viewpoint of expressing the texture of natural materials with the decorative sheet 20 . Inorganic particles can suppress luster, thereby weakening the artificial impression.

The shape of the particles 62 may be spherical or irregular. The content of the particles 62 may be 10 to 50 parts by mass, 15 to 40 parts by mass, or 18 to 30 parts by mass with respect to 100 parts by mass of the binder resin.

The binder resin 61 may contain a thermoplastic resin. Examples of thermoplastic resins include acrylic resins, cellulose resins, urethane resins, vinyl chloride resins, polyester resins, polyolefin resins, polycarbonate, nylon, polystyrene, and ABS resins.

From the viewpoint of imparting excellent abrasion resistance to the surface layer 50, the binder resin 61 may contain a cured product of a curable resin composition. The ratio of the cured product of the curable resin composition to the total amount of the binder resin may be 50% by mass or more, 70% by mass or more, 90% by mass or more, or even 100% by mass. Examples of the cured product of the curable resin composition include a cured product of a thermosetting resin composition and a cured product of an ionizing radiation-curable resin composition. A cured product of the thermosetting resin composition is excellent in abrasion resistance and stain resistance. The cured product of the ionizing radiation-curable resin composition is excellent in abrasion resistance and stain resistance, and is also excellent in performance maintenance over time.

A thermosetting resin composition is a composition containing at least a thermosetting resin, and is a resin composition that is cured by heating. Examples of thermosetting resins include acrylic resins, urethane resins, acrylic urethane resins, phenol resins, urea melamine resins, epoxy resins, unsaturated polyester resins, and silicone resins. In addition to these thermosetting resins, a curing agent, a curing catalyst, and the like may be added to the thermosetting resin composition. The thermosetting resin composition may be a two-component curing composition in which the main agent is a polyol-based resin and the curing agent is an isocyanate-based compound. Examples of polyol-based resins include acrylic polyols and polyester polyols.

The ionizing radiation curable resin composition may be an electron beam curable resin composition or an ultraviolet curable resin composition. The electron beam curable resin composition does not require a polymerization initiator, so it is excellent in that it has little odor and is less likely to be colored.

The ionizing radiation-curable resin composition is a composition containing a compound having an ionizing radiation-curable functional group (hereinafter also referred to as an "ionizing radiation-curable compound"). The ionizing radiation-curable functional group is a group that is cross-linked and cured by irradiation with ionizing radiation. Examples of ionizing radiation-curable functional groups include functional groups having ethylenic double bonds such as (meth)acryloyl groups, vinyl groups, and allyl groups. Epoxy groups and oxetanyl groups are also exemplified as ionizing radiation-curable functional groups. As used herein, a (meth)acryloyl group refers to an acryloyl group or a methacryloyl group. As used herein, (meth)acrylate refers to acrylate or methacrylate. Ionizing radiation means electromagnetic waves or charged particle beams that have energy quanta capable of polymerizing or cross-linking molecules. The ionizing radiation may be ultraviolet (UV) or electron beam (EB). Ionizing radiation also includes electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams. Specifically, the ionizing radiation-curable compound is appropriately selected from polymerizable monomers and polymerizable oligomers (sometimes referred to as "polymerizable prepolymers") conventionally used as ionizing radiation-curable resins. may be

The ionizing radiation-curable compound is preferably a compound having two or more ethylenically unsaturated bond groups. The ionizing radiation-curable compound is more preferably a polyfunctional (meth)acrylate compound having two or more ethylenically unsaturated bond groups. Polyfunctional (meth)acrylate compounds may be either monomers or oligomers.

Among polyfunctional (meth)acrylate compounds, bifunctional (meth)acrylate monomers include ethylene glycol di(meth)acrylate, bisphenol A tetraethoxy diacrylate, bisphenol A tetrapropoxy diacrylate, 1,6-hexane. A diol diacrylate etc. are illustrated.

Trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol tetra (Meth)acrylates, isocyanuric acid-modified tri(meth)acrylates, and the like are exemplified.

Examples of polyfunctional (meth)acrylate oligomers include acrylate polymers such as urethane (meth)acrylate, epoxy (meth)acrylate, polyester (meth)acrylate, and polyether (meth)acrylate.

