JP2023133013A - laminate - Google Patents

Abstract

To provide a laminate with excellent matting effect visibility and texture, and with a smooth tactile feel without snagging on a flat surface against hand movement.SOLUTION: The laminate has a substrate, a decoration layer and a matte layer in this order. A surface of the matte layer opposite to the decoration layer has an uneven shape comprising irregular wrinkles. In a measurement image obtained by measuring a measurement area (width 204 μm×length 272 μm) on the surface with a laser microscope (50-power objective lens), RSm (average length of curved elements) is 20.00 μm or more, and Sku (kurtosis) at a height of or above a reference plane in the measurement image is 4.00 or less.SELECTED DRAWING: None

Description

The present disclosure relates to a laminate.

Conventionally, for example, interior parts of buildings such as walls, ceilings, and floors; exterior parts such as outer walls, soffits, roofs, fences, and fences; window frames, doors, door frames, handrails, skirting boards, and surrounding edges. , fittings or fixtures for malls, etc. Also, general furniture such as chests of drawers, shelves, desks, etc.; kitchen furniture such as dining tables, sinks, etc.; decorative surface panels for cabinets, etc. of home appliances, OA equipment, etc.; interior or exterior parts of vehicles, etc. So-called decorative materials or decorative sheets are also used as articles to decorate and protect the surfaces of objects. As such decorative materials, for example, those having a surface layer having a desired function are used.

In order to improve the design of decorative materials used for these purposes, a method of improving the texture using a matte effect (also referred to as a "matte effect") is commonly used. As a decorative material using a matte effect, for example, Patent Document 1 discloses a material having a pattern layer and a concealing layer on one side of a base sheet, and a gloss adjusting layer such as a matte layer and a gloss layer on the other side. A decorative sheet is proposed. In the decorative sheet of Patent Document 1, the difference in gloss between the matte layer and the gloss layer of the gloss adjustment layer provides a design effect that brings out the pattern layer and the concealing layer. The layer uses a matte ink in which a total of 50 parts by weight of a matting agent of 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate is added to 100 parts by weight of resin.

Further, Patent Document 2 proposes a decorative material that has a printed layer and a transparent resin layer in this order on a base material, and has an embossed pattern on the outermost surface of the transparent resin layer.

Japanese Patent Application Publication No. 2000-062081 Japanese Patent Application Publication No. 2011-073207

As a method of improving the texture through a matting effect, a matting agent (also referred to as a "matting agent") is used as described in Patent Document 1, and the matting agent itself has a light diffusion effect to improve the texture. Main methods include a method of obtaining a dissipating effect, a method of forming an uneven shape on the outermost surface by embossing as in Patent Document 2 mentioned above, and the like.
However, when using a matting agent as in Patent Document 1, it is necessary to increase the amount of the matting agent used in order to improve the matting effect. It falls off from the paint film and damages the paint film, reducing its scratch resistance. Also, the loss of the matting agent causes changes in gloss, making scratches more noticeable, or contamination in the micro gaps at the interface between the matting agent and the resin. The surface properties tend to deteriorate due to the penetration of substances and the adsorption of contaminants to the matting agent itself, which reduces stain resistance. On the other hand, if the amount used is reduced in order to suppress the deterioration of the surface properties, the matting effect tends to decrease, and the surface properties and the matting effect are in an antinomic relationship. Therefore, there is a limit to the matte effect using matting agents.
Further, when embossing is used as in Patent Document 2, it takes a lot of time and effort to create a printing plate for embossing, which is not easy, and it is also necessary to prepare a printing plate for each desired pattern. Therefore, it cannot be said that this is a method that can easily respond to the diversity of customer demands.

By the way, customer demands are diverse, and they are now demanding not only the above-mentioned visual matte effect but also tactile expression. For example, when using a matting agent as in Patent Document 1, by increasing the amount used, the outline of the matting agent is exposed on the surface of the decorative sheet, resulting in a somewhat rough texture. There are cases where Further, when embossing is used as in Patent Document 2, a tactile sensation may occur due to the uneven shape of the surface formed by the embossing plate. However, in both cases, the focus is not on the expression of tactile sensation, and it cannot be said that sufficient expression of tactile sensation has been achieved. That is, conventional decorative sheets and materials cannot be said to have both an excellent matte effect and a good texture. In the present disclosure, among the tactile sensations, we particularly focused on "a tactile sensation that is pleasant to the touch", that is, "a tactile sensation that feels smooth on a flat surface without catching when the hand moves".

An object of the present disclosure is to provide a laminate that has excellent visibility and texture with a matte effect, does not catch on a flat surface when the hand moves, and has an excellent slippery feel. be.

In order to solve the above problems, the present disclosure
having a base material, a decorative layer and a matte layer in this order,
The surface of the matte layer opposite to the decorative layer has an uneven shape constituted by irregular wrinkles,
In the measurement image when measuring the measurement area (length 204 μm x width 272 μm) on the surface with a laser microscope (objective lens 50 times),
RSm (average length of curved elements) is 20.0 μm or more, and Sku (kurtosis) at a height above the reference plane in the measurement image is 4.0 or less.
laminate,
I will provide a.

According to the present disclosure, it is possible to provide a laminate that has excellent visibility and texture with a matte effect, is free from catching on a flat surface when the hand moves, and has an excellent slippery feel.

FIG. 1 is a schematic plan view showing an embodiment of a laminate of the present disclosure. FIG. 1 is a cross-sectional view showing an embodiment of a laminate of the present disclosure. FIG. 1 is a cross-sectional view showing an embodiment of a laminate of the present disclosure. This is a measurement screen of one measurement area (204 μm in length x 272 μm in width) on the surface of the laminate obtained in Example 1. This is a measurement screen of one measurement area (204 μm in length x 272 μm in width) on the surface of the laminate obtained in Example 2. This is a measurement screen of one measurement area (204 μm long x 272 μm wide) on the surface of the laminate obtained in Comparative Example 1. This is a measurement screen in which nine measurement areas on the surface of the laminate obtained in Example 1 are connected. This is a measurement screen in which nine measurement areas on the surface of the laminate obtained in Example 2 are connected. This is a measurement screen in which nine measurement areas on the surface of the laminate obtained in Comparative Example 1 are connected.

[Laminated body]
The laminate of the present disclosure will be described below. In addition, in this specification, numerical values related to "more than", "less than", and "~" in the description of numerical ranges are numerical values that can be arbitrarily combined, and the numerical values in the examples are numerical values that can be used as the upper and lower limits of the numerical range. It is.

The laminate of the present disclosure includes:
having a base material, a decorative layer and a matte layer in this order,
The surface of the matte layer opposite to the decorative layer The surface of the matte layer (which is also the surface opposite to the base material) may be simply referred to as the "surface") has an uneven shape composed of irregular wrinkles,
In the measurement image when measuring the measurement area (length 204 μm x width 272 μm) on the surface with a laser microscope (objective lens 50 times),
RSm (average length of curved elements) is 20.00 μm or more, and Sku (kurtosis) at a height above the reference plane in the measurement image is 4.00 or less.

[About surface shape]
First, the properties of the uneven shape (hereinafter also simply referred to as "surface shape") formed by irregular wrinkles on the surface of the matte layer of the laminate of the present disclosure will be described.
The surface shape of the laminate of the present disclosure has an uneven shape composed of irregular wrinkles, and when the measurement area (204 μm in length x 272 μm in width) on the surface was measured with a laser microscope (objective lens 50 times). In the measurement image, RSm (average length of curved elements) is 20.00 μm or more, and Sku (kurtosis) at a height above the reference plane in the measurement image is 4.00 or less. That is, in the laminate of the present disclosure, due to the presence of the uneven shape formed by irregular wrinkles, the surface properties of the RSm (average length of curved elements) and Sku (kurtosis) at a height above the reference plane are improved. is within a predetermined range.

These RSm (average length of curved elements), Rz (maximum height), which is the peak and height parameter of the contour curve described later, and Ra (arithmetic mean roughness), which is the parameter in the height direction of the contour curve, are , two-dimensional surface texture parameter, Sku (kurtosis) at a height above the reference plane is also called a three-dimensional surface texture parameter, and is a property obtained by analyzing the surface shape two-dimensionally or three-dimensionally, and depending on the degree of The visibility and texture of the fade effect, as well as the feel, can vary.
The laminate of the present disclosure has a surface shape in which the RSm (average length of curved elements) is 20.0 μm or more, and the Sku (kurtosis) at a height above the reference plane is 4.0 or less. Due to this property, it exhibits excellent visibility and texture with an excellent matte effect, and also has a tactile sensation that feels like it glides on a flat surface without getting caught when the hand moves. Hereinafter, "a tactile sensation that feels smooth on a flat surface when the hand moves without getting caught" may be referred to as a "sliding tactile sensation". Further, the "visibility and texture of the matte effect" may be hereinafter simply referred to as the "matte effect."

The tactile sensation of ``sliding on a flat surface with no catching in response to the movement of the hand'' is a sensual expression, but in this specification, ``the feeling of sliding on a flat surface without catching in response to the movement of the hand'' is a sensual expression. Generally, the tactile sensation includes all the tactile sensations that give the feeling of ``sliding on a flat surface without catching when the hand moves.'' More specifically, it refers to the tactile sensation you feel when you touch a smooth surface with the pads of your fingers while moving your hand. A similar tactile sensation to ``slippery'' is ``smooth tactile sensation,'' but ``smooth tactile sensation'' is closer to the tactile sensation of the surface of a dry object; They differ in that they have a tactile feel of a "smooth surface." Also, a tactile sensation similar to a ``slippery tactile sensation'' may include a ``moist tactile sensation,'' but the ``moist tactile sensation'' is closer to the tactile sensation of the surface of a wet object, with a slight ``catching'' sensation. It is different from a "slippery feel" in that it gives a feeling of slippery sensation.

It is difficult to generalize what has a "slippery feel" as it can vary depending on the surface treatment, and if it is a fabric (described later), the weaving method, etc., but for example, it is not a coated paper with a coated surface. Sateen weave using high-quality paper, fabrics such as oxford cloth using thin threads of 60 to 120 count, which are said to be from fine to extra-fine count, natural fibers such as silk and cotton, and synthetic fibers such as polyester and nylon. Examples include soft satin fabric, baby skin, etc. In addition, for example, fabrics such as natural fiber fabrics such as silk and Tencel (also referred to as "lyocell"); metals such as brass, gold, silver, copper, aluminum, steel, and stainless steel; among others, hairline processing, hairline processing, Items with various surface treatments such as silky blasting may also be cited as examples of items that may have a "slippery feel." Regarding surface treatments such as hairline processing and silky blasting on metals, there are some items that do not have a "smooth" feel depending on the degree of processing, but this does not include items that have undergone such processing. Not even. Furthermore, with regard to other fabrics, there are some that do not have a "slippery feel" depending on the thickness of the thread used, the weaving method, etc., but it goes without saying that such fabrics are not included.
Therefore, the laminate of the present disclosure is preferably used in applications where it is desired to express designs on the surfaces of these fabrics, metals, etc. In this case, the laminate of the present disclosure preferably has a decorative layer having a pattern on the surface of various materials such as cloth or metal so as to express a desired design. Details of the decorative layer included in the laminate of the present disclosure will be described later.

In the present disclosure, the surface texture of the surface of the laminate is a property that is analyzed from a measurement image obtained when a measurement area (204 μm in length x 272 μm in width) on the surface is measured using a laser microscope (objective lens magnified 50 times). This is the average value of the measured values measured in the nine measurement areas. Furthermore, the nine arbitrary locations may be located apart from each other, or may be close to or in contact with each other.
In addition, among these surface properties in one measurement area, RSm (average length of curved elements), Rz (maximum height) which is the peak and height parameter of the contour curve, and the height direction of the contour curve The two-dimensional surface texture parameter Ra (arithmetic mean roughness) is the vertical This is the average value of various surface textures obtained by measuring 8 cross sections in the direction and 7 cross sections in the transverse direction.

The surface texture measured as described above can be regarded as the surface texture of the surface shape of the laminate. This is because the surface texture measured in this manner satisfies the above-mentioned predetermined range, thereby providing a matte effect and a slippery feel.

(RSm (average length of curved elements))
RSm (average length of curved elements) obtained by the above measurement is RSm (average length of curved elements), which is a horizontal parameter of the contour curve, measured in accordance with JIS B0601:2013. RSm (average length of curved elements), which is a lateral parameter of the contour curve on the surface of the laminate of the present disclosure, is 20.00 μm or more. If the RSm is less than 20.00 μm, a matte effect and a slippery feel, especially a slippery feel, cannot be obtained.

RSm (average length of curve elements) is a parameter in the horizontal direction of the contour curve, and is the average length of the contour curve elements at the reference length. The smaller the value of RSm (average length of curved elements), the narrower the width of the convex portion, which is an index indicating that there is a tendency to have narrower convex portions. Therefore, if the RSm (average length of curved elements) is less than 20.00 μm, it tends to have many narrower convex portions, so roughness becomes noticeable and a slippery feel cannot be obtained. Considering this, RSm (average length of curved elements) is preferably 30.00 μm or more, more preferably 40.00 μm or more, and still more preferably 45.00 μm or more.

In addition, the larger the value of RSm (average length of curved elements), the wider the convex portion, and the surface shape has many wide convex portions, making it more likely that the hand will get caught on the plane when moving. It becomes easier. Considering this, the upper limit of RSm (average length of curved elements) is preferably 130.00 μm or less, more preferably 120.00 μm or less, and still more preferably 115.00 μm or less. When RSm (average length of curved elements) is within the above range, there will be a tendency to have many convex portions with appropriate widths, resulting in an improved matting effect as well as a slippery feel.
Note that in measuring RSm (average length of curved elements) in this specification, the cutoff value is 0.8 mm.

