JP7294482B1 - laminate - Google Patents

Abstract

[Problem] To provide a laminate that has excellent visibility and texture of a matte effect, does not get caught on a flat surface with respect to hand movements, and has an excellent slippery feel. A base material, a decorative layer and a matte layer are provided in this order, and the surface of the matte layer on the side opposite to the decorative layer has an uneven shape composed of irregular wrinkles. RSm (average length of curve element) is 20.00 μm or more in the measurement image when the measurement area (204 μm long × 272 μm wide) is measured with a laser microscope (50x objective lens), and in the measurement image Sku (kurtosis) at a height above the reference plane is 4.00 or less. [Selection figure] None

Description

The present disclosure relates to laminates.

Conventionally, for example, interior members of buildings such as walls, ceilings, and floors; exterior members such as outer walls, eaves, roofs, fences, and fences; , fittings or fixtures such as malls; general furniture such as wardrobes, shelves, desks; kitchen furniture such as dining tables and sinks; A so-called decorative material or decorative sheet is used as an article for decorating and protecting the surface of the glass. As such a decorative material, for example, a material having a surface layer having a desired function is used.

For decorative materials used in these applications, a method of improving the texture by using a matting effect (also referred to as a "mat effect") is widely used in order to improve the design. As a decorative material using a matting effect, for example, in Patent Document 1, a base sheet has a pattern layer and a concealing layer on one side, and has a gloss adjusting layer such as a matte layer or a gloss layer on the other side. A cosmetic sheet has been proposed. In the decorative sheet of Patent Document 1, the design effect of enhancing the pattern layer and the concealing layer is obtained due to the difference in gloss between the matte layer and the gloss layer of the gloss adjusting layer. For the layer, a matte ink is used in which a total of 50 parts by weight of matting agent, ie, 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, is added to 100 parts by weight of resin.

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

JP-A-2000-062081 JP 2011-073207 A

As a technique for improving the texture by the matting effect, a matting agent (also referred to as a "matting agent" or "matting agent") is used as in Patent Document 1 above, and the light diffusion effect of the matting agent itself is used to improve the texture. Main examples include a method for obtaining an extinguishing effect, a method for forming an uneven shape on the outermost surface by applying embossing as in Patent Document 2 above, and the like.
However, when a matting agent is used as in Patent Document 1, it is necessary to increase the amount of the matting agent to achieve a better matting effect. It falls off from the coating film and damages the coating film, resulting in a decrease in scratch resistance. In addition, the lack of the matting agent causes a change in gloss, making the scratches more noticeable, or contamination in the minute 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 lowers the stain resistance. On the other hand, if the amount used is reduced in order to suppress deterioration of the surface properties, the matting effect tends to be reduced, and the surface properties and the matting effect are in a dichotomy relationship. Therefore, there is a limit to the matte effect using matting agents.
In addition, when embossing is used as in Patent Document 2, preparation of embossing plates takes a lot of time and effort and is not easy. Therefore, it cannot be said that it is a method that can sufficiently respond to the diversity of customer demands.

By the way, customer demands are diversified, and not only the above-mentioned visual matte effect but also tactile expression is required. For example, in the case of using a matting agent such as that of Patent Document 1, by increasing the amount of the matting agent used, the outline of the matting agent appears on the surface of the decorative sheet, and a somewhat rough texture is expressed. sometimes. Moreover, when embossing is used as in Patent Document 2, a tactile sensation may be developed due to the uneven shape of the surface formed by the embossing plate. However, in any case, attention is not paid to the expression of the tactile sensation, and it cannot be said that the tactile sensation is sufficiently expressed. In other words, it cannot be said that conventional decorative sheets and decorative materials are capable of achieving both excellent matting effect and tactile feel. In the present disclosure, among tactile sensations, particular attention is paid to "a tactile sensation that is pleasant to the touch", that is, "a tactile sensation that is smooth on a flat surface without being caught by hand movements".

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

In order to solve the above problems, the present disclosure is
Having a base material, a decorative layer and a matte layer in that order,
The surface of the matte layer on the side opposite to the decorative layer has an uneven shape composed of irregular wrinkles,
In the measurement image when the measurement area (204 μm long × 272 μm wide) on the surface is measured with a laser microscope (50x objective lens),
RSm (average length of curvilinear element) 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 matte effect visibility and texture, does not get caught on a flat surface with respect to hand movements, and has an excellent slipping feel.