Urethane (meth)acrylates are obtained, for example, by reacting polyhydric alcohols and organic diisocyanates with hydroxy (meth)acrylates.

Preferred epoxy (meth)acrylates include (meth)acrylates obtained by reacting tri- or more functional aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with (meth)acrylic acid; (Meth)acrylates obtained by reacting aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, etc. with polybasic acids and (meth)acrylic acid, and bifunctional or higher aromatic epoxy resins, alicyclic It is a (meth)acrylate obtained by reacting a group epoxy resin, an aliphatic epoxy resin, or the like with a phenol and (meth)acrylic acid.

The ionizing radiation-curable resins may be used singly or in combination of two or more.

When the ionizing radiation-curable compound is an ultraviolet-curable compound, the ionizing radiation-curable resin composition may contain additives such as a photopolymerization initiator and a photopolymerization accelerator. Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, thioxanthones and the like. The photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and increase the curing speed. Examples of the photopolymerization accelerator include one or more selected from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, and the like.

The surface layer 50 may contain additives as necessary. Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, leveling agents, and the like.

For the surface layer 50, for example, a surface layer ink containing a material including a binder resin 61 and particles 62 constituting the surface layer 50 and a solvent added as necessary is applied onto the design layer 40, dried, and cured. can be made by

By the way, the surface layer 50 shown in FIGS. 2 and 3 includes a first layer 51 forming the surface 21 and a second layer 52 positioned between the first layer 51 and the design layer 40. there is The first layer 51 functions as a protective layer. The second layer 52 may function as a primer layer.

The second layer 52 as a primer layer may improve the adhesion of the first layer 51 to the design layer 40 . The primer layer is mainly composed of resin. The primer layer may contain additives such as ultraviolet absorbers and light stabilizers, if necessary. The second layer 52 as a primer layer may contain a thermoplastic resin. The thermoplastic resin can be the same as the thermoplastic resin used for the surface layer 50 described above. The second layer 52 as a primer layer may contain a cured product of a curable resin composition. A cured product of the curable resin composition can be produced in the same manner as the cured product of the curable resin composition used for the surface layer 50 described above.

The second layer 52 as a primer layer may contain an ultraviolet absorber and/or a light stabilizer in order to further improve weather resistance. The second layer 52 as a primer layer may contain a general-purpose ultraviolet absorber or a general-purpose light stabilizer. The thickness of the second layer 52 as a primer layer may be 0.01 μm or more and 5 μm or less, 0.7 μm or more and 5 μm or less, or 1 μm or more and 3 μm or less.

The first layer 51 may be a layer expected to function as the entire surface layer 50 described above. The first layer 51 as a protective layer may contain the same binder resin and particles as the binder resin and particles contained in the surface layer 50 described above. The first layer 51 as a protective layer may contain additives as necessary. Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, matting agents, leveling agents, and the like. The thickness of the first layer 51 as a protective layer may be 4 μm or more and 15 μm or less, 5 μm or more and 12 μm or less, or 6 μm or more and 10 μm or less.

The surface layer 50 shown in FIGS. 2-4 can be made by the method shown in FIG. 5, as an example.

First, as shown in FIG. 5A, a base material 25 on which a surface layer 50 is to be formed is prepared. The base material 25 may be a laminate including the base material 30 and the design layer 40 . The base material 25 is obtained by forming the design layer 40 on the base material 30 by printing. Next, as shown in FIG. 5B, a second layer resin composition 92 containing a thermoplastic resin is applied, and the coating film formed on the base material 25 is dried. A superimposed second layer 52 is obtained. After that, as shown in FIG. 5(c), a first layer resin composition 91 containing a cured product of the curable resin composition and particles 62 is applied, and the coating film obtained on the second layer 52 is cured. The first layer 51 is obtained by allowing the Thus, the surface layer 50 including the second layer 52 and the first layer 51 is obtained.

When the first layer 51 is formed, the surface layer 50 shown in FIGS. 2 to 4 is obtained by making the distribution of the particles 62 uneven on the second layer 52 . The density of the distribution of the particles 62 in the first layer 51 depends on the selection of materials for the curable resin and the particles 62, the surface treatment of the particles 62, the types and amounts of additives contained in the resin composition 91 for the first layer, and the coating. It can be adjusted by controlling the timing of curing the film, the curing speed of the coating film, and the like.