(Sku)
The Sku (kurtosis) obtained by the above measurement is the Sku (kurtosis) measured in accordance with ISO25178-2:2012, and serves as an index that indicates the degree of sharpness of the height distribution from the average plane. be. Sku (kurtosis) is a three-dimensional surface property parameter that is normally measured over the entire surface of the measurement area, and indicates the sharpness of the height distribution from the average surface over the entire surface. In this method, attention is paid to the Sku (kurtosis) at a height higher than the reference plane in the measurement image. That is, attention is focused on the degree of sharpness of the height distribution due to the convex portions at a height higher than the reference plane (which can also be called an average plane over the entire surface of the measurement area). When the surface of the laminate is touched with the hand, the convex portions that are not above the reference plane do not come into direct contact with the hand and do not easily contribute to the tactile sensation. Therefore, in the laminate of the present disclosure, by focusing on the shape of the convex portions above the reference surface, which are the convex portions that are directly touched when the surface is touched with the hand, the laminate can be slid more reliably. It is possible to obtain a pleasant tactile sensation. Note that in this specification, "Sku (kurtosis) at a height above the reference plane" is also simply referred to as "Sku (kurtosis)."

On the surface of the laminate of the present disclosure, Sku (kurtosis), which indicates the degree of sharpness of the height distribution from the reference plane at a height above the reference plane, is 4.0 or less. When Sku (kurtosis) exceeds 4.0, a matte effect and a slippery feel, especially a slippery feel, cannot be obtained.

When Sku (kurtosis) is 3, the surface shape becomes symmetrical (normal distribution) with respect to the reference plane for the entire surface, and when Sku exceeds 3, the height distribution has a sharp shape; This is a measurement value that indicates that the height distribution tends to have a collapsed shape when the value is less than . Therefore, the fact that Sku (kurtosis) at the height above the reference plane is 4.0 or less means that the height distribution (near the top of the convexity) of the convex part having a height above the reference plane is gentle. This means that there is a sharp shape (Sku (kurtosis) greater than 3 and 4.0 or less) or a crushed shape (Sku (kurtosis) less than 3). By having such a shape of the convex portion that is directly touched when the surface is touched with the hand, there is no catching on the plane when the hand moves, and a tactile sensation of sliding can be obtained.
On the other hand, when Sku (kurtosis) exceeds 4.0, the height distribution (near the top of the convex part) of the convex part having a height higher than the reference plane has a sharp shape, resulting in roughness. It becomes noticeable and you can no longer feel the slippery feel.

As mentioned above, the laminate of the present disclosure has an excellent matte effect and a slippery feel by having RSm (average length of curved elements) and Sku (kurtosis) within a predetermined numerical range. It will be done. That is, the laminate of the present disclosure has an uneven shape constituted by irregular wrinkles on the surface, which has a moderate width, and has many convex shapes that are gently pointed or flattened near the top. By adopting this shape, it has an excellent matte effect and a slippery feel.

As the Sku (kurtosis) increases, the shape near the top of the convex portion becomes sharper, so the roughness becomes more noticeable and the slippery feel decreases. Taking this into consideration, Sku (kurtosis) is preferably 3.9 or less, more preferably 3.7 or less, and even more preferably 3.5 or less in relation to the above-mentioned RSm (average length of curved elements). It is.
On the other hand, as the Sku (kurtosis) decreases, the shape near the top of the convex portion becomes gentler, so roughness is suppressed and the slippery feel is improved. Taking this into consideration, the lower limit of Sku (kurtosis) is preferably 1.0 or more, more preferably 1.5 or more, still more preferably 2.0 or more, even more preferably 2.2 or more.

As described above, the surface shape of the laminate of the present disclosure has a specific RSm (average length of curved elements) and Sku (kurtosis), and the specified RSm (average length of curved elements) It has the characteristics that the width of the convex part is moderate according to the Sku (Kurtosis), and the characteristic that the shape near the top of the convex part is a gently pointed or flattened shape according to the Sku (kurtosis) regulation.
The surface shape of the laminate of the present disclosure has convex portions with a moderate width that are gently pointed or crushed near the top, so that when the surface is touched with the pad of a finger, a moderate contact can be achieved. Frequently, a gently pointed or collapsed tip shape can be felt. It is thought that this kind of sensation leads to a tactile sensation that feels like it is sliding on a flat surface without getting caught when the hand moves. In addition, the presence of such convex portions results in relatively concave portions, which is thought to provide a matte effect. Details regarding the development of the matte effect will be described later.

The surface shape of the laminate of the present disclosure has an uneven shape constituted by irregular wrinkles that are visible in a plan view shown in FIG. 1, which will be described later. Regarding the surface shape of the laminate of the present disclosure, RSm (average length of curved elements) and Sku (kurtosis), preferably Rz (maximum height) and Ra (arithmetic mean roughness) described below, are RSm (average length of curved elements). Average length) makes it easier to fall within a specific numerical range. On the other hand, the uneven shape formed by irregular wrinkles has RSm (average length of curved elements) and Sku (curtosis) within a specific numerical range, preferably Rz (maximum height) and Ra (arithmetic mean), which will be described later. roughness) makes it easier to form. In this way, it can be said that RSm (average length of curved elements), Sku (kurtosis), etc., and the uneven shape formed by irregular wrinkles are two sides of the same coin. By having such a surface shape, the matting effect is improved as well as the slippery feel.

In the surface shape of the laminate, in order to set RSm (average length of curved elements) and Sku (kurtosis) within the above specific numerical range, preferably Rz (maximum height) and Ra (arithmetic mean roughness), which will be described later. As mentioned above,
(1) Forming an uneven shape composed of irregular wrinkles on the surface of the matte layer,
That is essential. for that purpose,
(2) Composition of the resin composition for forming a matte layer, especially the types of polymerizable monomers and polymerizable oligomers, number of functional groups, molecular weight, presence or absence of a wrinkle-forming stabilizer, and wrinkle formation if a wrinkle-forming stabilizer is used. Optimize the particle size and content of the agent,
(3) Optimize the irradiation conditions for the resin composition for matte formation, especially the wavelength of light with a wavelength of 100 nm or more and 380 nm or less that can cure and shrink the surface portion of the matte layer, integrated weight, ultraviolet output density, etc.
(4) In addition to the above, optimize the type and thickness of the base material, the thickness of the matte layer, etc.
It is preferable. By optimizing these, regarding the surface shape of the laminate of the present disclosure, RSm (average length of curved elements) and Sku (kurtosis) can be set within the above specific numerical ranges, and preferably Rz (maximum height ) and Ra (arithmetic mean roughness) can be easily kept within predetermined numerical ranges.

(Rz (maximum height))
It is preferable that the surface shape of the laminate of the present disclosure has an Rz (maximum height) of 5.00 μm or more. In the present disclosure, Rz (maximum height) is a horizontal parameter of the contour curve defined in JIS B0601:2013, and is one of the peak and height parameters of the contour curve. More specifically, it is the sum of the height of the highest peak and the depth of the deepest valley among the contour curves at the reference length.
The larger the value of Rz (maximum height) is, the larger (higher) the shape of the convex portions as seen from the valley is, and this is an index indicating that there is a tendency for more such convex portions to exist. Therefore, in a surface shape that satisfies the above-mentioned RSm (average length of curved elements) and Sku (kurtosis), if Rz (maximum height) is 5.00 μm or more, convexity according to the above-mentioned Sku (kurtosis) regulation will occur. The feature that the shape near the top of the part is gently pointed or flattened is emphasized, and the slippery feel is improved. The matting effect is also improved.

Rz (maximum height) is preferably 5.25 μm or more, more preferably 5.50 μm or more, even more preferably 6.00 μm or more, even more preferably 6.25 μm or more, and preferably 20.00 μm or less as an upper limit. , more preferably 18.00 μm or less, still more preferably 15.00 μm or less. When Rz (maximum height) is within the above range, the matte effect and slippery feel are improved.
Note that in measuring Rz (maximum height) in this specification, the cutoff value is 0.8 mm.

(Ra (arithmetic mean roughness))
The surface shape of the laminate of the present disclosure preferably has an Ra (arithmetic mean roughness) of 3.00 μm or less. In the present disclosure, Ra (arithmetic mean roughness) is one of the parameters in the height direction of the contour curve specified in JIS B0601:2013, and is the height difference from the average surface in the contour curve at the standard length. It is an average value. This is an index indicating that the smaller the numerical value of Ra (arithmetic mean roughness), the smaller the convex portions in the surface shape and the smaller the concave portions formed accordingly, which tends to result in a smoother and more uniform shape. Therefore, in a surface shape that satisfies the above RSm (average length of curved elements) and Sku (kurtosis), if Ra (arithmetic mean roughness) is 3.00 μm or less, the shape of the convex portions of the surface shape is improved. Since there are more uniform and gentle textures, an unusual tactile sensation is suppressed, and especially a slippery tactile sensation is improved. The matting effect is also improved.

Ra (arithmetic mean roughness) is preferably 2.80 μm or less, more preferably 2.60 μm or less, even more preferably 2.40 μm or less, and the lower limit is preferably 0.10 μm or more, more preferably 0.40 μm or more. , more preferably 0.60 μm or more. When Ra (arithmetic mean roughness) is within the above range, the matte effect and slippery feel are improved.
Note that in measuring Ra (arithmetic mean roughness) in this specification, the cutoff value is 0.8 mm.

[About layer structure]
The laminate of the present disclosure includes a base material, a decorative layer, and a matte layer in this order, and has the layer structure shown in FIG. 2. In addition, from the viewpoint of responding more flexibly to various required performances according to various demands, such as mechanical strength, suitability for post-processing, and design appearance, as well as suitability for manufacturing and handling, as shown in Figure 3, Also included are laminates formed by laminating layers other than the base material, the decorative layer, and the matte layer.
Each layer constituting the laminate of the present disclosure will be explained below, starting from the base material.

〔Base material〕
The form (or shape) of the base material forming the laminate of the present disclosure is not particularly limited, and is preferably selected from various shapes such as a film, sheet, plate, polyhedron, polygonal prism, cylinder, sphere, and spheroid. Can be adopted. Here, a film, a sheet, and a board are referred to as a film, a sheet, and a board based on their relatively thin thickness, but in this specification, there is no particular significance in strictly distinguishing between these three, and the film, sheet, and board are , the difference between sheets and boards shall not cause any difference in the interpretation of rights in this disclosure. Therefore, in this specification, films, sheets, and plates may be collectively referred to as "sheets", "sheet-like", etc.
The shape of the base material of the laminate of the present disclosure is preferably sheet-like. When the base material is in the form of a sheet, suitability for manufacturing is improved because it is easy to provide a matte layer, which will be described later, and suitability for post-processing is improved because it is easy to integrate, for example, with a resin molded product by pasting.

The constituent material of the base material is not particularly limited, and various materials such as resins, metals, nonmetallic inorganic materials, fibrous materials, and wood-based materials can be appropriately selected depending on the purpose. It is possible to use a single layer of base materials made of these various materials, or a plurality of layers made of a combination of two or more layers of base materials made of these various materials. In the case of multiple layers, two or more layers of different materials can be laminated and integrated to complement the various functions of the materials of each layer.

When adopting a multi-layer base material, each layer constituting the multi-layer is referred to as "A/B", for example, a laminate formed by laminating a layer made of material A and a layer made of material B. When writing;
(1) Resin/wood material (2) Resin/metal (3) Resin/fibrous material (4) Resin/nonmetallic inorganic material (5) Resin 1/Resin 2 (for example, "olefin resin/acrylic resin", etc.) (In case of having multiple layers composed of different resins)
(6) Metal/wood material (7) Metal/non-metal inorganic material (8) Metal/fibrous material (9) Metal 1/Metal 2 (for example, multiple materials made of different metals such as "copper/chromium") layer)
(10) Preferred embodiments include nonmetallic inorganic materials/fibrous materials.
In addition, when the base material has multiple layers, an adhesive layer, a pressure-sensitive adhesive layer, and a primer layer (also called an anchor layer and an easy-to-adhesion layer) are added between each of the multiple layers to improve the adhesion of each adjacent layer. ).

Examples of resins that can be used for the base material include various synthetic resins and natural resins. Examples of the synthetic resin include thermoplastic resins and curable resins, and thermoplastic resins are preferable in consideration of suitability for manufacturing the laminate, suitability for handling, suitability for post-processing, and the like.

Examples of thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; polyethylene Polyester resins such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester thermoplastic elastomer; polymethyl poly(meth)acrylate, poly(meth)ethyl acrylate, poly( Acrylic resins such as butyl meth)acrylate and methyl (meth)acrylate-butyl (meth)acrylate copolymers; Polyamide resins such as nylon 6 and nylon 66; Celluloses such as cellulose triacetate, cellophane, and celluloid. Resin: Styrene resin such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin); Polovinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin , polyarylate resin, polyimide resin, etc. are preferably mentioned.
Preferable examples of the natural resin include natural rubber, pine resin, amber, and the like.
Further, as the curable resin, thermosetting resins, ionizing radiation curable resins, etc., which are exemplified as constituent materials of the matte layer described later, are preferably mentioned.