1 is a schematic plan view showing an embodiment of a laminate of the present disclosure; FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present disclosure; FIG. 1 is a cross-sectional view showing one embodiment of a laminate of the present disclosure; FIG. 1 is a measurement screen of one measurement area (length 204 μm×width 272 μm) on the surface of the laminate obtained in Example 1. FIG. 2 is a measurement screen of one measurement area (length 204 μm×width 272 μm) on the surface of the laminate obtained in Example 2. FIG. 2 is a measurement screen of one measurement area (length 204 μm×width 272 μm) on the surface of the laminate obtained in Comparative Example 1. FIG. 2 is a measurement screen in which nine measurement regions on the surface of the laminate obtained in Example 1 are connected. 10 is a measurement screen in which nine measurement regions on the surface of the laminate obtained in Example 2 are connected. 2 is a measurement screen in which nine measurement regions on the surface of the laminate obtained in Comparative Example 1 are connected.

[Laminate]
The laminate of the present disclosure will be described below. In this specification, the numerical values related to "more than", "less than", and "to" regarding 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 for the upper and lower limits of the numerical range. is.

The laminate of the present disclosure is
Having a base material, a decorative layer and a matte layer in that order,
The surface of the matte layer opposite to the decorative layer (the laminate is used so that the matte layer side can be visually recognized by the user, and hereinafter, the surface of the matte layer opposite to the decorative layer ( It is also the surface of the matte layer opposite to the base material.) is sometimes simply referred to as the “surface”.) has an uneven shape composed of irregular wrinkles,
In the measurement image when the measurement area (length 204 μm × width 272 μm) on the surface is measured with a laser microscope (50x objective lens),
RSm (average length of curvilinear element) 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. In the measured image, RSm (average length of curvilinear element) is 20.00 μm or more, and Sku (kurtosis) at a height above the reference plane in the measured image is 4.00 or less. That is, the laminate of the present disclosure has an uneven shape composed of irregular wrinkles, so that the RSm (average length of the curvilinear element) and the surface properties of Sku (kurtosis) at a height above the reference plane is within a predetermined range.

These RSm (average length of curve element), Rz (maximum height) which is a peak and height parameter of the contour curve described later, and Ra (arithmetic mean roughness) which is a 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. The visibility and texture of the erasing effect, as well as the tactile feel, may vary.
The laminate of the present disclosure has a surface shape in which RSm (average length of curvilinear element) is 20.0 μm or more and Sku (kurtosis) at a height above the reference plane is 4.0 or less By having such properties, it exhibits excellent visibility and texture of a matte effect, and also exhibits a tactile sensation that does not get caught on a flat surface with respect to the movement of the hand and that feels as if it is sliding. Hereinafter, "a tactile sensation that does not catch the movement of the hand on a flat surface and that is slippery" may be referred to as a "slippery tactile sensation". Further, the "visibility and texture of matte effect" may be simply referred to as "matte effect" hereinafter.

A tactile sensation that is "free and slippery on a flat surface against hand movement" is a sensual expression, but in this specification, it is "free and slippery on a flat surface against hand movement". The tactile sensation generally includes all tactile sensations that feel "slipping on a flat surface without being caught by hand movements". More specifically, it means the tactile sensation felt when touching a smooth and smooth surface while moving the hand and touching it with the pad of the finger. As a tactile sensation similar to the 'slippery touch', there is a 'smooth touch', but the 'smooth touch' is closer to the touch of the surface of a dry object, and the 'slippery touch' is It is different in that it has a "smooth and smooth surface" tactile sensation. In addition, "moist touch" is also mentioned as a touch similar to "slippery touch". It is different from the "slippery touch" in that the

It cannot be said unconditionally that a material having a "slippery touch" can vary depending on the processing of its surface, and the weaving method of the fabric described later, but for example, it is not a coated paper with a coated surface. High-quality paper, fabrics such as oxford cloth using fine threads of about 60 to 120 counts, which are said to be fine to ultra-fine, satin weave using natural fibers such as silk and cotton, as well as synthetic fibers such as polyester and nylon. satin cloth, baby skin and the like. In addition, 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; Those subjected to various surface treatments such as silky blasting; Regarding surface processing such as hairline processing and silky blast processing on metal, there are some that do not have a "smooth" feel depending on the degree of processing, but it does not include those that have undergone such processing. Not even. Also, with regard to other fabrics, etc., there are some that do not have a "slippery touch" 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 these fabrics, metal surfaces, and the like. 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 and 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 properties of the surface of the laminate are properties analyzed from a measurement image obtained by measuring a measurement area (204 μm long × 272 μm wide) on the surface with a laser microscope (50x objective lens). shall be the average value of the measured values measured in the nine measurement areas. Also, the arbitrary nine locations may be locations separated from each other, or may be adjacent to or in contact with each other.
In addition, among these surface properties in one measurement area, RSm (average length of the curve element), 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 of Ra (arithmetic average roughness), which is a parameter, is the measurement image obtained when the one measurement area (vertical 204 μm × horizontal 272 μm) is measured with a laser microscope (objective lens 50 times). It is the average value of various surface properties obtained by measuring 8 cross sections in the direction and 7 cross sections in the lateral 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 when the surface property measured in this manner satisfies the above-described predetermined range, a matte effect and a slippery feel are obtained.