Further, the inventors confirmed that the distribution of the particles 62 in the first layer 51 could also be adjusted by selecting materials for the first layer 51 and the second layer 52 . This point will be described together with the conjectured mechanism, but the present embodiment is not bound by this conjecture.

The thermoplastic resin of the second layer resin composition 92 may contain a urethane resin or an acrylic urethane resin, and the curable resin composition of the first layer resin composition 91 may contain an acrylic resin or an acrylic urethane resin. good. Here, the acrylic urethane resin refers to a resin obtained by polymerizing isocyanate using acrylic polyol as a main component. In this example, the resin composition 92 for the second layer forms the second layer 52 as a thermoplastic resin layer containing urethane resin or a thermoplastic resin layer containing acrylic urethane resin. A first layer resin composition 91 is applied onto the second layer 52 . The first layer 51 obtained by curing the coating film of the first layer resin composition 91 on the second layer 52 had the configuration shown in FIGS.

Based on these results, it was inferred that the following phenomenon occurred. First, the second layer 52 containing thermoplastic urethane resin or thermoplastic acrylic urethane resin does not have sufficient solvent resistance. The thermoplastic resin of the second layer 52 is softened or dissolved by the acrylic resin or acrylic urethane resin contained in the resin composition 91 for the first layer. Then, at least the surface layer portion of the softened or dissolved second layer 52 is mixed with the curable resin in the first layer resin composition 91 . By mixing the uncured curable resin in the first layer resin composition 91 with the second layer 52, the ratio of the particles 62 to the first layer resin composition 91 forming the binder resin 61 increases. . At this time, the particles 62 flow together with the curable resin composition in the coating film formed by the resin composition 91 for the first layer, and the distribution of the particles 62 is uneven. As a result, it was presumed that the first layer 51 having the structure shown in FIGS. 2 to 4 was obtained.

Surface layer 50 may include an intermediate layer 55 between first layer 51 and second layer 52 . The intermediate layer 55 may contain a mixture of the curable resin contained in the first layer resin composition 91 and the thermoplastic resin contained in the second layer 52 . That is, the intermediate layer 55 can also be expressed as a portion of the second layer 52 into which the curable resin contained in the first layer resin composition 91 has permeated.

<Other layers>
The decorative sheet 20 may contain layers other than the base material 30 , the design layer 40 and the surface layer 50 . As other layers, the raised layer 45 and the adhesive layer are exemplified.

(Moriage layer)
As shown in FIG. 6 , the surface layer 50 of the decorative sheet 20 may further include a raised layer 45 . The raised layer 45 functions as an irregularity imparting layer and produces a strong tactile sensation.

As shown in FIG. 6 , the raised layer 45 may be positioned between the first layer 51 and the design layer 40 . In the example shown in FIG. 6, the raised layer 45 is located between the first layer 51 and the second layer 52 . The raised layer 45 has a raised portion 46 provided only in a region overlapping with a partial region of the design layer 40 . This build-up layer 45 may contain a binder resin and particles. The binder resin and particles contained in the build-up layer 45 may be the same as the binder resin and particles contained in the surface layer 50, respectively. The thickness of the raised layer 45 may be 15 μm or more and 70 μm or less, or may be 20 μm or more and 60 μm or less. According to the raised layer 45, the dispersedly arranged raised layer 45 can produce a strong tactile sensation. As a result, the decorative sheet 20 can more faithfully express the texture of the natural material.

The area where the raised portion 46 is provided may be arranged according to the design expressed by the design layer 40 . For example, the raised portion 46 may be arranged in a region where the late wood part of the annual ring overlaps with the late wood part or early wood part of the so-called floating grain pattern. A ridge 46 may be placed in an area overlapping the wood grain conduit portion or non-conduit portion having the conduit grooves. The raised portion 46 may be arranged in a region that overlaps the tile pattern or brick pattern joint groove portion having joint grooves or the non-joint groove portion.