Examples of metals that can be used for the base material include aluminum or aluminum alloys such as aluminum and duralumin; iron or iron alloys such as iron, carbon steel, and stainless steel; copper or copper alloys such as copper, brass, and bronze; gold, silver Preferred examples include chromium, nickel, cobalt, tin, and titanium. Further, as the base material made of metal, those whose surfaces are coated with these metals by plating or the like are also preferably mentioned.

Examples of non-metallic inorganic materials that can be used as the base material include non-ceramic ceramic materials such as cement, ALC (lightweight cellular concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramics such as ceramics, earthenware, glass, and enamel. Material: Natural stones such as limestone (including marble), granite, andesite, etc. are preferably mentioned.

Examples of fibrous materials that can be used as the base material include tissue paper, kraft paper, high-quality paper, Japanese paper, titanium paper, linter paper, parchment paper, paraffin paper, parchment paper, glassine paper, backing paper for wallpaper, paperboard, and gypsum board. Paper such as base paper; preferred examples include woven or nonwoven fabrics made of polyester resin fibers, acrylic resin fibers, protein or cellulose-based natural fibers such as silk, cotton, and hemp, fibers such as glass fibers, and carbon fibers. Among these materials, acrylic resin, Various resins such as styrene-butadiene rubber, melamine resin, and urethane resin may be added (impregnated with these resins after papermaking or filled in during papermaking). Preferred examples of the paper to which resin is added include interpaper reinforced paper, resin-impregnated paper, and the like.
In addition, as a laminate formed by laminating a layer composed of a fibrous material and a layer composed of a resin, a vinyl chloride resin layer, an olefin resin layer, a vinyl chloride resin layer, an olefin resin layer, etc. Preferred examples include raw wallpapers in which layers made of various resins such as acrylic resin layers are laminated.

Examples of wood-based materials that can be used as the base material include veneers, plywood, and laminated wood made of various woods such as cedar, cypress, pine, zelkova, oak, oak, walnut, lauan, teak, and rubber wood. Preferred examples include particle board and medium density fiberboard (MDF).

As the base material, any base material made of the above-mentioned materials can be used without limitation, and it may be selected as appropriate depending on the desired properties and the like. From the viewpoint of improving the matting effect and the slippery feel, a base material made of a resin or a fibrous material is preferable, and a base material made of a resin is more preferable.
Among the resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferred, olefin resins, vinyl chloride resins, and polyester resins are more preferred; as olefin resins, polyethylene and polypropylene are preferred; as vinyl chloride resins, polyvinyl chloride is preferred. Preferably, the polyester resin is polyethylene terephthalate. Moreover, among the fibrous materials, paper is preferable. By using a base material made of these materials, it is particularly easy to obtain the above-mentioned surface shape, and it becomes easy to improve the slippery feel.

The shape and dimensions of the base material consisting of a single layer or a laminate are not particularly limited and may be appropriately selected in consideration of the intended use, desired performances, suitability for post-processing, and the like.
When adopting the shape of a film, sheet, or plate, the thickness is a typical dimension in the design of the laminate, but there is no particular restriction on the thickness. In consideration of economic efficiency and the like, the thickness may preferably be selected from the range of 10 μm or more and 10 cm or less. When adopting a film or sheet shape, it is preferably selected from a range of 20 μm or more and 300 μm or less, and when a plate shape is employed, it is preferably selected from a range of 1 mm or more and 2 cm or less.

The base material is selected from the viewpoint of improving adhesion with other layers constituting the laminate, such as the matte layer described below, and adhesion with adherends such as resin molded products on which the laminate is laminated. One surface can be subjected to physical surface treatment such as an acid value method or a roughening method, or surface treatment to improve adhesion properties such as chemical surface treatment.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, etc., and examples of the roughening method include sandblasting, solvent treatment, and the like. These surface treatments may be appropriately selected depending on the type of substrate, and corona discharge treatment is preferred from the viewpoint of the effect of surface treatment on improving adhesion and workability.

The base material may be colored or uncolored (may be transparent), and if it is colored, there is no particular restriction on the manner of coloring, and it may be transparently colored, Opaque coloring (concealing coloring) may be used, and these can be selected arbitrarily.

When the base material is colored, examples of colorants include white pigments such as titanium white, inorganic pigments such as iron black, yellow lead, titanium yellow, Bengara, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. , isoindolinone yellow, phthalocyanine blue, nickel-azo complex, azomethine azo black pigment, perylene black pigment, and other organic pigments or dyes; metal pigments made of flaky foil pieces of aluminum, brass, etc.; titanium dioxide-coated mica, bases Examples include coloring agents such as pearlescent pigments made of scaly foil pieces such as lead carbonate. For example, if the surface hue of adherend materials such as resin molded products on which the laminate is laminated varies, and you want to hide the surface hue and improve the stability of the color tone of the decorative layer provided as desired, , an inorganic pigment such as a white pigment may be used.

When coloring a base material made of resin, use any of the following methods: adding a coloring agent to the resin (kneading, kneading), or forming a film of paint containing the resin and colorant. Can be done. When coloring a base material made of a fibrous material such as paper, woven fabric, or nonwoven fabric, it can be carried out by any means such as mixing with pulp or fibrous material, or by forming a coating film, or by a combination of these methods.
When a base material made of a wood-based material is colored, it can be carried out by dyeing with a dye, forming a coating film, or a combination thereof. When coloring a metal base material, in addition to coating film formation, an electrolytic coloring method in which a metal oxide film is formed on the surface using an anodic oxidation method can be employed. Further, when a base material made of a non-metallic inorganic material is colored, it can be carried out by forming a coating film, adding it into the base material, or a combination thereof.

Additives may be added to the base material, if necessary. Additives are mainly used for resins, such as inorganic materials such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. etc. The blending amount of the additive is not particularly limited as long as it does not impede the surface properties, processing properties, etc., and can be appropriately set according to the required properties.

From the viewpoint of improving the weather resistance of the laminate of the present disclosure, it is preferable to use weathering agents such as ultraviolet absorbers and light stabilizers among the above additives.
Examples of the ultraviolet absorber and light stabilizer include those listed below as those that can be included in the matte layer.
These UV absorbers, weathering agents such as light stabilizers, and other various additives can be used alone or in combination.

In the present disclosure, the above-mentioned base materials can be used alone or in combination. It may be a combination of multiple paper base materials, a paper base material and a fiber base material, a paper base material and a resin base material, a fiber base material and a resin base material, a paper base material, a fiber base material and a resin base material. It may also be a combination of materials. Further, the resin base material may have a single layer structure of the above-mentioned resin base material or a multilayer structure made of the same or different resins.

The thickness of the base material is as described above, but when the base material is a film or sheet of the above resin, it is preferably 20 μm or more, and the upper limit is preferably 300 μm or less, and it is suitable for manufacturing, handling, post-processing, and Considering mechanical strength, economic efficiency, etc., the thickness is more preferably 40 μm or more, more preferably 200 μm or less as an upper limit, and still more preferably 100 μm or less.
For the same reason, when the base material is paper, the basis weight is usually preferably 20 to 150 g/m ² , more preferably 30 to 100 g/m ² .

[Matte layer]
The matte layer in the laminate of the present disclosure is a layer provided on the decorative layer described below, and its surface has the above-mentioned surface shape, that is, an uneven shape constituted by irregular wrinkles, and has an RSm (curvilinear element). It is a layer having a surface shape in which the average length) is 20.00 μm or more and the Sku (kurtosis) is 4.00 or less. Moreover, as shown in FIGS. 2 and 3, the layer is provided so that the surface having the surface shape is the surface opposite to the base material side.
Therefore, since the laminate of the present disclosure has a matte layer on its surface, considering the mechanical strength, manufacturing suitability, etc. of the laminate, the matte layer is a cured product of a resin composition, preferably a cured product. The layer is preferably formed of a cured product of a curable resin composition containing a resin.

The above-mentioned resin composition forming the matte layer may be a resin composition containing a resin and a wrinkle formation stabilizer ( (hereinafter sometimes referred to as "resin composition for forming a matte layer") is preferred. That is, in the present disclosure, the matte layer is preferably a layer containing a resin and a wrinkle formation stabilizer.

(Wrinkle formation stabilizer)
The wrinkle formation stabilizer stabilizes the formation of irregular wrinkles on at least one surface of the matte layer, thereby developing an uneven shape constituted by irregular wrinkles. The visibility of the matte effect is uniformly expressed over the entire surface of the matte layer, and local unevenness of gloss is reduced, resulting in stable visibility of the matte effect and the entire surface of the matte layer. It has the function of imparting uniformity to the surface condition by stably forming irregular wrinkles over the entire surface. The irregular wrinkles of the matte layer also greatly contribute to the development of a slippery feel. In this specification, "stable visibility of matting effect" may be expressed as "stable visibility of matting effect" or similar expressions hereinafter. Further, "uniformity of surface state" is sometimes referred to as "texture."
Therefore, even if the so-called "matting agent" in the prior art and the "wrinkle formation stabilizer" in the present disclosure have the same constituent materials and the same average particle diameter, the matting mechanism (effect) of both is the same. They differ in the relationship between the structure for producing matteness, the amount used, and the degree of surface gloss (gloss value). It also differs from a "matting agent" in that it produces a slippery feel by forming irregular wrinkles.

In the conventional technology such as Patent Document 1 mentioned above, the matting agent that has been used for matte expression is one that itself exhibits the visibility of the matte effect due to the light diffusion effect caused by its physical shape. It is. Specifically, what is generally called a matting agent generally has a difference in refractive index between the matting agent particles and the surrounding resin and air, and the reflection and refraction of light rays corresponds to the contour shape of the particles. The visibility of the matte effect is achieved by the light diffusion effect by the interface. On the other hand, in the laminate of the present disclosure, the wrinkle-forming stabilizer does not produce the visibility of a matting effect due to light diffusion due to reflection and refraction of light rays by the particles themselves, but due to the wrinkle-forming stabilizer. By stabilizing the formation of irregular wrinkles on the surface of the eraser layer, the light diffusion effect at the refractive index difference interface between the surface and air stably imparts the visibility of the matte effect and texture to the laminate. That is what it is. Therefore, the wrinkle-forming stabilizer used in the present disclosure is different from the matting agent that itself exhibits the visibility of the matting effect, even if the constituent substances and average particle diameter of the two are the same. The mechanism and action of matting, the structure for producing matting, etc. are different.

Furthermore, the "wrinkle formation stabilizer" and the "matting agent" also differ in the relationship between content and surface gloss (gloss value). 60° gloss value G of the surface when the same substance A is used as a wrinkle formation initiator AW (W: wrinkle, wrinkle) and is contained in a specific amount C to form wrinkles on the surface G _60° ^AW (C) is clearly lower than the 60° gloss value G _60° ^AM (C) of the surface when the same substance A is used as a mere matting agent AM and no wrinkles are formed on the surface even if it is contained in a specific amount C. . That is, the following relational expression holds true.
G _60° ^AW (C)<G _60° ^AM (C)

The matte layer in the laminate of the present disclosure may contain an agent conventionally used as a matting agent, but it is possible to stably obtain an extremely excellent matting effect that cannot be obtained even with the use of a matting agent. Considering the characteristics of the effect of the invention that a smooth and slippery feel can be obtained, it is preferable that no matting agent is included. As described above, the laminate of the present disclosure has extremely excellent visibility and texture of a matte effect even if it does not substantially contain a matting agent that has been conventionally used to obtain visibility of a matte effect. It can be said that it is a thing. Here, "not containing a matting agent" means not only that it does not contain any matting agent at all, but also that even if it does contain a matting agent, it does not have the visibility of a matting effect based on the action and effect of the matting agent itself. , specifically means that the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, more preferably 3.0 parts by mass or less, based on 100 parts by mass of the resin. .
In addition, in this specification, the "matting agent" specifically refers to the thickness of the layer that can contain the matting agent, that is, the thickness of the matting layer, from the viewpoint of forming convex portions by the cueing effect as described above. It means particles having an average particle diameter with the lower limit being either more than 100% of the diameter or more than 30 μm, whichever is smaller.

In the present disclosure, the wrinkle formation stabilizer is particularly limited as long as it is not a matting agent and has an average particle diameter of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. It can be used without
Considering the improvement of the matting effect and slippery feel, the average particle size of the wrinkle-forming stabilizer whose upper limit is 100% or less of the thickness of the matting layer or 30 μm or less, whichever is smaller, is It is preferable to use at least one of two types of wrinkle-forming stabilizers that are differentiated by particle size. Specifically, the two types of wrinkle-forming stabilizers are wrinkle-forming stabilizer 1 whose average particle diameter is 1 μm or more and whose upper limit is 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. , and Wrinkle Formation Stabilizer 2 having an average particle diameter of less than 1 μm.

In the present disclosure, by using at least one of the two types of wrinkle formation stabilizers, the formation of irregular wrinkles can be stabilized, an excellent matting effect can be stably obtained, and a slippery feel can also be obtained. . In the present disclosure, wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used alone, or wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 can be used together. It is more preferable to use wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2 together. When used together, the matte effect and slippery feel are improved.

As the wrinkle formation stabilizer, for example, organic particles or inorganic particles can be used.
Examples of organic substances constituting the organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine resin, and polyester resin. etc.
Examples of the inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, and barium sulfate, and among these, silica is preferred because of its excellent transparency.

The shape of the wrinkle-forming stabilizer is not particularly limited, and examples thereof include spherical, polyhedral, scaly, amorphous, and the like.