(RSm (average length of curvilinear element))
RSm (average length of curve element) obtained by the above measurement is RSm (average length of curve element) which is a lateral parameter of the contour curve measured in accordance with JIS B0601:2013. RSm (mean length of curvilinear element), 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 RSm is less than 20.00 μm, a matte effect and a slippery feel, especially a slippery feel, cannot be obtained.

RSm (mean length of curve element) is the lateral parameter of the contour curve and is the average length of the contour element over the reference length. The smaller the numerical value of RSm (average length of curvilinear element), 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 curvilinear element) is less than 20.00 μm, it tends to have a large number of projections with narrower widths. Considering this, RSm (average length of curvilinear element) is preferably 30.00 μm or more, more preferably 40.00 μm or more, and even more preferably 45.00 μm or more.

In addition, the larger the numerical value of RSm (the average length of the curvilinear element), the wider the width of the protrusions, and the surface shape has many wide protrusions, and the movement of the hand is conspicuous on the plane. easier. Considering this, the upper limit of RSm (average length of curvilinear element) is preferably 130.00 μm or less, more preferably 120.00 μm or less, and even more preferably 115.00 μm or less. When RSm (average length of curvilinear elements) is within the above range, there tends to be a large number of protrusions with appropriate widths, so that a slippery feel and matte effect are improved.
The cutoff value for measuring RSm (average length of curvilinear element) in this specification is 0.8 mm.

(Sku (Kurtosis))
Sku (kurtosis) obtained by the above measurement is Sku (kurtosis) measured in accordance with ISO25178-2:2012, and serves as an index indicating the degree of sharpness of the height distribution from the average surface. be. Sku (kurtosis) is a three-dimensional surface property parameter that is usually 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 , attention is paid to Sku (kurtosis) at a height above the reference plane in the measurement image among Sku (kurtosis). In other words, attention is focused on the sharpness of the height distribution due to the convex portion at a height higher than the reference plane (which can be said to be the average plane for the entire measurement area). When the surface of the laminate is touched with a hand, the protrusions that are not above the reference plane do not come into direct contact with the hand and hardly contribute to the tactile sensation. Therefore, in the laminate of the present disclosure, by focusing on the shape of the convex portion above the reference surface, which is the convex portion that is directly touched when the surface is touched by hand, it is possible to more reliably slide. It is possible to obtain a good tactile sensation. In this specification, "Sku (Kurtosis) at a height above the reference plane" is also simply referred to as "Sku (Kurtosis)".

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

When Sku (kurtosis) is 3, the surface shape is 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, and Sku is 3. It is a measured value that can be grasped that there is a tendency to have a shape in which the height distribution is collapsed when it is less than. Therefore, the fact that the Sku (kurtosis) at a height above the reference plane is 4.0 or less means that the height distribution (near the top of the protrusion) of the convex portion having a height above the reference plane is moderate. It means that there are sharp shapes (Sku (kurtosis) of more than 3 and 4.0 or less) or crushed shapes (Sku (kurtosis) of less than 3). When the surface is directly touched by the hand, the protrusions have such a shape, so that the movement of the hand is not caught on the flat surface, and a smooth feel can be obtained.
On the other hand, when the Sku (kurtosis) exceeds 4.0, the height distribution (near the top of the convex portion) of the convex portion having a height equal to or higher than the reference plane has a sharp shape, so that the roughness is caused. It becomes conspicuous and the slippery touch cannot be obtained.

As described above, the laminate of the present disclosure has RSm (average length of curvilinear elements) and Sku (kurtosis) within a predetermined numerical range, so that an excellent matte effect and a slippery feel can be obtained. be done. That is, the laminate of the present disclosure has a moderate width as an uneven shape composed of irregular wrinkles on the surface, and has many convex shapes that are gently pointed or collapsed near the top. By adopting the shape, it has an excellent matte effect and a slippery feel.

As Sku (kurtosis) increases, the shape near the top of the convex portion becomes sharper, so that the roughness becomes noticeable and the slippery feel is reduced. Considering this, Sku (kurtosis) is preferably 3.9 or less, more preferably 3.7 or less, and still more preferably 3.5 or less in relation to the aforementioned RSm (average length of curve element) is.
On the other hand, as the Sku (kurtosis) becomes smaller, the vicinity of the apex of the convex portion has a gentler shape, which suppresses roughness and improves the smooth feel. Considering this, 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, and 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 curvilinear element) and Sku (kurtosis), and the definition of RSm (average length of curvilinear element) It combines the feature that the width of the protrusion is appropriate according to the Sku (Kurtosis) definition, and the feature that the shape near the top of the protrusion is gently pointed or collapsed according to the Sku (Kurtosis) definition.
The surface shape of the laminate of the present disclosure has a convex portion with a moderate width that is gently pointed or crushed in the vicinity of the top, so when the surface is touched with the pad of a finger, moderate contact Frequently, a gently pointed or flattened tip shape can be felt. It is believed that such a sensation leads to a tactile sensation that does not get caught on a flat surface with respect to the movement of the hand and that it is slippery. In addition, it is considered that the presence of such convex portions results in relatively concave portions, and thus a matting effect is also obtained. The details of the expression of the matte effect will be described later.