(bonding layer)
The decorative sheet 20 may include a bonding layer 27, as indicated by a two-dot chain line in FIG. The bonding layer 27 is overlaid on the opposite side of the base material 30 to the design layer 40 . This bonding layer 27 constitutes the surface of the decorative sheet 20 opposite to the surface 21 . The base material 30 is positioned between the bonding layer 27 and the design layer 40 . The bonding layer 27 can be used when bonding the decorative sheet 20 to another member, for example, the decorative sheet 20 to the support member 15 . The bonding layer 27 is not particularly limited. The bonding layer 27 may be a layer of an adhesive material or an adhesive material.

This embodiment relates to the following [1] to [15].
[1] a surface layer that constitutes the surface;
and a design layer superimposed on the surface layer,
The 60° gloss value measured on the surface is 8 or less,
A decorative sheet, wherein the 85° gloss value measured on the surface is smaller than the 60° gloss value measured on the surface.
[2] The decorative sheet of [1], wherein the rate of change in the 60° gloss value before and after the abrasion resistance test is 30% or less.
[2A] The 60° gloss value measured on the surface after a rubbing test in which steel wool pressed against the surface with a load of 300 g / m ² is reciprocated 20 times with a stroke of 120 mm, and the surface before the rubbing test The ratio of the difference from the 60° gloss value measured in the above to the 60° gloss value measured on the surface before the rubbing test is 30% or less.
[3] The decorative sheet according to any one of [1] to [2A], wherein the surface has an 85° gloss value of 4 or less.
[4] The surface layer includes a first layer forming the surface and a second layer positioned between the first layer and the design layer,
The first layer includes a binder resin containing a cured product of a curable resin composition containing an acrylic resin or an acrylic urethane resin, and particles held by the binder resin,
The decorative sheet according to any one of [1] to [3], wherein the second layer contains a thermoplastic resin containing urethane resin or acrylic urethane resin.
[5] The surface layer contains a binder resin and particles,
The surface layer includes peaks having a thickness of 1.5 times or more the average thickness of the surface layer,
The mountain portion includes a plurality of particles,
The decorative sheet according to any one of [1] to [4], wherein the peak angle is 165° or less.
[6] The decorative sheet according to [5], wherein the peaks have an average interval of 500 μm or less.
[7] The decorative sheet of [5] or [6], wherein the average particle size of the particles is smaller than the average thickness of the peaks.
[8] The decorative sheet according to any one of [5] to [7], wherein the peak angle is greater than 120°.
[9] The surface layer includes a binder resin and particles,
The decorative sheet according to any one of [1] to [8], wherein the average particle size of the particles is larger than the average thickness of the surface layer.
[9A] The surface layer includes a first layer constituting the surface and a second layer positioned between the first layer and the design layer,
The first layer contains a binder resin and particles,
The decorative sheet according to any one of [1] to [9], wherein the average particle size of the particles is smaller than the average thickness of the first layer.
[10] The decorative sheet according to any one of [1] to [9A], wherein the surface layer has an average thickness of 5 μm or more and 20 μm or less.
[11] The surface layer includes a binder resin and particles,
The decorative sheet according to any one of [1] to [10], wherein the particles have an average particle size of 8 μm or more and 20 μm or less.
[12] The surface layer comprises a first layer constituting the surface, a second layer positioned between the first layer and the design layer, and a layer positioned between the first layer and the second layer. It is further equipped with a raised layer,
The decorative sheet according to any one of [1] to [11], wherein the raised layer includes a raised portion provided only in a region overlapping with a partial region of the second layer.
[13] a surface layer constituting the surface;
and a design layer superimposed on the surface layer,
The surface layer includes a first layer constituting the surface and a second layer positioned between the first layer and the design layer,
The first layer includes a binder resin containing a cured product of a curable resin composition containing an acrylic resin or an acrylic urethane resin, and particles held by the binder resin,
The second layer contains a thermoplastic resin containing urethane resin or acrylic urethane resin,
The average thickness of the surface layer is 5 μm or more and 20 μm or less,
The decorative sheet, wherein the particles have an average particle size of 8 μm or more and 20 μm or less.
[14] a surface layer constituting the surface;
and a design layer superimposed on the surface layer,
The surface layer contains a binder resin and particles,
The surface layer includes peaks having a thickness of 1.5 times or more the average thickness of the surface layer,
The mountain portion includes a plurality of particles,
The decorative sheet, wherein the peak angle is 165° or less.
[15] A step of forming a second layer containing a thermoplastic resin by coating a base material containing a design layer with a second layer resin composition containing a urethane resin or an acrylic urethane resin and drying the composition;
Applying a resin composition for the first layer containing a curable resin composition containing an acrylic resin or an acrylic urethane resin and particles having an average particle size of 8 μm to 20 μm onto the second layer and curing the composition. forming the first layer by
A method for producing a decorative sheet, wherein the surface layer including the first layer and the second layer has an average thickness of 5 μm or more and 20 μm or less.