The upper limit of the average particle diameter of the wrinkle formation stabilizer 1 is 1 μm or more and 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. Considering stably improving the matting effect and improving the slippery feel, the average particle diameter of the wrinkle-forming stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably is 1.8 μm or more, and the upper limit is preferably 90% or less of the thickness of the matte layer, more preferably 80% or less of the thickness of the matte layer, More preferably, it is 70% or less of the thickness of the matte layer, and the absolute value is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, even more preferably 7 μm or less. The upper limit for the thickness and the upper limit for the absolute value may be arbitrarily combined, whichever is smaller. For example, the upper limit may be 90% or less of the thickness of the matte layer and 20 μm or less, whichever is smaller, or the upper limit may be 90% or less of the thickness of the matte layer or 10 μm or less, whichever is smaller. You can also do it. Note that the thickness of the matte layer will be described later.

The average particle size of the wrinkle formation stabilizer 2 is less than 1 μm. Considering that the formation of irregular wrinkles is stabilized, the matting effect is stably improved, and the slippery feel is improved, the average particle diameter of the wrinkle formation stabilizer 2 is preferably 1 nm or more, and more preferably 1 nm or more. Preferably it is 3 nm or more, more preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm or less, still more preferably 500 nm or less.
In this specification, the average particle diameter of the wrinkle-forming stabilizer is measured as a volume average value d50 in particle size distribution measurement using a laser beam diffraction method.

Considering that the wrinkle formation stabilizer stabilizes the formation of irregular wrinkles, stably improves the matting effect, and improves the slippery feel, it is recommended that the wrinkle formation stabilizer (wrinkle formation stabilizer 1 and wrinkle formation stabilizer When used together with Formation Stabilizer 2, the total content of these is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass, based on 100 parts by mass of the resin forming the matte layer. It is at least 1.0 parts by mass, more preferably at least 1.0 parts by mass, even more preferably at least 1.2 parts by mass. On the other hand, the upper limit is preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, even more preferably 10.0 parts by mass or less, even more preferably 7.5 parts by mass or less, particularly preferably 6 .0 part by mass or less. There is no particular limit on the upper limit in terms of improving stable matte effect and improving slippery feel, but if the upper limit is within the above range, for example, coating of a resin composition for forming a matte layer will be difficult. The productivity of decorative materials due to its properties, etc., and the visibility and texture of the matte effect are efficiently improved.

When Wrinkle Formation Stabilizer 1 and Wrinkle Formation Stabilizer 2 are used together, there are no particular restrictions on the content of each of Wrinkle Formation Stabilizer 1 and Wrinkle Formation Stabilizer 2, as long as the total content is within the above range. However, the content of the wrinkle formation stabilizer 2 is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more, based on 100 parts by mass of the resin. The upper limit is preferably 10.0 parts by mass or less, more preferably 7.5 parts by mass or less, still more preferably 5.0 parts by mass or less, even more preferably 3.5 parts by mass or less. Further, the blending ratio of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 is preferably 5.0 to 95.0 as the blending amount of wrinkle-forming stabilizer 1 when the total amount of these is 100 parts by mass. Parts by weight, more preferably 10.0 to 90.0 parts by weight, still more preferably 15.0 to 75.0 parts by weight, even more preferably 30.0 to 50.0 parts by weight.

As the wrinkle formation stabilizer, organic particles and inorganic particles can be used as mentioned above, but the types of these particles themselves may include those conventionally used as matting agents, for example, as described in the above patent document. A matting agent such as spherical alumina or calcium carbonate is used in the matte layer of the decorative sheet described in Item 1. In order for a matting agent such as spherical alumina or calcium carbonate to exhibit the visibility of a matting effect by itself due to the light diffusion effect caused by its physical shape, as described in Patent Document 1, It is necessary to use the resin in a total content of about 50 parts by weight, including 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of the resin. However, in the present disclosure, as described above, even if the content is small, that is, the content is necessary to express the visibility of the matte effect by itself due to the light diffusion effect caused by the physical shape. Even with a lower content, an extremely superior matting effect compared to the effect obtained with a matting agent is obtained, and a slippery feel is also obtained.
Therefore, even though the laminate of the present disclosure does not substantially contain a matting agent, irregular wrinkles are stably formed on the surface, which is superior to the case where a matting agent is used. It can be said that the visibility of the matte effect is stably obtained, and at the same time, the texture is also obtained, and it is also possible to obtain a slippery feel.

(Surface shape of matte layer)
The matte layer in the laminate of the present disclosure is a layer having the above-mentioned surface shape, and is preferably made of a cured product of a resin composition for forming a matte layer containing the above-mentioned specific wrinkle-forming stabilizer in a specific content. It is a layer composed of As mentioned above, by stabilizing the formation of irregular wrinkles on the surface of the matte layer, a stable matte effect is produced due to the light diffusion effect caused by the shape of the wrinkles, and a slippery feel is also created. It becomes the layer to do. FIG. 1 is a schematic plan view showing one embodiment of the laminate of the present disclosure, and is a schematic representation of an image of the surface of the laminate obtained in an example. FIG. 1 shows that the laminate of the present disclosure has irregular wrinkles formed on its surface, that is, the surface of the matte layer. Here, "planar view" means viewing the surface of the laminate from the positive direction of the Z-axis in the XYZ coordinate system shown in FIGS. 1 to 3.

Irregular wrinkles appearing on at least one surface of the matte layer are based on the above-mentioned surface shape, that is, RSm (average length of curved elements) and Sku (kurtosis) within the above-mentioned specific numerical range, preferably other Rz (maximum height) and Ra (arithmetic mean roughness). It is stable in formation, stably exhibits a matting effect, and also exhibits a slippery feel.
Regarding irregular wrinkles, in order to obtain an excellent matting effect and a slippery feel, at least one surface of the matting layer needs to have an uneven shape constituted by irregular wrinkles. In order to improve the matte effect as well as the slippery feel, irregular wrinkles are formed by a plurality of protrusions formed by a plurality of protrusions and a recess formed by being surrounded by a plurality of protrusions. The protrusion preferably has a linear protrusion. In this specification, a "striated protrusion" (hereinafter also referred to as "striated protrusion") means that the ratio of length to width (length/width) of the protrusion is 3 or more, preferably 5. The above means more preferably 10 or more, and the method for determining the length and width will be described later.
In the present disclosure, more preferable irregular wrinkles are those constituted by a plurality of protrusions formed by a plurality of linear protrusions and a recess formed by being surrounded by a plurality of linear protrusions.

An example of the aspect regarding these irregular wrinkles is the aspect shown in FIG. 1, for example. FIG. 1 shows that the surface of the laminate, that is, the surface of the matte layer, has irregular wrinkles in plan view, and that the irregular wrinkles are formed by a plurality of curved linear protrusions. It is configured by including a plurality of convex parts 3 and a concave part 2 formed by being surrounded by a plurality of protrusions (a plurality of convex parts 3), and that at least a part of the plurality of curved convex parts 3 is formed. It is also shown that the meandering recesses 2 are each formed by meandering linear protrusions and are surrounded by the meandering linear protrusions. The laminate of the present disclosure stably exhibits a matting effect due to the stable formation of irregular wrinkles shown in FIG. 1, and also exhibits a slippery feel.

Here, "curved" means having one or more portions where the extending direction of the continuous filamentous convex portions 3 is reversed from one side to the other side in plan view. As an example of a portion where the extending direction is reversed from one side to the other side, for example, when the width of the planar view shape of the linear convex portion 3 is ignored (when the width of the planar view shape is considered to be 0) When approximated by a continuous curve, examples include forms having inflection points. In addition, when the width of the linear convex portion 3 in plan view is approximated by a straight line, it has a portion that is approximated by a V-shaped broken line or two sides sandwiching one vertex of a triangle. etc.

Furthermore, "meandering" refers to a portion where the extending direction of the convex portions 3 of continuous filaments is reversed from one side to the other side (hereinafter also referred to as "reversed portion") in plan view. It has a portion where the extending direction of the filamentous protrusion 3 is alternately reversed in two adjacent places when the filamentous protrusion 3 is advanced in its extending direction. It means that. For example, when the width of the linear convex portion 3 in plan view is approximated by a continuous curve, there is a form having a portion approximated by the Roman letter "S". Further, when the width of the linear convex portion 3 in plan view is approximated by a straight line, there may be a form having a portion approximated by the Roman letter "W".

As used herein, "irregular" means a shape that has a certain rule, or a shape that cannot be said to be arranged according to a certain rule, that is, a pattern. A typical example of a non-irregular shape, that is, a regular shape, is a so-called "lenticular lens" in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to the longitudinal direction of the unit lenses. Examples include shapes arranged with a certain periodicity in a specific direction, such as "lenticular lenses". Therefore, the irregular wrinkles in the present disclosure mean that the shape of one protrusion itself is irregular rather than a shape that is formed according to a certain rule such as periodicity, and that the shape of one protrusion itself is irregular, and that it is caused by a plurality of protrusions formed by a plurality of protrusions. This includes the fact that the shape of the part is not formed and arranged according to a fixed rule but is irregular, and that the shape of the recess surrounded by such a plurality of protrusions is also irregular. .
In the laminate of the present disclosure, the shape itself of one protrusion (one protrusion), the shape and arrangement of each of the plurality of protrusions (the plurality of protrusions), and the shape of the recess surrounded by the plurality of protrusions. If any of these are irregular, a matte effect and a slippery feel can be obtained by having irregular wrinkles, but it is preferable that both of them be irregular. By having irregular wrinkles, the laminate of the present disclosure improves the visibility and texture of its matte effect, stably exhibits an extremely excellent matte effect, and exhibits a slippery feel. Become something.

As described above, the matte layer has an uneven shape constituted by irregular wrinkles on at least one surface thereof. The convex portions and concave portions in the uneven shape are defined as, for example, by using the difference in brightness between images on the surface of the laminate of the present disclosure, the darkest part in the density distribution image is set to gradation 255, and the lightest part in the density distribution image is set to gradation 255. Assuming that the tone is 0, the gradations 0 to 255 may be divided by binarization processing such that the gradations 0 to 127 are concave portions and the gradations 128 to 255 are convex portions.

The surface of the laminate of the present disclosure only needs to have an uneven shape made up of irregular wrinkles on at least a part thereof, and preferably has an uneven shape made up of irregular wrinkles over the entire surface. There is no particular restriction on the location where irregular wrinkles are formed (i.e., the location where the matte layer is present) as long as it is on the surface of the laminate. It produces a matte effect and a slippery feel. For example, if an uneven shape formed by irregular wrinkles (i.e., a matte layer) is formed on a part corresponding to the pattern of the decorative layer, for example, on a pattern layer, the pattern will appear as a part where the pattern is more matte than the surrounding area. Since it is visible, it is possible to improve the design quality. In this case, there will be areas where the matte layer is provided and areas where it is not provided, but as long as the above surface properties are satisfied, a matte effect and a slippery feel can be obtained.

Further, as shown in FIG. 1, it has a plurality of protrusions formed by a plurality of irregular but uniform protrusions, and a recess surrounded by the protrusions. is preferred. Therefore, a shape in which the width of the first convex part (protrusion) changes drastically is difficult to achieve the above-mentioned surface shape, is not a preferable form for obtaining the visibility and texture of the matte effect, and is not suitable for slipping. This cannot be said to be a preferable embodiment for obtaining such a tactile sensation. Regarding the shape of the convex portions (protrusions) and concave portions that form irregular wrinkles, specific aspects that can be advantageous in stably improving the matting effect and improving the slippery feel are explained below. do. When the irregular wrinkles have the following shape, the above-mentioned surface shape is easily exhibited, and the matte effect and slippery feel are improved.

Regarding the uneven shape formed by irregular wrinkles formed on at least one surface of the matte layer, the height of the protrusions (height of the protrusions) is preferably 0.5 μm or more, more preferably 1 μm or more. , more preferably 2 μm or more, and the upper limit is about 10 μm or less. Further, the width of the convex portion is preferably 0.1 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, and even more preferably 3 μm. It is as follows. When the height and width of the convex portions are within the above ranges, the surface shape described above is easily exhibited, and in relation to the concave portions, the matting effect is stably improved and the slippery feel is improved.
Here, the above-mentioned dimensions of the convex portions are the average values of arbitrary ten convex portions (protrusions) at ten arbitrary locations (100 μm square area x 10 locations) of the laminate of the present disclosure, that is, a total of 100 convex portions. It is. In addition, as shown in Figure 1, the width of the protrusion (protrusion) 1 is not the same, but is wide and narrow, so the width of the protrusion (protrusion) 1 is the same as the width of the protrusion (protrusion) 1. The average value of the widths at five arbitrary locations in . The same applies to the height of the convex portion (protrusion).

The depth of the recess is preferably 0.5 μm or more, more preferably 1 μm or more, even more preferably 2 μm or more, and the upper limit is about 10 μm or less. Further, the width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more, and the upper limit is preferably 10 μm or less, more preferably 3 μm or less, and still more preferably 2 μm or less. It is. When the depth and width of the concave portions are within the above ranges, the surface shape described above is easily exhibited, and in relation to the convex portions, the matting effect is stably improved and the slippery feel is improved.
Here, the dimensions of the concave portion are determined in the same manner as the dimensions of the convex portion described above.

The distance from the top of the convex part to the bottom of the concave part, that is, the height difference between the convex part and the concave part, is preferably 1 μm or more, more preferably 2 μm or more, even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably Preferably it is 8 μm or less, more preferably 7 μm or less. When the distance is within the above range, the surface shape described above is easily exhibited, the matting effect is stably improved, and the slippery feel is improved.
Here, the dimensions of the concave portion are determined in the same manner as the dimensions of the convex portion described above.