The surface shape of the laminate of the present disclosure has an uneven shape composed of irregular wrinkles 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 curvilinear element) and Sku (kurtosis), preferably Rz (maximum height) and Ra (arithmetic mean roughness) described later are RSm (curvilinear element average length) tends to fall within a specific numerical range. On the other hand, the uneven shape composed of irregular wrinkles has RSm (average length of curvilinear element) and Sku (kurtosis) within a specific numerical range, preferably Rz (maximum height) and Ra (arithmetic mean It becomes easy to form by having roughness). In this way, it can be said that RSm (average length of curvilinear element), Sku (kurtosis), and the like are inextricably linked with the irregular shape formed by irregular wrinkles. And, by having such a surface shape, the matting effect is improved as well as the slippery feel.

In the surface shape of the laminate, RSm (average length of curvilinear element) and Sku (kurtosis) within the above specific numerical ranges, preferably Rz (maximum height) and Ra (arithmetic mean roughness) described later , as already mentioned,
(1) forming an uneven shape composed of irregular wrinkles on the surface of the matte layer;
is essential. for that purpose,
(2) Composition formulation of the resin composition for forming the matte layer, particularly the type of polymerizable monomer and polymerizable oligomer, the number of functional groups, the molecular weight, the presence or absence of a wrinkle-forming stabilizer, and wrinkle-forming when using a wrinkle-forming stabilizer Optimizing the particle size and content of the agent,
(3) optimizing the irradiation conditions of the resin composition for matting formation, particularly the wavelength of light having a wavelength of 100 nm or more and 380 nm or less that can cause curing shrinkage of the surface portion of the matte layer, the integrated weight, the ultraviolet power density, etc.
(4) In addition to the above, optimize the type and thickness of the base material, the thickness of the matte layer, etc.
is preferred. By optimizing these, for the surface shape of the laminate of the present disclosure, RSm (average length of curvilinear element) and Sku (kurtosis) are within the above specific numerical ranges, preferably Rz (maximum height ) and Ra (arithmetic mean roughness) within a predetermined numerical range.

(Rz (maximum height))
The surface shape of the laminate of the present disclosure preferably has an Rz (maximum height) of 5.00 μm or more. In the present disclosure, Rz (maximum height) is a lateral parameter of the contour curve defined in JIS B0601:2013, and is one of the crest 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 in the contour curve at the reference length.
The larger the numerical value of Rz (maximum height) is, the larger (higher) the projections are when viewed from the valley, which is an index indicating that there are many such projections. Therefore, in a surface shape that satisfies the above RSm (average length of curvilinear element) and Sku (Kurtosis), if Rz (maximum height) is 5.00 μm or more, convex The feature that the shape near the top of the part is gently pointed or flattened is emphasized, and the slippery feel is improved. Moreover, the matting effect is also improved.

Rz (maximum height) is preferably 5.25 μm or more, more preferably 5.50 μm or more, still more preferably 6.00 μm or more, still more preferably 6.25 μm or more, and the upper limit is preferably 20.00 μm or less. , more preferably 18.00 μm or less, still more preferably 15.00 μm or less. When the Rz (maximum height) is within the above range, the matte effect and the slippery feel are improved.
Note that the cutoff value for the measurement of Rz (maximum height) in this specification 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 profile curve defined in JIS B0601: 2013, and is the height difference from the average surface in the profile curve at the reference length. Average value. The smaller the numerical value of Ra (arithmetic mean roughness), the smaller the projections in the surface shape and the smaller the recesses formed accordingly, which is an index indicating that the surface tends to have a smoother and more uniform shape. Therefore, in a surface shape that satisfies the above RSm (average length of curvilinear element) and Sku (kurtosis), if Ra (arithmetic mean roughness) is 3.00 μm or less, the shape of the convex portion of the surface shape can be further improved. Since there are more uniform and gentle things, the erratic touch is suppressed, and especially the slippery touch is improved. Moreover, the matting effect is also improved.

Ra (arithmetic mean roughness) is preferably 2.80 μm or less, more preferably 2.60 μm or less, still 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. , and more preferably 0.60 μm or more. When Ra (arithmetic mean roughness) is within the above range, the matte effect and the slippery feel are improved.
In addition, in measuring Ra (arithmetic mean roughness) in this specification, the cutoff value is 0.8 mm.