EXAMPLES This embodiment will be described in more detail by way of examples. This embodiment is not limited to the following examples.

1. Preparation of Decorative Sheet Examples and Comparative Examples of decorative sheets were prepared as follows.

[Example 1]
A colored base paper for building materials (“CHPS45 (model number)”, basis weight: 45 g/m ² , manufactured by Tenma Tokushushi Co., Ltd.) was used as the base material. A resin composition for a colored layer containing a mixed resin of an acrylic resin and a urethane resin as a binder, and titanium white, red iron oxide and yellow lead as coloring materials was prepared. A colored layer having a thickness of 3 μm was formed by applying the resin composition for a colored layer to the surface of the base material that had been treated for easy adhesion by gravure printing. Next, a resin composition for pattern layer containing nitrocellulose as a binder and red iron oxide as a coloring material was prepared. By applying the resin composition for pattern layer onto the colored layer, a pattern layer with a wood grain pattern including conduit grooves was formed. A design layer was formed on the substrate by the colored layer and the design layer.

A second layer ink A1 containing a thermoplastic urethane resin having the following formulation was prepared. The second layer was formed by applying the ink A1 for the second layer to the entire surface of the design layer and drying it. The thickness of the second layer was 5 μm. Next, a first layer ink A1 containing an electron beam-curable acrylic resin having the following formulation was prepared. The ink A1 for the first layer was applied to the entire surface of the second layer by a roll coating method. After that, the coating film of the first layer ink A1 on the second layer was irradiated with an electron beam (applied voltage: 175 KeV, 5 Mrad (50 kGy)) to cure the coating film to form the first layer. . The average thickness of the first layer was 8 µm. A surface layer comprising a first layer as a primer layer and a second layer as a protective layer was obtained on the design layer. The average thickness of the surface layer was 13 μm.

<Ink A1 for second layer>
・ Thermoplastic urethane resin 100 parts by mass ・ Solvent appropriate amount

<Ink A1 for first layer>
・Electron beam curable polyfunctional acrylate resin: 100 parts by mass ・Inorganic particles: 20 parts by mass (spherical silica particles, average particle size 15 μm)
・Appropriate amount of solvent

The decorative sheet of Example 1 had the configuration shown in FIGS. That is, the surface layer of the decorative sheet of Example 1 included a bulging portion with a large thickness. The bulging portion was formed by fixing a plurality of particles with a binder resin. A part of the bulging portion constituted a peak having a thickness 1.5 times or more the average thickness of the surface layer and an apex angle θt of 165° or less. The apex angle θt of many peaks was greater than 120°. The average thickness of the peaks was 25 μm. The average interval between peaks was 340 μm.

[Example 2]
A decorative sheet of Example 2 was produced in the same manner as in Example 1, except that the amount of ink A1 for the first layer was reduced to form the first layer. The average thickness of the first layer was 4 μm. The average thickness of the surface layer was 9 μm.

The surface layer of the decorative sheet of Example 2 contained bulging portions with increased thickness. A part of the bulging portion was formed by fixing a plurality of particles with a binder resin. A part of the bulging portion constituted a peak having a thickness 1.5 times or more the average thickness of the surface layer and an apex angle θt of 165° or less. The number of particles contained in one crest in Example 2 was smaller than the number of particles contained in one crest in Example 1. The surface layer of Example 2 also contained bulges containing single particles. The apex angle θt of the peaks of Example 2 was smaller than the apex angle θt of the peaks of Example 1. When the thickness of the peaks containing a plurality of particles was measured at 30 points, the average thickness of the peaks was 22 μm. When the distance between the peaks containing a plurality of particles was measured at 30 points, the average distance between the peaks was 460 μm.