The occupation ratio of the convex portion is preferably 15% or more, more preferably 20% or more, even more preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, and still more preferably 60% or less. It is. When the proportion of the convex portions is within the above range, the surface shape described above is easily exhibited, and in relation to the proportion of the concave portions surrounded by the convex portions, the matting effect is stably improved and the surface has a slippery feel. will improve.
Here, the occupancy rate of the convex portions is the average value of the occupancy rate of the convex portions at arbitrary 10 locations (100 μm square area x 10 locations) of the laminate of the present disclosure.

The convex portions and the concave portions may have portions having substantially the same direction and substantially the same width, but in consideration of improving the matte effect and improving the slippery feel, it is preferable that the length thereof be short. Specifically, the continuous length of convex portions and concave portions having approximately the same direction and approximately the same width is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, and the lower limit is preferably 5 μm or more, More preferably, it is 10 μm or more, and still more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, so that the matting effect is stably improved and the slippery feel is improved.
Here, 80% or more of arbitrary 10 protrusions and depressions (i.e., a total of 100 protrusions and depressions) at 10 arbitrary locations (100 μm square area x 10 locations) of the laminate of the present disclosure It is preferable that the condition is satisfied, more preferably 85% or more, still more preferably 90% or more, even more preferably 95% or more. In addition, in this specification, "substantially" in "substantially the same" means approximately the same, without branching, and in the case of direction, it means a difference within ±3°, and in the case of width, it means ±5 Means a difference within %.

The number of convex portions (protrusions) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, even more preferably 30 or more, and the upper limit is preferably 200 or less, more preferably 100 or less, and Preferably it is 70 or less. When the number of convex portions is within the above range, the matting effect is stably improved and the slippery feel is improved.
The number of convex portions is the average value of the number of convex portions at 10 locations (area of 100 μm square x 10 locations) of the laminate of the present disclosure.

FIG. 2 is a sectional view showing an embodiment of the laminate of the present disclosure, and is a sectional view of the laminate 1 taken along a plane parallel to its thickness direction. The thickness direction of the laminate 1 is the Z direction in FIG.
The shape of the recess may be, for example, an acute angle as shown in 2a of FIG. 2, a semicircle or a semiellipse as shown in 2b, or a combination thereof. Alternatively, a shape such as 2c in FIG. 2 may be used, in which one convex portion has a concave portion in part.
On the other hand, the shape of the convex portion is semicircular or semielliptic, although the width may be wide or narrow as shown in 3a and 3b in FIG.

The thickness of the matte layer is not particularly limited as long as it can stably produce a matte effect and form the above-mentioned irregular wrinkles to the extent that it can provide a slippery feel. However, considering ease of production, etc., it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, even more preferably 4 μm or more, even more preferably 5 μm or more, and preferably 300 μm or less as an upper limit. , more preferably 200 μm or less, still more preferably 150 μm or less, even more preferably 100 μm or less.
In this specification, the thickness of the matte layer is determined by measuring the thickness at 20 locations from an image taken using a scanning electron microscope (SEM) on the cross section of the laminate, and taking the average value of the values at 20 locations. . Note that the accelerating voltage of the SEM is 3 kV, and the magnification is set according to the thickness. The same applies to the thicknesses of other layers.

The matte layer is a layer that exhibits the above-mentioned surface shape on its entire surface, and since the laminate of the present disclosure only needs to have the surface shape on at least a portion of the surface, at least a portion of the surface of the laminate It may be provided on the entire surface thereof.
If the matte layer is provided in a location where the consumer can see and touch the laminate, that is, if the surface shape is provided in a location where the consumer can see and touch the laminate, the matte layer will be matte. The effects of the invention, such as a dissipating effect and a slippery feel, can be obtained.

Furthermore, even when the base material is in the form of a film, sheet, or plate, the matte layer only needs to be provided at a location in the laminate that is visible and touched by the consumer, and at least one of the surfaces thereof is From the viewpoint of improving the matte effect and the slippery feel, as shown in FIGS. 2 and 3, it may be provided over the entire surface of one side. It is preferable that the

(resin)
The resin forming the matte layer may be a resin that forms a matte layer-forming resin composition containing a predetermined amount of the above-mentioned wrinkle-forming stabilizer and becomes a cured product by curing. good. Examples of such resins include ionizing radiation-curable resins. The matte layer is a layer that can be provided on the outermost surface of the laminate of the present disclosure, as also shown in FIGS. 4 to 6. Therefore, in addition to being a resin that easily forms wrinkles due to wrinkle-forming stabilizers, it also has surface properties such as processing properties, stain resistance, scratch resistance, and weather resistance, in order to improve usability as a laminate. It is preferable that the resin be easily cured, and ionizing radiation-curable resins are preferable resins from these viewpoints. In the laminate of the present disclosure, since the content of the wrinkle-forming stabilizer contained in the matte layer is extremely small, the performance of the resin forming the matte layer is more directly exhibited as a surface property. .

The ionizing radiation-curable resin is a resin having an ionizing radiation-curable functional group, and the ionizing radiation-curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, such as a (meth)acryloyl group, a vinyl group, Preferred examples include functional groups having an ethylenic double bond such as allyl groups. In addition, in this specification, a (meth)acryloyl group shows an acryloyl group or a methacryloyl group. Moreover, in this specification, (meth)acrylate refers to acrylate or methacrylate.
In addition, ionizing radiation refers to electromagnetic waves or charged particle beams that have energy quantum that can polymerize and/or crosslink molecules, and ultraviolet (UV) or electron beam (EB) are usually used. In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.

Ionizing radiation curable resins include electron beam curable resins and ultraviolet ray curable resins. Considering that the wrinkle formation stabilizer stabilizes the formation of wrinkles, stably improves the matting effect, and improves the slippery feel, ultraviolet curable resins are preferred.
Specifically, the ionizing radiation-curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation-curable resins.

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and it is preferable to use at least a polyfunctional monomer, especially a polyfunctional (meth)acrylate monomer. Here, "(meth)acrylate" means "acrylate or methacrylate".
Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and at least a (meth)acryloyl group as the ionizing radiation-curable functional group. It will be done.

Considering that it stabilizes the formation of wrinkles, stably improves the matting effect, improves the slippery feel, and further improves surface properties such as post-processing properties, scratch resistance, and weather resistance. The number of functional groups of the polyfunctional (meth)acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less. Further, when the number of functional groups is as described above, the above-mentioned surface shape is particularly easily obtained, and the slippery feel is easily improved.
These polyfunctional (meth)acrylates may be used alone or in combination.

In addition, in order to particularly improve the slippery feel, it is preferable to use a monofunctional monomer in combination with the above-mentioned polyfunctional monomer. As the monofunctional monomer, a (meth)acrylate monomer having a (meth)acryloyl group as an ionizing radiation-curable functional group is preferable, similarly to the polyfunctional monomer.

Examples of the polymerizable oligomer include polyfunctional oligomers having two or more ionizing radiation-curable functional groups in the molecule, preferably polyfunctional (meth)acryloyl groups having at least (meth)acryloyl groups as ionizing radiation-curable functional groups. Examples include acrylate oligomers. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers.
In addition, other polymerizable oligomers include highly hydrophobic polybutadiene (meth)acrylate oligomers that have (meth)acrylate groups in their side chains, and silicone (meth)acrylate oligomers that have polysiloxane bonds in their main chains. , aminoplast resin (meth)acrylate oligomers modified from aminoplast resins with many reactive groups in small molecules, and molecules of novolak-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers having cationically polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination.
Examples of polymerizable oligomers include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, and acrylic (meth)acrylate oligomers. Acrylate oligomers are preferred, urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred. By using these polymerizable oligomers, it is possible to stabilize the formation of wrinkles, stably improve the matting effect, improve the slippery feel, and further improve post-processing properties, scratch resistance, and Surface properties such as weather resistance can be improved.

The number of functional groups in these polymerizable oligomers is preferably 2 or more and 8 or less, and the upper limit is more preferably 6 or less, and even more preferably 4 or less. When the number of functional groups is within the above range, the formation of wrinkles can be stabilized, the matting effect can be stably improved, the slippery feel can be improved, and the processing properties, scratch resistance and Surface properties such as weather resistance can be improved.
Furthermore, for the same reason, the weight average molecular weight of these polymerizable oligomers is preferably 900 or more and 7,500 or less, more preferably 1,000 or more and 7,000 or less, and 1,200 or more and 6,000 or less. More preferably, it is 1,400 or more and 2,900 or less. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted to standard polystyrene.

In the present disclosure, as the resin forming the matte layer, it is preferable to use a combination of the above polymerizable oligomer and polymerizable monomer. In this case, the polymerizable oligomer is preferably a polyfunctional urethane (meth)acrylate oligomer, more preferably a polyfunctional urethane acrylate oligomer. Furthermore, as the polymerizable monomer, it is preferable to use at least a monofunctional monomer, more preferably a combination of a monofunctional monomer and a polyfunctional monomer, and a monofunctional (meth)acrylate monomer and a polyfunctional (meth)acrylate monomer. It is more preferable to use them in combination. It can stabilize the formation of wrinkles, stably improve the matting effect, and improve the slippery feel, and can also improve surface properties such as processing characteristics, scratch resistance, and weather resistance. .
When used in combination, for the same reason, the content of the polymerizable oligomer relative to 100 parts by mass of the total of the polymerizable oligomer and the polymerizable monomer is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and Preferably 20 parts by mass or more, even more preferably 25 parts by mass or more, and the upper limit is preferably 60 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass or less, even more preferably 35 parts by mass. It is as follows.

(Resin composition)
The matte layer is preferably constituted by a cured product of a resin composition containing the wrinkle formation stabilizer in a predetermined content, and the resin composition preferably contains the resin and the wrinkle formation stabilizer in a predetermined content. It is included in In addition to the wrinkle formation stabilizer and resin described above, the resin composition used in the present disclosure may contain other components depending on desired performance and the like.

When the resin is an ultraviolet curable resin that is cured by ultraviolet light, it preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. By including these additives, the resin can be cured even with ultraviolet rays (without using ionizing radiation), and surface properties useful for practical use can be obtained.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyl oxime ester, thioxanthone, and the like.
In addition, the photopolymerization accelerator can reduce polymerization inhibition caused by air during curing and accelerate the curing speed, and includes, for example, p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester, etc. One or more types may be selected.

Since the matte layer is a layer that can be provided on the outermost surface of the laminate of the present disclosure, it is preferably a layer that has weather resistance, and may contain various weather resistance agents such as ultraviolet absorbers and light stabilizers. preferable.
As the UV absorber, any UV absorber commonly used in decorative materials, decorative sheets, etc. can be used without particular restrictions, such as benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, hydroxyphenyl, etc. Examples include triazine-based ultraviolet absorbers. As the light stabilizer, any light stabilizer commonly used in decorative materials, decorative sheets, etc. can be used without particular limitation, and examples thereof include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers. Further, these ultraviolet absorbers and light stabilizers may have a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, vinyl group, or allyl group in the molecule.
These weathering agents such as ultraviolet absorbers and light stabilizers can be used alone or in combination.

[60° gross value and 85° gross value]
The laminate of the present disclosure is a laminate with excellent matte effect visibility and texture. In this specification, "matte" means that the gloss is difficult to visually recognize, and it cannot be said unconditionally because it varies depending on the color tone, pattern, etc. of the laminate, but for example, the 60° gloss value is 20.0 or less, preferably If it is about 10.0 or less, it is generally treated as "matte".

Until now, for laminates exhibiting black or other dark colors, it has been possible to obtain excellent visibility with a 60° gloss value of 20.0 or less, preferably 10.0 or less, even if a matting agent is used. It was. Here, "dark color" means low brightness, for example, the L ^* value in the CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* color system measured in accordance with JIS Z8781-4:2013 (hereinafter referred to as (sometimes simply referred to as "L ^* value") is usually about 40 or less, preferably 30 or less.
However, since a large amount of matting agent is used, streaks and unevenness occur during layer formation, so it is not easy to manufacture, and the surface properties deteriorate. For example, for laminates exhibiting black or other tones other than dark colors, even if a matting agent is used, there is a lower limit to the 60° gloss value, which is the same as for laminates exhibiting black, and in any case, the surface properties may be affected. It has not been possible to easily obtain a laminate that is excellent in visibility and texture of the matte effect. Such a tendency becomes more pronounced as the 60° gross value becomes smaller.

In the laminate of the present disclosure, by using a wrinkle-forming stabilizer in combination with a predetermined average particle diameter and by controlling the content to a small amount as described above, an extremely excellent matting effect can be stably visually recognized. Not only has a good texture and texture been achieved, but a slippery feel has also been achieved. In addition, by keeping the amount of wrinkle-forming stabilizer used to an extremely small amount, it is possible to suppress a significant increase in the viscosity of the resin composition, making it easier to form a layer, and achieving excellent results according to the characteristics of the resin used for the matte layer. It naturally has surface properties such as stain resistance, scratch resistance, and weather resistance.

As mentioned above, the laminate of the present disclosure cannot be absolutely defined because it changes depending on the color tone, but for example, if the laminate exhibits black or other dark color, the 60° gloss value on the matte layer side is 10.0. Further, the visibility of the matte effect is extremely excellent with the following values: 7.5 or less, 5.0 or less, 4.0 or less, and 3.5 or less.