[Regarding layer structure]
The laminate of the present disclosure has a base material, a decorative layer and a matte layer in that order, and has the layer structure shown in FIG. In addition, from the viewpoint of flexibly responding to various demands such as the mechanical strength of the article, post-processing suitability, design appearance, etc., and from the viewpoint of manufacturing suitability, use handling suitability, etc., as shown in Fig. 3 A laminate obtained by laminating layers other than a base material, a decorative layer and a matte layer is also included.
Hereinafter, each layer constituting the laminate of the present disclosure will be described starting from the base material.

〔Base material〕
The substrate forming the laminate of the present disclosure is not particularly limited in its form (or shape), and is preferably selected from various shapes such as film, sheet or plate, polyhedron, polygonal prism, cylinder, sphere, and spheroid. can be adopted. Here, films, sheets and plates are referred to as films, sheets and plates according to their relatively thin thickness. , sheet and board differences shall not lead to any difference in the interpretation of rights of this disclosure. Therefore, in this specification, films, sheets and plates are sometimes collectively referred to as "sheets", "sheet-like" and the like.
The shape of the base material of the laminate of the present disclosure is preferably sheet-like. When the substrate is in the form of a sheet, it is particularly easy to form a matte layer, which will be described later, so that production aptitude is improved.

The constituent material of the base material is not particularly limited, and various materials such as resins, metals, non-metallic inorganic materials, fibrous materials, and woody materials can be appropriately selected according to the application. A base material composed of these various materials can be used as a single layer, or a plurality of layers in which two or more layers of base materials composed of these various materials are combined. In the case of multiple layers, two or more layers of different materials can be laminated and integrated to complement each other's functions of the materials of each layer.

When a multi-layer substrate is employed, each layer constituting the multiple layers, for example, a layer made of material A and a layer made of material B are laminated to form a laminate "A / B". When notating;
(1) Resin/wood material (2) Resin/metal (3) Resin/fibrous material (4) Resin/non-metallic inorganic material (5) Resin 1/resin 2 (for example, "olefin resin/acrylic resin" etc. If you have multiple layers composed of different resins)
(6) Metal/wood-based materials (7) Metal/non-metallic inorganic materials (8) Metal/fibrous materials (9) Metal 1/metal 2 (for example, multiple metals composed of different metals such as "copper/chromium" layer)
(10) Preferred examples include non-metallic inorganic materials/fibrous materials.
In addition, when the base material has a plurality of layers, an adhesive layer, a pressure-sensitive adhesive layer, a primer layer (both an anchor layer and an easy-adhesion layer) are provided between each layer to improve the adhesiveness of each adjacent layer. ) may be further included.

Various synthetic resins, natural resins and the like can be used as resins that can be used for the base material. Examples of synthetic resins include thermoplastic resins and curable resins, and thermoplastic resins are preferred in consideration of the suitability for production, handling, and post-processing of laminates.

Thermoplastic resins include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomers, and various olefin-based thermoplastic elastomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymer; polyethylene Polyester resins such as terephthalate, polybutylene terephthalate, polyethylene naphthalate, ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester thermoplastic elastomer; poly(methyl) acrylate, poly(meth)ethyl acrylate, poly( acrylic resins such as butyl methacrylate and methyl (meth)acrylate-butyl (meth)acrylate copolymer; polyamide resins such as nylon 6 and nylon 66; cellulose triacetate, cellophane, celluloid and the like Resin; Styrene resin such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin); Polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin , polyarylate resins, and polyimide resins.
Preferred natural resins include natural rubber, pine resin, amber, and the like.
Moreover, as the curable resin, a thermosetting resin, an ionizing radiation curable resin, and the like, which are exemplified as constituent materials of the later-described matte layer, are preferably exemplified.

Examples of metals that can be used for the substrate include aluminum and aluminum alloys such as duralumin; iron and iron alloys such as iron, carbon steel and stainless steel; copper and copper alloys such as copper, brass and bronze; gold and silver. , chromium, nickel, cobalt, tin, and titanium. Moreover, as the base material composed of metal, those having the surface thereof coated with such metal by plating or the like are also preferably exemplified.

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

Examples of fibrous materials that can be used for the base material include thin paper, kraft paper, fine paper, Japanese paper, titanium paper, linter paper, parchment paper, paraffin paper, parchment paper, glassine paper, backing paper for wallpaper, paperboard, and gypsum board. Paper such as base paper; woven fabrics or non-woven fabrics made of fibers such as polyester resin fibers, acrylic resin fibers, proteins such as silk, cotton and hemp, natural fibers such as cellulose, glass fibers and carbon fibers are preferred. Among these materials, in order to improve the interlaminar strength between the fibers of the paper base material composed of paper or with other base materials used in combination with the paper base material, and to prevent fluffing, acrylic resins, Various resins such as styrene-butadiene rubber, melamine resin, and urethane resin may be added (impregnated with these resins after paper making or incorporated during paper making). As the paper to which the resin is added, for example, inter-paper reinforced paper, resin-impregnated paper and the like are preferably mentioned.
In addition, as a laminate obtained by laminating a layer composed of a fibrous material and a layer composed of a resin, a vinyl chloride resin layer and an olefin resin are added to the surface of wallpaper backing paper commonly used in the field of building materials. Preferred examples include wallpaper raw fabrics in which layers composed of various resins such as layers and acrylic resin layers are laminated.