[Comparative Example 1]
A decorative sheet of Comparative Example 1 was produced in the same manner as in Example 1, except that the second layer was formed using the second layer ink B1 containing a two-component curable acrylic urethane resin. The thickness of the second layer was 5 μm. The average thickness of the surface layer was 13 μm.

<Second layer ink B1>
・Electron beam curable polyfunctional acrylic urethane resin: 100 parts by mass (main agent: acrylic polyol, curing agent: hexamethylene diisocyanate)
・Appropriate amount of solvent

The surface layer of the decorative sheet of Comparative Example 1 included bulging portions with increased thickness. There was also a bulging portion formed by fixing a plurality of particles with a binder resin. However, this bulging portion was gentle and did not constitute a crest. Specifically, in Comparative Example 1, the bulging portion containing a plurality of particles has a thickness less than 1.5 times the average thickness of the surface layer, or has an apex angle θt greater than 165°. was When the thickness of the bulging portion containing a plurality of particles was measured at 30 points, the average thickness of the bulging portion was 22 μm. When the distance between the bulging portions containing a plurality of particles was measured at 30 points, the average distance between the bulging portions was 340 μm.

[Comparative Example 2]
A decorative sheet of Comparative Example 2 was produced in the same manner as in Example 1, except that the first layer was formed using ink B2 for the first layer having an average particle size of 6 μm. The average thickness of the first layer was 8 µm. The average thickness of the surface layer was 13 μm.

<Ink B2 for first layer>
・Electron beam curable polyfunctional acrylate resin: 100 parts by mass ・Inorganic particles: 20 parts by mass (spherical silica particles, average particle diameter 6 μm)
・Appropriate amount of solvent

The surface layer of the decorative sheet of Comparative Example 2 included bulging portions with increased thickness. There was also a bulging portion formed by fixing a plurality of particles with a binder resin. However, this bulging portion was gentle and did not constitute a crest. Specifically, in Comparative Example 2, the bulging portion containing a plurality of particles has a thickness less than 1.5 times the average thickness of the surface layer, or has an apex angle θt greater than 165°. was When the thickness of the bulging portion containing a plurality of particles was measured at 30 points, the average thickness of the bulging portion was 20 μm. When the distance between the bulging portions containing a plurality of particles was measured at 30 points, the average distance between the bulging portions was 480 μm.

[Comparative Example 3]
A decorative sheet of Comparative Example 3 was produced in the same manner as in Comparative Example 2, except that the amount of the first layer ink B2 was reduced to form the first layer. The average thickness of the first layer was 4 μm. The average thickness of the surface layer was 9 μm.

The surface layer of the decorative sheet of Comparative Example 3 included bulging portions with increased thickness. Many of the bulges contained single particles held together by a binder resin. There was also a bulging portion formed by fixing a plurality of particles with a binder resin. However, this bulging portion was gentle and did not constitute a crest. Specifically, in Comparative Example 3, the bulging portion containing a plurality of particles had a thickness less than 1.5 times the average thickness of the surface layer, or had an apex angle θt greater than 165°. was When the thickness of the bulging portion containing a plurality of particles was measured at 30 points, the average thickness of the bulging portion was 12 μm. When the distance between the bulging portions containing a plurality of particles was measured at 30 points, the average distance between the bulging portions was 870 μm.

[Reference example]
A veneer made by slicing natural oak was prepared. This veneer is a plate material used for furniture and fittings, and was given a soap finish finish using soap.

2. Measurements and Evaluations Measurements and evaluations of the decorative sheets of Examples and Comparative Examples were performed as follows. The atmosphere during each measurement and evaluation was set at a temperature of 23±5° C. and a relative humidity of 40% or more and 65% or less. Moreover, before starting each measurement and evaluation, the target sample was exposed to the atmosphere for 30 minutes or more, and then the measurement and evaluation were performed.

Table 1 shows the average thickness of the surface layer (μm), the average particle size of the particles contained in the surface layer (μm), the average thickness of the ridges (μm), and the average spacing of the ridges (μm) for each example. ) is entered. Regarding the example in which the ridges did not exist, the columns for the average thickness of the ridges (μm) and the average interval between the ridges (μm) are shown in parentheses. The average thickness (μm) of the part and the average interval (μm) of the bulging part composed of a plurality of particles are entered.