Further, a laminate exhibiting a color tone other than black or other dark color may also have the above-mentioned 60° gloss value. The 60° gloss value of the matte layer side of the laminate of the present disclosure is substantially the same as the 60° gloss value of the surface of the layer forming the outermost surface of the laminate, unless there is another layer. , which is the 60° gloss value of the surface of the matte layer. In the case where the layer further includes another layer and is provided on the surface side of the matte layer, the 60° gloss value means the 60° gloss value of the other layer, but the laminate of the present disclosure The specific 60° gloss value of is essentially due to the structure of the matte layer.
In this specification, the 60° gloss value on the matte layer side refers to the 60° specular gloss measured in accordance with JIS K 5600-4-7:1999, and is measured using a gloss meter, etc. at any 10 locations. This is the average value of the values that can be measured from the matte layer side using this method.

Further, the laminate of the present disclosure has an 85° gloss value of preferably 25.0 or less, more preferably 20.0 or less, and can be treated as "matte" from this point as well. Note that when the 85° gloss of the laminate of the present disclosure is extremely low, for example, less than about 7.0, the matte layer has irregularities other than irregular wrinkles, such as macroscopic irregularities (citron skin, There is a tendency to form a satin-like texture, etc. Therefore, in order to achieve the good slippery feel in the laminate of the present disclosure, a lower value is not necessarily more preferable, and it goes without saying that there is a substantial lower limit.
As mentioned above, the laminate of the present disclosure cannot be defined unconditionally because it changes depending on the color tone, but for example, if the laminate exhibits black or other dark color, the 85° gloss value of the matte layer side is set as 25.0 or less, 20.0 or less, and even 15.0 or less, which can exhibit extremely excellent visibility of matte effect. Further, similarly to the 60° gloss value, regarding the 85° gloss value, a laminate exhibiting a color tone other than black or other dark color may also have the above-mentioned 85° gloss value.
Similar to the 60° gloss value, the 85° gloss value is the 85° specular gloss measured in accordance with JIS K 5600-4-7:1999, and is the gloss value measured at 10 arbitrary points using a gloss meter etc. This is the average value of the values that can be measured from the layer side.

[Decorative layer]
The laminate of the present disclosure includes a decorative layer to improve design. The decorative layer is a layer provided between the above-mentioned base material and the matte layer. Moreover, when the transparent resin layer described below is provided, the base material, the decorative layer, the transparent resin layer, and the matte layer may be provided in this order.

The decorative layer may be, for example, a colored layer covering the entire surface, or a pattern layer formed by printing various patterns using ink and a printing machine. Here, the "colored layer covering the entire surface" is also called the "solid colored layer" and is the layer indicated by "6a" in FIGS. 2 and 3, and the "picture layer" is the layer "6a" in FIGS. 2 and 3. 6b". Furthermore, as shown in FIGS. 2 and 3, a solid colored layer and a pattern layer may be combined.

The pattern of the pattern layer is not particularly limited and may be any desired pattern, such as wood grain patterns such as annual rings and conduit grooves on the surface of a wooden board, stone grain patterns on the surface of a stone board such as marble and granite, etc. Examples include grain patterns on the surface of cloth, grain patterns on the surface of leather, geometric patterns, letters, figures, and combinations of these.
In addition, patterns such as cloth grain patterns, metal surface treatment patterns such as hair lines, leather grain patterns, etc., which are exemplified as having a "slippery feel" and are patterns of cloth, metal surfaces, and baby skin, are also preferably cited. It will be done. A more realistic design can be expressed by combining the "slippery feel" of the laminate of the present disclosure with a pattern of an object having a "slippery feel."

The ink used for the decorative layer is a mixture of a binder resin, a pigment, a coloring agent such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. used.
There are no particular restrictions on the binder resin for the decorative layer, and examples include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer. Resins such as polymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins, and cellulose acetate resins are mentioned. Further, various types of resins can be used, such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound.

As the colorant, pigments with excellent hiding properties and weather resistance are preferred. As the pigment, the same pigments as those exemplified as pigments that can be used for the base material can be used.
The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass, based on 100 parts by mass of the resin constituting the decorative layer. The following are more preferred.

The decorative layer may contain additives such as UV absorbers, weathering agents such as light stabilizers, and colorants.
The thickness of the decorative layer may be appropriately selected depending on the desired pattern, and in consideration of hiding the ground color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, and 1 μm or less. The thickness is more preferably 10 μm or more, and even more preferably 2 μm or more and 5 μm or less.

[Total light transmittance]
The laminate of the present disclosure may employ a base material made of a non-transparent material as described above, a decorative layer described below, etc., and may also be used as an exterior member, an interior member, etc. It's something you get. Considering that the base material has the above-mentioned base material and the decorative layer described below, and that it is used for the above-mentioned purposes, the total light transmittance of the laminate of the present disclosure measured in accordance with JIS K7361-1:1997 is preferably is 20% or less, more preferably 15% or less, even more preferably 10% or less.
In this specification, the total light transmittance of the laminate is the total light transmittance measured in accordance with JIS K7361-1:1997, and is the average value of measurements at ten arbitrary locations.

[Other layers]
The laminate of the present disclosure may have other layers such as a primer layer, a transparent resin layer, an adhesive layer, etc., as necessary, in addition to the base material, matte layer, and decorative layer. A cross-sectional view showing an embodiment of the laminate of the present disclosure having these layers is shown in FIG. FIG. 3 is a sectional view showing an embodiment of the laminate of the present disclosure, and is a sectional view of the laminate 1 taken along a plane parallel to its thickness direction. Here, the "thickness direction" means the Z direction in FIG.
The matte decorative material 1 shown in FIG. 3 includes a base material 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a matte layer 4 in this order.

(Primer layer)
For example, when the laminate of the present disclosure is composed of a plurality of layers, it may include a primer layer in order to improve interlayer adhesion between the plurality of layers.
For example, a primer layer can be provided between the matte layer and the base material, or between the transparent resin layer and the matte layer as shown in FIG. 3, in order to improve interlayer adhesion.

The primer layer is mainly composed of a binder resin, and may contain additives such as an ultraviolet absorber and a light stabilizer, if necessary.

Binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and polycarbonate-based urethane-acrylic copolymers (with carbonate bonds in the polymer main chain). urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the terminal or side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer Preferred examples include resins such as coalescent resin, chlorinated propylene resin, nitrocellulose resin (nitrified cotton), and cellulose acetate resin, and these can be used alone or in combination.
Further, the binder resin may be obtained by adding a curing agent such as an isocyanate curing agent or an epoxy curing agent to these resins and crosslinking and curing the resin. Among these, those obtained by crosslinking and curing a polyol resin such as an acrylic polyol resin with an isocyanate curing agent are preferable, and those obtained by crosslinking and curing an acrylic polyol resin with an isocyanate curing agent are more preferable.

The thickness of the primer layer is preferably 0.1 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and even more preferably 2 μm or more and 6 μm or less.

When the laminate of the present disclosure has a base material, a primer is applied on the opposite side of the base material to the side on which the matte layer is provided, for the purpose of improving adhesion to adherends such as resin molded products. (also referred to as a "back primer layer").

(Transparent resin layer)
The laminate of the present disclosure may include a transparent resin layer in order to increase its strength and to protect the decorative layer. The transparent resin layer may be provided between the decorative layer and the matte layer in order to protect the decorative layer.

Examples of the resin constituting the transparent resin layer include polyolefin resin, polyester resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin (hereinafter also referred to as "ABS resin"), acrylic resin, vinyl chloride resin, etc. Among these, polyolefin resins and vinyl chloride resins are preferred from the viewpoint of suitability for post-processing. Further, two or more of these various resins may be used in a stacked manner or in a mixed manner.

The transparent resin layer may be transparent enough to allow the decorative layer to be visually recognized, and may be colorless and transparent, colored transparent, or semitransparent. That is, in this specification, "transparency" means not only colorless and transparent but also colored transparent and translucent.

The transparent resin layer may contain weathering agents such as ultraviolet absorbers and light stabilizers, and additives such as colorants.
The thickness of the transparent resin layer is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and even more preferably 60 μm or more and 100 μm or less, considering protection of the decorative layer and suitability for post-processing.

(glue)
When the laminate of the present disclosure includes a base material and a transparent resin layer, an adhesive layer may be provided between the base material and the transparent resin layer in order to improve the adhesion between both layers.
Further, the positional relationship between the adhesive layer and the decorative layer is not particularly limited, and specifically, the decorative layer, the adhesive layer, and the transparent resin layer may be provided in this order from the side closest to the base material, or the An adhesive layer, a decorative layer, and a transparent resin layer may be provided in this order from the side closest to the material.

The adhesive layer can be made of an adhesive such as a urethane adhesive, an acrylic adhesive, an epoxy adhesive, or a rubber adhesive. Among these adhesives, urethane adhesives are preferred in terms of adhesive strength.
Examples of the urethane adhesive include adhesives that utilize a two-component curable urethane resin containing various polyol compounds such as polyether polyol, polyester polyol, and acrylic polyol, and a curing agent such as an isocyanate compound.

In order to efficiently obtain a desired adhesive force, the thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less.

[Method for manufacturing laminate]
A first method for producing a laminate of the present disclosure includes a decorative layer forming step of providing a decorative layer on a base material, and a resin composition for forming a matte layer containing a curable resin and a wrinkle formation stabilizer on the decorative layer. The present invention is characterized by comprising a matte layer forming step of applying a material and irradiating it with light having a wavelength of at least 100 nm or more and 380 nm or less to form a matte layer.
According to the first manufacturing method, for example, as shown in FIG. It is possible to manufacture a laminate having a concavo-convex shape, and having a specific RSm (average length of curved elements) and Sku (kurtosis).

In the method for producing a laminate of the present disclosure, in forming a matte layer, ultraviolet rays with a low wavelength of at least 100 nm or more and 380 nm or less are applied to a resin composition for matte formation containing a wrinkle formation stabilizer that forms a matte layer. Irradiation is essential. By irradiating and curing the above-mentioned low wavelength ultraviolet rays, irregular wrinkles can be formed on at least one surface of the matte layer, giving the laminate (matte layer) a matte effect and a slippery feel. It becomes possible to impart a tactile sensation.

Regarding the mechanism by which wrinkles are formed on at least one surface of the matte layer and a matte effect and slippery feel are developed by irradiating such low wavelength ultraviolet rays to a resin composition for forming a matte layer. The details of this are unknown, but it is assumed that the mechanism is as follows.

When low-wavelength ultraviolet rays are irradiated on a coated layer of a matte layer-forming resin composition applied to a predetermined thickness, the energy of the ultraviolet rays penetrates only the surface area, and the energy does not reach lower layers. , only the surface portion of the resin composition begins to harden. Therefore, it is thought that only the surface undergoes curing shrinkage, resulting in the formation of irregular wrinkles. In this way, it is thought that the formation of irregular wrinkles occurs when only a certain thickness direction from the surface of the resin composition for forming a matte layer is cured by irradiation with low wavelength ultraviolet rays.

In addition, from a comparison between the Examples and Comparative Examples described later, it was found that when no wrinkle-forming stabilizer is included, the formation of irregular wrinkles becomes unstable, and the visibility and texture of the matting effect are stable over the entire surface of the matting layer. Therefore, it does not develop to a sufficient degree, and does not sufficiently develop a slippery feel. From this, the stable development of the matting effect and the slippery feel cannot be explained solely by curing only the surface portion by low wavelength ultraviolet rays. That is, in order for the laminate of the present disclosure to stably have irregular wrinkles and thereby exhibit a matte effect and a slippery feel, it is essential that the laminate contains a wrinkle formation stabilizer.
Considering that a stable matte effect and a slippery feel due to the formation of irregular wrinkles were not obtained when wrinkle formation stabilizers were not included, wrinkle formation stabilizers were found to be effective in suppressing the core of wrinkle formation. The resin on the surface of the resin composition gathers around the core to form wrinkle convex portions (protrusions), and along with the formation of the convex portions (protrusions), concave portions are formed. As a result, the formation of irregular wrinkles is stabilized, and it is thought that a matting effect and a slippery feel are stably developed.

The wrinkle-forming stabilizer used in the production method of the present disclosure, the resin composition for forming a matte layer containing the wrinkle-forming stabilizer is the wrinkle-forming stabilizer, the resin composition for forming a matte layer that can be used in the laminate of the present disclosure described above. The content is the same as that explained for the resin composition for.

In the manufacturing method of the present disclosure, the resin composition for forming a matte layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. By this irradiation, as described above, the energy of the ultraviolet rays penetrates only into the surface portion, and the energy does not reach the lower layers, so that only the surface portion of the resin composition begins to harden. Therefore, only the surface undergoes curing shrinkage, thereby stabilizing the formation of irregular wrinkles, and the surface layer of the resin composition becomes a cured product, forming a matte layer. After this, curing progresses from the near-surface portion where curing progresses slowly to the deep portion away from the depth direction, and the layer of the resin composition becomes a cured product, thereby curing over the entire thickness of the resin composition, In addition, it forms a matte layer having irregular wrinkles on the surface that exhibits a light-diffusing effect and provides a slippery feel. In order to promote the progress of hardening to deep parts, it is preferable to perform another irradiation treatment after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, as described later.