Examples of woody materials that can be used as the base material include veneers, plywoods, laminated lumbers, and the like, which are composed of various types of wood such as cedar, cypress, pine, zelkova, oak, oak, walnut, lauan, teak, and rubber trees. Particle board, medium density fiber board (MDF), etc. are preferably mentioned.

As the base material, any base material composed of the materials described above can be used without limitation, and the material may be appropriately selected according to desired properties and the like. From the viewpoint of improving the matte effect and the slippery feel, a base material composed of a resin or a fibrous material is preferable, and a base material composed of a resin is more preferable.
Among resins, olefin resins, vinyl chloride resins, polyester resins, and acrylic resins are preferable, olefin resins, vinyl chloride resins, and polyester resins are more preferable, polyethylene and polypropylene are preferable as olefin resins, and polyvinyl chloride is preferable as vinyl chloride resins. Polyethylene terephthalate is preferred as the polyester resin. Moreover, among fibrous materials, paper is preferable. By using a base material composed of these materials, it is particularly easy to obtain the surface shape described above, and it is easy to improve the slippery feel.

The shape and dimensions of the single-layer or laminate substrate are not particularly limited, and may be appropriately selected in consideration of the intended use, desired properties, post-processing suitability, and the like.
When adopting the shape of a film, a sheet or a plate, thickness is a representative dimension for the design of the laminate, but the thickness is not particularly limited, and the suitability for manufacture, suitability for use and handling, suitability for post-processing, and mechanical strength In view of economy, etc., the thickness should preferably be selected from the range of 10 μm or more and 10 cm or less. When adopting the shape of a film or sheet, it is preferably selected from the range of 20 μm or more and 300 μm or less, and when adopting the shape of a plate, it is preferably selected from the range of 1 mm or more and 2 cm or less.

The base material has at least One surface can be subjected to a physical surface treatment such as an acid value method or a roughening method, or a surface treatment such as a chemical surface treatment for improving easy adhesion.
Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, and the like. Examples of roughening methods include sandblasting and solvent treatment. These surface treatments may be appropriately selected according to the type of base material, and corona discharge treatment is preferred from the viewpoint of the effect of improving easy adhesion by surface treatment, workability, and the like.

The substrate may be colored or may not be colored (it may be transparent), and when colored, the mode of coloring is not particularly limited, and may be transparently colored, Opaque coloring (concealing coloring) may be used, and these can be selected arbitrarily.

When the substrate is colored, examples of coloring agents include white pigments such as titanium white, inorganic pigments such as iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. , isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethine azo black pigments, perylene black pigments, and other organic pigments or dyes; metal pigments made of scale-like foil pieces such as aluminum and brass; titanium dioxide-coated mica, bases coloring agents such as pearl luster (pearl) pigments composed of scaly foil pieces such as organic lead carbonate. For example, when the surface hue of an adherend such as a resin molded article on which a laminate is laminated varies, it is desired to conceal 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 with a resin, any means such as adding (kneading or kneading) a coloring agent into the resin, or forming a coating film of a paint containing a resin and a coloring agent, should be adopted. can be done. When a base material made of fibrous material such as paper, woven fabric, or non-woven fabric is to be colored, it can be carried out by any means such as mixing with pulp or fibrous material, forming a coating film, or the like, or a combination thereof.
When coloring a base material made of a wood-based material, it can be carried out by dyeing with a dye, coating film formation, or a combination of these methods. In the case of coloring a substrate made of metal, in addition to coating film formation, an electrolytic coloring method or the like can be employed in which a metal oxide film is formed on the surface using an anodizing method. In addition, when the base material is colored with a non-metallic inorganic material, it can be carried out by either means of forming a coating film or adding it to the base material, or a combination of these means.

Additives may be added to the base material, if necessary. Additives, mainly in the case of resins, include, for example, inorganics such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. etc. The amount of the additive compounded is not particularly limited as long as it does not impair the surface characteristics, processing characteristics, etc., and can be appropriately set according to the required characteristics.

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

In the present disclosure, the above substrates may be used singly or in combination. A combination of a plurality of paper substrates may be used, or a paper substrate and a fiber substrate, a paper substrate and a resin substrate, a fiber substrate and a resin substrate, a paper substrate, a fiber substrate and a resin substrate. It may be a combination of materials. In addition, the resin base material may be composed of a single layer of the above resin base material, or a multilayer structure of the same or different resins.