<Gloss value measurement>
For each example, the gloss value on the surface formed by the surface layer of the decorative sheet was measured. The measured gloss values were 20° gloss value, 60° gloss value, and 85° gloss value. The gloss value conforms to JIS Z 8741 and is measured by BYK-Gardner's micro-TRI-gloss Cat. No. Measured using 4563. The 20° gloss value was measured with an incident angle of 20°. The 60° gloss value was measured with an incident angle of 60°. The 85° gloss value was measured with an incident angle of 85°. Table 1 shows the measurement results of the gloss values.

<Gloss characteristic evaluation>
Twenty subjects evaluated the gloss characteristics of the decorative sheets obtained in Examples and Comparative Examples. The 20 subjects were five people each in their 20s, 30s, 40s, and 50s. Each subject visually observed the decorative sheet from the surface layer side and evaluated whether or not the gloss property was excellent. The evaluation criteria for whether or not the glossiness was excellent was whether or not the decorative sheet had the same glossiness as the glossiness of the reference example. Table 1 shows the aggregated evaluation results of gloss characteristics classified according to the following criteria.
A: More than 18 out of 20 people answered that the gloss characteristics were excellent.
B: 15 or more and 17 or less out of 20 people answered that the gloss characteristics were excellent.
C: 11 or more and 14 or less out of 20 people answered that the gloss characteristics were excellent.
D: Less than 10 out of 20 people answered that the gloss characteristics were excellent.

<Tactile evaluation>
Twenty subjects evaluated the tactile sensation of the decorative sheets obtained in Examples and Comparative Examples. The 20 subjects were five people each in their 20s, 30s, 40s, and 50s. Each subject touched the surface layer of the decorative sheet with the pad of the index finger of the dominant hand, and evaluated whether the tactile sensation was excellent. The evaluation criteria for whether or not the tactile sensation was excellent was whether or not the tactile sensation obtained from the decorative sheet was the same as that obtained from the reference examples. Table 1 shows the aggregated evaluation results of tactile sensation classified according to the following criteria.
A: More than 18 out of 20 people answered that the tactile sensation was excellent.
B: 15 or more and 17 or less out of 20 people answered that the tactile sensation was excellent.
C: 11 or more and 14 or less out of 20 people answered that the tactile sensation was excellent.
D: Less than 10 out of 20 people answered that the tactile sensation was excellent.

<Comprehensive evaluation of texture>
With regard to the decorative sheets obtained in Examples and Comparative Examples, 20 test subjects comprehensively evaluated the texture of the decorative sheets in consideration of the tactile sensation, gloss characteristics, and the like. The 20 subjects were five people each in their 20s, 30s, 40s, and 50s. Each subject evaluated whether or not the texture of the decorative sheet was superior through tactile and visual senses. The evaluation criteria for whether or not the texture was excellent was whether or not the decorative sheet had a texture similar to that of the reference example. Table 1 shows the total evaluation results of the texture, classified according to the following criteria.
A: More than 18 out of 20 people answered that the texture was excellent.
B: 15 or more and 17 or less out of 20 people answered that the texture was excellent.
C: 11 or more and 14 or less out of 20 people answered that the texture was excellent.
D: Less than 10 out of 20 people answered that the texture was excellent.

<Scratch resistance evaluation>
The 60° gloss value was measured before and after the abrasion resistance test. As a rub resistance test, steel wool pressed against the surface with a load of 300 g/m ² was reciprocated 20 times with a stroke of 120 mm. The rate of change in the 60° gloss value was calculated from the 60° gloss values before and after the abrasion resistance test. The rate of change in the 60° gloss value is "the rate of change in the 60° gloss value before and after the abrasion resistance test" = (| "60° gloss value before the abrasion resistance test" - "60° gloss value after the abrasion resistance test" |)/“60° gloss value before abrasion resistance test”)×100 (%). The samples of each example had a rate of change of 35% or less, which is required for general use of decorative sheets. Table 1 shows the evaluation results classified according to the following criteria.
A: The rate of change in 60° gloss value was 25% or less.
B: The rate of change in 60° gloss value was 30% or less.
C: Change rate of 60° gloss value was 35% or less.
D: The rate of change in 60° gloss value exceeded 35%.