Examples of light with a wavelength of at least 100 nm or more and 380 nm or less include rare gases such as Ar, Kr, Xe, and Ne, halides of rare gases such as halogens such as F, Cl, I, and Br, or mixtures of these gases. "Excimer light" including light in the ultraviolet wavelength range from an excited state dimer, ie, an excimer, formed by discharge is preferable. The wavelength of excimer light and the excimer used as the light source include, for example, light with a wavelength of 126 nm radiated from an Ar ₂ excimer (hereinafter abbreviated as "126 nm (Ar ₂ )"), 146 nm (Kr ₂ ), and 157 nm. (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), 351 nm (XeF), and other wavelength light can be preferably employed. As the excimer light, either spontaneous emission light or a laser beam with high coherence (coherence) due to stimulated emission can be used, but it is usually sufficient to use spontaneous emission light. Note that a discharge lamp that emits light (ultraviolet light) is also called an "excimer lamp."
Excimer light has a single wavelength peak and is characterized by a narrower wavelength half-width than normal ultraviolet light (for example, ultraviolet light emitted from metal halide lamps, mercury lamps, etc.). By using such excimer light, the formation of irregular wrinkles is stabilized, the matting effect is stably improved, and the slippery feel is also improved.

In order to stabilize the formation of irregular wrinkles, stably improve the matting effect, and improve the slippery feel, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, even more preferably 150 nm or more, Even more preferably it is 155 nm or more, and the upper limit is preferably 320 nm or less, more preferably 300 nm or less, still more preferably 250 nm or less, even more preferably 200 nm or less, and most preferably 172 nm (Xe ₂ ). As described above, in the present disclosure, in order to stably improve the matting effect and improve the slippery feel, it is preferable to use shorter wavelength light, such as medium wavelength ultraviolet light (wavelength: 280 to 320 nm), It can be said that short wavelength ultraviolet light (wavelength: 280 nm or less) is more preferable, and short wavelength ultraviolet light is even more preferable.

In the present disclosure, the integrated light amount of the wavelength light is preferably 1 mJ/cm ² or more from the viewpoint of stabilizing the formation of irregular wrinkles, stably improving the matting effect, and improving the slippery feel. , more preferably 10 mJ/cm ² or more, still more preferably 30 mJ/cm ² or more, even more preferably 50 mJ/cm ² or more. There is no particular limit to the upper limit, and in consideration of productivity such as reducing the number of lamps required for irradiation with wavelength light and improving production efficiency, it is preferably 1,000 mJ/ ^cm2 or less, more preferably 500 mJ/cm2 or less. cm ² or less, more preferably 300 mJ/cm ² or less. For the same reason, the ultraviolet output density is preferably 0.001 W/cm or more, more preferably 0.01 W/cm or more, even more preferably 0.03 W/cm, and preferably 10 W/cm or less as an upper limit. , more preferably 5 W/cm or less, still more preferably 3 W/cm or less.
Further, the oxygen concentration when irradiating the wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, still more preferably 500 ppm or less, even more preferably 300 ppm or less.

In the matte layer forming step in the method for manufacturing a laminate of the present disclosure, in addition to the above-mentioned irradiation with light with a wavelength of at least 100 nm or more and 380 nm or less, other treatments that contribute to curing of the resin composition for forming the matte layer are performed. You may go.
For example, in order to stabilize the formation of irregular wrinkles due to the difference in the degree of hardening between the surface portion and the deep portion located away from the surface in the depth direction, and to promote the progress of hardening toward the deep portion, for example, After pre-curing the entire resin composition for forming a matte layer by irradiating it with light with a wavelength of more than 380 nm, preferably with light with a wavelength of about 385 nm or more and less than 400 nm, the resin composition is irradiated with light with a wavelength of more than 100 nm and less than 380 nm. Alternatively, post-curing may be performed to further cure the resin composition after irradiation with light having a wavelength of 100 nm or more and 380 nm or less. The necessity of pre-curing and post-curing may be determined as appropriate depending on the desired properties of the matte layer, such as processing properties and surface properties such as stain resistance. Furthermore, although the above-mentioned wavelength of light belongs to ultraviolet rays, it is also possible to use other ionizing radiation such as electron beams, etc. in addition to ultraviolet rays. For example, in the post-curing, electron beams can be preferably used from the viewpoint of improving the surface properties of the matte layer.

In the manufacturing method of the present disclosure, the matte layer is produced by applying a resin composition for forming the matte layer using a known method such as an inkjet method, a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, a comma coating method, etc. In order to particularly improve the slippery feel, the coating layer (uncured resin layer) applied by the inkjet method or gravure printing method should be formed by irradiating it with light with a wavelength of at least 100 nm or more and 380 nm or less. Can be done.

In addition, the laminate obtained by the manufacturing method of the present disclosure has other layers such as a transparent resin layer in addition to the base material and the decorative layer, which are described as layers that can be employed in the laminate of the present disclosure. obtain.
For example, the adhesive layer and the primer layer can be formed by applying a coating liquid containing a composition for forming each layer using the above-mentioned known method, and drying and curing the coating liquid as necessary. Moreover, when forming a transparent resin layer, the resin film forming the transparent resin layer can be formed by dry lamination or the like.

(Application)
The laminate of the present disclosure can be used as a decorative member as it is, or as a decorative member by being laminated on an adherend, as described later.

Further, the laminate of the present disclosure can also be used as a molding sheet or a transfer sheet. When used as a shaping sheet, it can be used as an embossing plate used for embossing, a shaping sheet, etc., and thereby a decorative member or thermosetting resin decorative board in which the surface shape of the laminate of the present disclosure is shaped. etc. can be manufactured.

[Cosmetic parts]
The laminate of the present disclosure can be used as a decorative member as it is, or can be laminated, composited, or combined with an adherend to be used as a decorative member. Which one to use may be determined as desired. It is preferable that the laminate of the present disclosure employs a sheet-like base material as a base material and is used as a decorative sheet.

In the case where the decorative member has an adherend, the decorative member has the adherend and the laminate of the present disclosure described above, and specifically, the decorative member includes the surface of the adherend that requires decoration, the base material of the laminate, and the laminate of the present disclosure. are stacked facing each other. Furthermore, when the laminate has an adherend, the laminate of the present disclosure preferably has a film or sheet form in consideration of ease of lamination.

(adherent material)
Examples of the adherend include plate materials such as flat plates and curved plates made of various materials, three-dimensional articles such as cylinders and polygonal columns, sheets (or films), and the like. For example, it can be used as board materials such as wood veneers made of various woods such as cedar, cypress, pine, and lauan, wood plywood, laminated wood, particle boards, and wood fiberboards such as MDF (medium density fiberboard), and three-dimensional shaped products. Wooden members used as plates, three-dimensional articles, or sheets made of metals such as iron, aluminum, copper, and alloys containing one or more of these metals; Ceramics such as glass and china, plaster, and cement , ALC (lightweight aerated concrete), calcium silicate, and other non-ceramic ceramic materials used as plates and three-dimensional products; polyolefin resins such as acrylic resins, polyester resins, polystyrene resins, and polypropylene; -butadiene-styrene copolymer) resin, phenol resin, vinyl chloride resin, cellulose resin, rubber, and other resin members used as plates, three-dimensional articles, sheets, etc. Further, these members can be used alone or in combination.

The adherend material may be selected from the above according to the intended use, and can be used for interior building materials such as walls, ceilings, and floors, or for exterior materials such as exterior walls, roofs, soffits, fences, gates, and windows. When used as fittings or fixtures such as frames, doors, handrails, baseboards, surrounding edges, moldings, etc., it is preferable to use at least one member selected from wooden members, metal members, and resin members, such as entrance doors, etc. When used as exterior members, window frames, doors, and other fittings, it is preferable to use at least one member selected from metal members and resin members.

The thickness of the adherend may be appropriately selected depending on the purpose and material, and is preferably 0.1 mm or more and 100 mm or less, more preferably 0.3 mm or more and 5 mm, and even more preferably 0.5 mm or more and 3 mm or less.

(adhesive layer)
The adherend and the laminate are preferably attached via an adhesive layer in order to obtain excellent adhesion.

The adhesive used in the adhesive layer is not particularly limited, and any known adhesive may be used, and may be appropriately selected depending on the application. For example, adhesives such as moisture-curing adhesives, anaerobic-curing adhesives, dry-curing adhesives, UV-curing adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives are preferred. It will be done.

Examples of resins used in these adhesives include acrylic resins, urethane resins, vinyl chloride resins, vinyl acetate resins, vinyl chloride-vinyl acetate copolymers, styrene-acrylic copolymers, polyester resins, amide resins, Examples include cyanoacrylate resins and epoxy resins, and these can be used alone or in combination. Furthermore, a two-component curing type urethane adhesive or ester adhesive using an isocyanate compound or the like as a curing agent can also be applied.
Moreover, an adhesive can also be used for the adhesive layer. As the adhesive, various adhesives such as acrylic, urethane, silicone, and rubber adhesives can be appropriately selected and used.

The thickness of the adhesive layer is not particularly limited, but in order to obtain excellent adhesiveness, it is preferably 1 μm or more and 100 μm or less, more preferably 5 μm or more and 50 μm or less, and even more preferably 10 μm or more and 30 μm or less.

[Total light transmittance]
A decorative member using the laminate of the present disclosure may be used in cases where the laminate includes a base material, a decorative layer, etc. made of a non-transparent material as described above, or an adherend made of a non-transparent material. may be adopted, and may also be used for applications such as exterior members and interior members. Considering the above, the total light transmittance of the decorative member using the laminate of the present disclosure measured in accordance with JIS K7361-1:1997 is preferably 20% or less, more preferably 15% or less, and even more preferably is less than 10%.

(Method for manufacturing decorative parts)
The decorative member can be manufactured through a process of laminating the laminate of the present disclosure and an adherend.
This step is a step of laminating the adherend and the laminate of the present disclosure, in which the surface of the adherend that requires decoration and the surface of the laminate of the present disclosure on the base material side face each other. . Examples of the method for laminating the adherend and the laminate include a lamination method in which the laminate is laminated on a plate-shaped adherend by pressing with a pressure roller via an adhesive layer.

When using a hot melt adhesive (also referred to as a "thermal adhesive") as the adhesive, the heating temperature is preferably 160°C or higher and 200°C or lower, although it depends on the type of resin that makes up the adhesive. For hot melt adhesives, the temperature is preferably 100°C or higher and 130°C or lower. Further, in the case of vacuum forming processing, it is generally performed while heating, and the temperature is preferably 80°C or more and 130°C or less, more preferably 90°C or more and 120°C or less.

The decorative member obtained in the above manner can be arbitrarily cut, and arbitrary decorations such as grooving and chamfering can be applied to the surface and end portion using a cutting machine such as a router or a cutter. and various uses, such as interior parts of buildings such as walls, ceilings, and floors; exterior parts such as exterior walls, soffits, roofs, fences, and fences; window frames, doors, door frames, handrails, baseboards, Fittings or fixtures for surrounding edges, moldings, etc.; Also, general furniture such as chests of drawers, shelves, desks, etc.; kitchen furniture such as dining tables, sinks; decorative surface panels for cabinets of home appliances, OA equipment, etc.; interior or exterior use of vehicles. Suitable for use as a member, etc.

In addition to the above-mentioned decorative members used in buildings, etc., the laminate of the present disclosure can be packaged as a single unit, or in the form of lamination, composite, or combination with other materials (adherents). Materials, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, various certificates, keys for various keyboards, transparent plates (window glass, etc.) for windows, doors, partitions, etc., artificial leather, etc. It can be used for. In these uses, it is preferable that the laminate of the present disclosure, which usually produces a matte effect and a slippery feel, is placed on the outermost surface, but other uses may be used depending on the use, purpose, etc. Of course, it is also possible to make it into a form.

(Laminated body of the present disclosure)
The laminate of the present disclosure described above is as follows.
1. having a base material, a decorative layer and a matte layer in this order,
The surface of the matte layer opposite to the decorative layer has an uneven shape constituted by irregular wrinkles,
In the measurement image when measuring the measurement area (length 204 μm x width 272 μm) on the surface with a laser microscope (objective lens 50 times),
RSm (average length of curved elements) is 20.00 μm or more, and Sku (kurtosis) at a height above the reference plane in the measurement image is 4.00 or less.
laminate.
2. 2. The laminate according to item 1, wherein Rz (maximum height), which is a peak and height parameter of the contour curve, is 5.00 μm or more on the measurement screen.
3. 3. The laminate according to 1 or 2 above, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve, is 3.00 μm or less on the measurement screen.
4. Any one of 1 to 3 above, wherein the irregular wrinkles are constituted by a plurality of protrusions formed by a plurality of linear protrusions and a recess formed by being surrounded by the plurality of linear protrusions. The laminate described in .
5. The matte layer is composed of a cured product of a resin composition containing a resin and a wrinkle-forming stabilizer, and the wrinkle-forming stabilizer has a thickness of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. 5. The laminate according to any one of 1 to 4 above, which has an average particle diameter as an upper limit and contains the wrinkle formation stabilizer in an amount of 0.5 parts by mass or more based on 100 parts by mass of the resin.
6. 6. The laminate according to any one of 1 to 5 above, wherein the base material is in the form of a sheet.
7. 7. The laminate according to any one of 1 to 6 above, wherein the matte layer is provided over the entire surface of one side of the base material.
8. 8. The laminate according to any one of 1 to 7 above, wherein the surface shape has a 60° gloss value of 20.0 or less.
9. 9. The laminate according to any one of 1 to 8 above, which has a total light transmittance of 20% or less as measured in accordance with JIS K7361-1:1997.
10. 10. The laminate according to any one of 1 to 9 above, which is used as a decorative sheet.

Next, the present disclosure will be explained in more detail with reference to examples, but the present disclosure is not limited to these examples in any way.