The thickness of the substrate is as described above. Considering mechanical strength, economic efficiency, etc., it is more preferably 40 μm or more, and the upper limit is more preferably 200 μm or less, and further preferably 100 μm or less.
For the same reason, when the substrate is paper, the basis weight is generally preferably 20-150 g/m ² , more preferably 30-100 g/m ² .

[Matte layer]
The matte layer in the laminate of the present disclosure is a layer provided on the decorative layer described later, and its surface has the above-described surface shape, that is, an uneven shape composed of irregular wrinkles, RSm (curved element is 20.00 μm or more and Sku (kurtosis) is 4.00 or less. Also, as shown in FIGS. 2 and 3, the layer is provided such that the surface having the surface shape is the surface opposite to the substrate side.
Therefore, since the laminate of the present disclosure has a matte layer on its surface, considering the mechanical strength of the laminate, manufacturing suitability, etc., the matte layer is a cured product of the resin composition, preferably a cured product It is preferably a layer composed of a cured product of a curable resin composition containing a resin.

As the resin composition for forming the matte layer, a resin composition containing a resin and a wrinkle-forming stabilizer ( Hereinafter, it may be referred to as "a resin composition for forming a matte layer".) is preferable. That is, the matte layer in the present disclosure is preferably a layer containing a resin and a wrinkle stabilizer.

(wrinkle-forming stabilizer)
The wrinkle-forming stabilizer stabilizes the formation of irregular wrinkles on at least one surface of the matte layer, thereby developing an irregular shape composed of irregular wrinkles. Then, by uniformly expressing the visibility of the matte effect over the entire surface of the matte layer and reducing partial gloss unevenness, the visibility of the matte effect is stable, and the entire surface of the matte layer It has the function of imparting a uniform surface condition by stably forming irregular wrinkles over the surface. Irregular wrinkles in the matte layer greatly contribute to the development of a slippery feel. In the present specification, the expression "visibility of stable matting effect" and similar expressions may be used hereinafter for "visibility of stable matting effect". Also, "uniformity of surface condition" may be referred to as "texture".
Therefore, the so-called "matting agent" in the prior art and the "wrinkle-forming stabilizer" in the present disclosure have the same matting mechanism (action) even if the constituent substances and the average particle size are the same. , the relationship between the structure for expressing matte, the amount used, and the degree of surface gloss (gloss value). It also differs from the "matting agent" in that it develops a slippery feel by forming irregular wrinkles.

Matting agents that have been used for matte expression in the prior art such as the above-mentioned Patent Document 1 express the visibility of the matting effect themselves due to the light diffusion effect caused by the physical shape. is. Specifically, what is generally called a matting agent generally has a refractive index difference between the matting agent particles and the surrounding resin and air, and the light reflection and refraction properties corresponding to the contour shape of the particles The visibility of the matte effect is expressed by the light diffusion effect of the interface. On the other hand, in the laminate of the present disclosure, the wrinkle stabilizer is not due to light diffusion due to reflection and refraction of light rays by the particles themselves to develop the visibility of the matting effect, but rather to the wrinkle stabilizer. By stabilizing the formation of irregular wrinkles on the surface of the extinguishing layer, the light diffusion effect at the interface between the surface and the air with a difference in refractive index stably imparts the visibility of the matte effect and texture to the laminate. That's what it means. Therefore, even if the wrinkle-forming stabilizer used in the present disclosure is the same as the matting agent that itself exhibits the visibility of the matting effect, even if both constituent substances and average particle sizes are the same, both are different in the matting mechanism and action, the structure for developing matting, and the like.

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

The matting layer in the laminate of the present disclosure may contain an agent that has been conventionally used as a matting agent. Considering the characteristics of the effect of the present invention that a slippery touch is obtained, it is preferable that the matting agent is not included. Thus, the laminate of the present disclosure has extremely excellent matte effect visibility and texture even without substantially containing matting agents that have been used to obtain matte effect visibility in the past. It can be said that it is a thing. Here, "does not contain a matting agent" means not containing a matting agent at all, and even if it does contain a matting agent, it does not have the visibility of the matting effect based on the action and effect of the matting agent itself. Specifically, it means that the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, and more preferably 3.0 parts by mass or less per 100 parts by mass of the resin. .
In the specification of the present application, the term “matting agent” refers specifically to a layer that can contain the matting agent, that is, the matting layer thickness means particles having an average particle size with a lower limit of greater than 100% of the height and greater than 30 μm, whichever is smaller.