10: decorative material, 15: support material, 20: decorative sheet, 21: surface, 25: base material, 27: bonding layer, 30: base material, 40: design layer, 45: raised layer, 46: raised portion, 50 : surface layer, 51: first layer, 52: second layer, 55: intermediate layer, 61: binder resin, 62: particles, 71: swelling portion, 71t: top portion, 71m1: first average thickness position, 71m2: Second average thickness position, 71L1: first straight line, 71L2: second straight line, 71M: mountain portion, 72: valley portion, 91: resin composition for first layer, 92: resin composition for second layer, D1: First direction D1, D2: Second direction D2, D3: Third direction D3, θt: Vertical angle

Claims (15)

a surface layer that constitutes the surface;
and a design layer superimposed on the surface layer,
The 60° gloss value measured on the surface is 8 or less,
A decorative sheet, wherein the 85° gloss value measured on the surface is smaller than the 60° gloss value measured on the surface. 2. The decorative sheet according to claim 1, wherein the rate of change in 60[deg.] gloss value before and after the abrasion resistance test is 30% or less. 3. The decorative sheet according to claim 1, wherein the surface has an 85[deg.] gloss value of 4 or less. The surface layer includes a first layer constituting the surface and a second layer positioned between the first layer and the design layer,
The first layer includes a binder resin containing a cured product of a curable resin composition containing an acrylic resin or an acrylic urethane resin, and particles held by the binder resin,
The decorative sheet according to any one of claims 1 to 3, wherein the second layer contains a thermoplastic resin containing urethane resin or acrylic urethane resin. The surface layer contains a binder resin and particles,
The surface layer includes peaks having a thickness of 1.5 times or more the average thickness of the surface layer,
The mountain portion includes a plurality of particles,
The decorative sheet according to any one of claims 1 to 4, wherein the peak angle is 165° or less. 6. The decorative sheet according to claim 5, wherein the peaks have an average interval of 500 [mu]m or less. The decorative sheet according to claim 5 or 6, wherein the average particle size of the particles is smaller than the average thickness of the peaks. The decorative sheet according to any one of claims 5 to 7, wherein the peak angle is greater than 120°. The surface layer contains a binder resin and particles,
The decorative sheet according to any one of claims 1 to 8, wherein the average particle size of the particles is larger than the average thickness of the surface layer. The decorative sheet according to any one of claims 1 to 9, wherein the surface layer has an average thickness of 5 µm or more and 20 µm or less. The surface layer contains a binder resin and particles,
The decorative sheet according to any one of claims 1 to 10, wherein the particles have an average particle size of 8 µm or more and 20 µm or less. The surface layer includes a first layer constituting the surface, a second layer positioned between the first layer and the design layer, and a raised layer positioned between the first layer and the second layer. further comprising
The decorative sheet according to any one of claims 1 to 11, wherein the raised layer includes a raised portion provided only in a region overlapping with a partial region of the second layer. a surface layer that constitutes the surface;
and a design layer superimposed on the surface layer,
The surface layer includes a first layer constituting the surface and a second layer positioned between the first layer and the design layer,
The first layer includes a binder resin containing a cured product of a curable resin composition containing an acrylic resin or an acrylic urethane resin, and particles held by the binder resin,
The second layer contains a thermoplastic resin containing urethane resin or acrylic urethane resin,
The average thickness of the surface layer is 5 μm or more and 20 μm or less,
The decorative sheet, wherein the particles have an average particle size of 8 μm or more and 20 μm or less. a surface layer that constitutes the surface;
and a design layer superimposed on the surface layer,
The surface layer contains a binder resin and particles,
The surface layer includes peaks having a thickness of 1.5 times or more the average thickness of the surface layer,
The mountain portion includes a plurality of particles,
The decorative sheet, wherein the peak angle is 165° or less. A step of forming a second layer containing a thermoplastic resin by applying a second layer resin composition containing a urethane resin or an acrylic urethane resin to a base material containing a design layer and drying the composition;
Applying a resin composition for the first layer containing a curable resin composition containing an acrylic resin or an acrylic urethane resin and particles having an average particle size of 8 μm to 20 μm onto the second layer and curing the composition. forming the first layer by
A method for producing a decorative sheet, wherein the surface layer including the first layer and the second layer has an average thickness of 5 μm or more and 20 μm or less.

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