(Measurement of surface texture)
RSm (average length of curved elements), Sku (kurtosis), Rz (maximum height), and Ra (arithmetic mean roughness) of the laminates obtained in Examples and Comparative Examples are based on the surface shape of the laminate. A shape analysis laser microscope (VK-X150 (control unit)/VK- X160 (Measurement Unit)" manufactured by Keyence Corporation), objective lens: 50 times, laser wavelength: 658 nm, measurement mode: surface shape mode, measurement pitch: 0.13 μm, measurement quality: high speed mode. Here, Sku (kurtosis) was defined as the Sku (kurtosis) at a height above the reference plane on the measurement screen corresponding to the measurement area. In addition, among the surface properties in one measurement area, RSm (average length of curved elements), Rz (maximum height), and Ra (arithmetic mean roughness) are the measurements corresponding to the one measurement area. In the screen, the average value of various surface properties obtained by measuring 8 cross sections in the vertical direction and 7 cross sections in the horizontal direction was taken as the average value, and this was similarly performed for nine arbitrary locations. The average value of the surface textures at nine locations was taken as the various surface textures of the laminate.
Further, the cutoff values for RSm (average length of curved elements), Rz (maximum height), and Ra (arithmetic mean roughness) were set to 0.8 mm.

(Evaluation method: 60° gross value and 85° gross value)
For the laminates obtained in the Examples and Comparative Examples, 10 arbitrary points were measured in accordance with JIS K5600-4-7:1999 using a gloss meter ("Microgloss (model name)", manufactured by BYK Gardner). 60° specular gloss (60° gloss value) and 85° specular gloss (85° gloss value) were measured.

(Evaluation of texture (uniformity of surface condition))
Regarding the laminates obtained in the Examples and Comparative Examples, 20 arbitrary adults evaluated the surface texture (uniformity of the surface condition) using the following criteria.
A: More than 18 people evaluated that the surface condition was uniform and the visibility of the matte effect was high.
B: 15 to 17 people evaluated that the surface condition was uniform and the visibility of the matte effect was high.
C: 14 or less people evaluated that the surface condition was uniform and the visibility of the matte effect was high.

(Evaluation of slippery feel)
Regarding the laminates obtained in the Examples and Comparative Examples, 20 arbitrary adults were asked to evaluate the surface texture using plain satin fabric without embroidery, background patterns, etc. as a reference for the slippery texture. The results were evaluated using the following criteria.
A: More than 18 people evaluated that the tactile sensation was close to the standard, and that the tactile sensation did not catch on a flat surface when the hand moved, and that it felt like it was sliding.
B: 15 to 17 people evaluated that the tactile sensation was close to the standard, and that the tactile sensation did not catch on a plane when the hand moved, and that it felt like it was sliding.
C: 14 or fewer people evaluated that the tactile sensation was close to the standard, and that there was no catching on a flat surface with respect to hand movements, and that the tactile sensation was slippery.

[Example 1]
A corona discharge-treated polypropylene sheet (thickness: 60 μm) is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one side of the base material using a gravure method to color it. A decorative layer (thickness: 3 μm) consisting of a layer and a pattern layer is provided, and a primer layer (thickness: 2 μm) is provided by applying a resin composition containing a two-component curable acrylic-urethane resin onto the decorative layer. On the layer, a resin composition for forming a matte layer (30 parts by mass of polyfunctional urethane acrylate oligomer 1 (average number of functional groups: 3, average molecular weight: 2400), polyfunctional acrylate monomer 1 (bifunctional, molecular weight: 296): 40 parts by mass, monofunctional acrylate monomer (molecular weight: 226): 30 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle diameter: 4 μm): 5.0 parts by mass, photopolymerization initiator (benzophenone type): 0 .8 parts by mass) was applied over the entire surface by gravure method (coating amount: 5 g/m ² (dry), matte layer thickness: 5 μm).
Next, ultraviolet rays were irradiated using a UV irradiation device composed of an LED (wavelength: 395 nm, amount of ultraviolet rays: 6 W/cm ² ), and ultraviolet rays were irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), UV output density: 1 W/cm, integrated light amount: 10 to 100 mJ/cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), and further irradiated using a high-pressure mercury lamp (UV output density: 200 W/cm) to form a matte layer. A laminate having a base material, a decorative layer, a primer layer and a matte layer in this order was obtained. When the 60° gloss value and the 85° gloss value of the obtained laminate were measured from the matte layer side, they were 2.0 and 17.3, respectively. In addition, the surface properties were measured and the texture and tactile sensation were evaluated using the methods described above. These results are shown in Table 1.

[Example 2]
In Example 1, polyfunctional urethane acrylate oligomer 1 contained in the resin composition for forming a matte layer was mixed with 30 parts by mass of polyfunctional urethane acrylate oligomer 2 (average number of functional groups: 3, average molecular weight: 1590) and polyfunctional acrylate monomer. 1 was changed to 30 parts by mass of polyfunctional acrylate monomer 2 (bifunctional, molecular weight: 1342) and 40 parts by mass of monofunctional acrylate monomer, and the amount of wrinkle formation stabilizer 1 (silica particles, average particle diameter: 4 μm) was changed. Using 2.0 parts by mass and further 3.0 parts by mass of wrinkle-forming stabilizer 2 (silica particles, average particle size: 20 nm), the resin composition for forming a matte layer was applied from the entire surface coating by gravure method. A laminate was obtained in the same manner as in Example 1, except that the coating was applied in a pattern (a pattern having random circular blank areas (uncoated areas) with an average diameter of 70 μm) by the inkjet method. Note that the length from the center of a blank area to an adjacent blank area was within a range of 100 to 300 μm.
Regarding the obtained laminate, the 60° gloss value, 85° gloss value, and surface texture of the matte layer side were measured by the above method, and the texture and tactile sensation were evaluated. These results are shown in Table 1.

[Example 3]
In Example 2, regarding the resin components contained in the resin composition for forming a matte layer, polyfunctional urethane acrylate oligomer 2 and polyfunctional acrylate monomer 2 were changed to polyfunctional urethane acrylate oligomer 1 and polyfunctional acrylate monomer 1, respectively. A laminate was obtained in the same manner as in Example 2 except for the following.

[Comparative example 1]
In Example 1, the resin components contained in the resin composition for forming a matte layer were 40 parts by mass of polyfunctional urethane acrylate oligomer 1 (average number of functional groups: 3, average molecular weight: 2400) and polyfunctional acrylate monomer 2 (2 Functionality, molecular weight: 1342) 30 parts by mass, and the amount of wrinkle-forming stabilizer used was 0 parts by mass, that is, no wrinkle-forming stabilizer was used, and instead, 10 parts by mass of a matting agent (average particle diameter: 8.0 μm) A laminate was obtained in the same manner as in Example 1, except that 10% of the laminate was used.
Regarding the obtained laminate, the 60° gloss value, 85° gloss value, and surface texture of the matte layer side were measured by the above method, and the texture and tactile sensation were evaluated. These results are shown in Table 1.

[Comparative example 2]
In Example 1, the resin components contained in the resin composition for forming a matte layer were 20 parts by mass of polyfunctional urethane acrylate oligomer 2 (average number of functional groups: 3, average molecular weight: 1590), polyfunctional urethane acrylate oligomer 3 ( A laminate was obtained in the same manner as in Example 1, except that the average number of functional groups: 3, average molecular weight: 3000) was 20 parts by mass, and the polyfunctional acrylate monomer 1 (bifunctional, molecular weight: 296) was 30 parts by mass. .
Regarding the obtained laminate, the 60° gloss value, 85° gloss value, and surface texture of the matte layer side were measured using the methods described above, and the texture and tactile sensation were evaluated. These results are shown in Table 1.

From the results in Table 1, the laminate of the present disclosure has a 60° gloss value of 1.5 to 2.2 on the matte layer side, and is a laminate with extremely excellent visibility of the matte effect. It was confirmed that the texture was excellent. It was also confirmed that it had an excellent slippery feel. Furthermore, the laminate of Example 1, which has a matte layer provided on at least a portion of its surface, has excellent visibility and texture with a matte effect, and has an excellent slippery feel. It was confirmed that
On the other hand, the laminate of Comparative Example 1, which does not contain a wrinkle-forming stabilizer, has irregularities on the surface even if it contains a matting agent in an amount of 10.0 parts by mass, which is larger than the content of the wrinkle-forming stabilizer in the example. It was confirmed that there was no formation of wrinkles and the texture was poor, and that the surface shape had a large Sku (kurtosis) and lacked a slippery feel. Moreover, the tactile feel of the laminate of Comparative Example 1 was poor in slippery tactile sensation, and was rather rough to the touch. It was confirmed that the laminate of Comparative Example 2 also had a particularly large Sku (kurtosis), so it lacked a slippery feel and was also inferior in texture.

4 to 6 are measurement screens taken by a shape analysis laser microscope in one measurement area (204 μm in length x 272 μm in width) of the laminates of Examples 1 and 2 and Comparative Example 1, respectively.
As shown in FIGS. 4 and 5, the surface shapes of the laminates of Examples 1 and 2 were confirmed to have an uneven shape due to irregular wrinkles, and it is understood that a slippery feel was obtained.

On the other hand, as shown in FIG. 6, the surface shape of the laminate of Comparative Example 1 has convex portions appearing here and there, which are thought to be caused by the matting agent, and the convex portions are wide. Because it was too soft, it did not have a slippery feel.
In this way, from the measurement screen, the laminate of the present disclosure has an uneven shape due to irregular wrinkles on its surface, and this uneven shape has excellent visibility and texture with an excellent matte effect. It has also been confirmed that it has the effect of providing an excellent slippery feel.

7 to 9 show measurements taken using a shape analysis laser microscope at nine measurement areas (one measurement area is 204 μm long x 272 μm wide) of the laminates of Examples 1 and 2 and Comparative Example 1, respectively. The screens are connected (because there was some overlap, the connected measurement screen corresponds to a measurement area of 545 μm in height x 743 μm in width). By observing the connected measurement screens in this way, it is possible to get an overview of the uneven shape caused by irregular wrinkles in the laminate obtained in each example. Regarding this measurement screen, the various surface textures measured in the same manner as above (measurement of surface texture), except that 25 cross sections in the vertical direction and 20 cross sections in the horizontal direction were measured, are listed in Table 1 above. The values were almost the same as those for the surface texture. Therefore, it can be said that the method of connecting the measurement screens of nine measurement areas is effective in understanding the uneven shape due to irregular wrinkles in the laminate and in measuring the surface texture.

The laminate of the present disclosure has excellent visibility and texture with an excellent matte effect, and has an excellent slippery feel, so it can be used for various purposes, such as interior materials of buildings such as walls, ceilings, and floors. Exterior materials such as outer walls, eaves, roofs, fences, and fences; Fittings or fixtures such as window frames, doors, door frames, handrails, skirting boards, edges, and moldings; Also, chests of drawers, shelves, desks, etc. It is suitably used as a decorative member for various parts such as general furniture; kitchen furniture such as dining tables and sinks; decorative surface boards for cabinets such as home appliances and OA equipment; and decorative members for various parts such as interior or exterior parts of vehicles.
In addition to the above-mentioned decorative members used in buildings, etc., the laminate of the present disclosure can be packaged as a single unit, or in the form of lamination, composite, or combination with other materials (adherents). Materials, whiteboards or blackboards, various cards such as credit cards, cash cards, telephone cards, various certificates, keys for various keyboards, transparent plates (window glass, etc.) for windows, doors, partitions, etc., artificial leather, etc. It is also suitably used as

1: Laminated body 2: Concave portion 3: Convex portion (protrusion)
4: Matte layer 5: Base material 6: Decorative layer 6a: Colored layer 6b: Pattern layer 7: Adhesive layer 8: Transparent resin layer 9: Primer layer

Claims (10)

having a base material, a decorative layer and a matte layer in this order,
The surface of the matte layer opposite to the decorative layer has an uneven shape constituted by irregular wrinkles,
In the measurement image when measuring the measurement area (length 204 μm x width 272 μm) on the surface with a laser microscope (objective lens 50 times),
RSm (average length of curved elements) is 20.00 μm or more, and Sku (kurtosis) at a height above the reference plane in the measurement image is 4.00 or less.
laminate. The laminate according to claim 1, wherein Rz (maximum height), which is a peak and height parameter of the contour curve, is 5.00 μm or more on the measurement screen. The laminate according to claim 1 or 2, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve, is 3.00 μm or less on the measurement screen. Any one of claims 1 to 3, wherein the irregular wrinkles are constituted by a plurality of convex portions formed by a plurality of linear protrusions and a recessed portion surrounded and formed by the plurality of linear protrusions. The laminate according to item 1. The matte layer is composed of a cured product of a resin composition containing a resin and a wrinkle-forming stabilizer, and the wrinkle-forming stabilizer has a thickness of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. The laminate according to any one of claims 1 to 4, which has an average particle diameter as an upper limit and contains the wrinkle formation stabilizer in an amount of 0.5 parts by mass or more based on 100 parts by mass of the resin. The laminate according to any one of claims 1 to 5, wherein the base material is in the form of a sheet. The laminate according to any one of claims 1 to 6, wherein the matte layer is provided over the entire surface of one side of the base material. The laminate according to any one of claims 1 to 7, wherein the 60° gloss value of the surface shape is 20.0 or less. The laminate according to any one of claims 1 to 8, which has a total light transmittance of 20% or less as measured in accordance with JIS K7361-1:1997. The laminate according to any one of claims 1 to 9, which is used as a decorative sheet.