In the present disclosure, the wrinkle-forming stabilizer is not a matting agent, and is particularly limited as long as the average particle size is 100% or less of the matte layer thickness or 30 μm or less, whichever is smaller. can be used without
In consideration of improving the matting effect and smooth touch, the average particle size of the wrinkle-forming stabilizer having an upper limit of 100% or less of the thickness of the matte layer and 30 μm or less, whichever is smaller, is It is preferred to use at least one of two types of wrinkle-forming stabilizers distinguished by particle size. Specifically, the two types of wrinkle-forming stabilizers have an average particle size of 1 μm or more and a wrinkle-forming stabilizer 1 whose upper limit is the smaller of 100% or less of the thickness of the matte layer and 30 μm or less. and wrinkle stabilizer 2 having an average particle size of less than 1 μm.

In the present disclosure, the use of at least one of the two wrinkle-forming stabilizers stabilizes the formation of irregular wrinkles, stably provides excellent matting effect, and also provides smooth touch. . In the present disclosure, Wrinkle Stabilizer 1, Wrinkle Stabilizer 2 can be used alone, and Wrinkle Stabilizer 1 and Wrinkle Stabilizer 2 can be used together. It is more preferable to use wrinkle-forming stabilizer 1 and wrinkling-forming stabilizer 2 together. By using them together, the matte effect and the slippery feel are improved.

As the wrinkle-forming stabilizer, for example, organic particles or inorganic particles can be used.
Examples of organic substances constituting organic particles include polymethyl methacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluorine-based resin and polyester-based resin. etc.
Inorganic substances constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, barium sulfate, and the like. 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, and irregular shapes.

The upper limit of the average particle size of the wrinkle-forming 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 size of the wrinkle-forming stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, and even more preferably 1.5 μm or more. 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, It is more preferably 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, and even more preferably 7 μm or less. Any combination of the upper limit of the thickness and the upper limit of the absolute value may be set to the smaller one. For example, the upper limit may be 90% or less of the matte layer thickness or 20 μm or less, whichever is smaller, or the smaller one of 90% or less and 10 μm or less of the matte layer thickness may be the upper limit. can also The thickness of the matte layer will be described later.

The average particle size of wrinkle stabilizer 2 is less than 1 μm. Considering stabilizing the formation of irregular wrinkles, stably improving the matting effect, and improving the smooth touch, the average particle size of the wrinkle-forming stabilizer 2 is preferably 1 nm or more, and more It is preferably 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, and still more preferably 500 nm or less.
In the present specification, the average particle size of the wrinkle-forming stabilizer is measured as the volume average value d50 in particle size distribution measurement by laser light diffraction method.

Considering that the wrinkle-forming stabilizer stabilizes the formation of irregular wrinkles, stably improves the matting effect, and improves the slippery feel, the wrinkle-forming stabilizer (wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer The total content of these when used together with the formation stabilizer 2) is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass, relative to 100 parts by mass of the resin forming the matte layer. It is at least 1.0 part by mass, more preferably at least 1.2 part by mass. On the other hand, the upper limit of the .0 parts by mass or less. Regarding the upper limit, there is no particular limitation in terms of improving the stable matting effect and improving the slippery feel, but if the upper limit is within the above range, for example, coating of a resin composition for forming a matte layer The productivity of the decorative material due to its properties, etc., and the visibility and texture of the matting effect are efficiently improved.

When the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 are used in combination, the content of each of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is not particularly limited as long as the total content is within the above range. However, the content of the wrinkle-forming stabilizer 2 is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1.0 parts by mass or more with respect to 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, and even more preferably 3.5 parts by mass or less. Further, the blending ratio of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is preferably 5.0 to 95.0 as the blending amount of the wrinkle-forming stabilizer 1 when the total amount of these is 100 parts by mass. Parts by mass, more preferably 10.0 to 90.0 parts by mass, still more preferably 15.0 to 75.0 parts by mass, still more preferably 30.0 to 50.0 parts by mass.

As the wrinkle-forming stabilizer, organic particles and inorganic particles can be used as described above. Matting agents such as spherical alumina and calcium carbonate are used in the matte layer of the decorative sheet described in 1 above. In order for matting agents such as spherical alumina and calcium carbonate to express the visibility of the matting effect themselves due to the light diffusion effect resulting from their physical shape, as described in Patent Document 1, It is necessary to use 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate in a total amount of about 50 parts by weight per 100 parts by weight of resin. However, in the present disclosure, even if the content is small as described above, that is, the content necessary for expressing the visibility of the matte effect itself due to the light diffusion effect caused by the physical shape Even with a smaller content, a very excellent matting effect is obtained compared to the effect obtained by the matting agent, and a slippery feel is also obtained.
Therefore, the laminate of the present disclosure is superior to the case using a matting agent by stably forming irregular wrinkles on the surface despite being substantially free of the matting agent. It can be said that the visibility of the matte effect is stably obtained, and at the same time, a texture is obtained, and a slippery touch is also obtained.

(Surface shape of matte layer)
The matte layer in the laminate of the present disclosure is a layer having the above-described surface shape, preferably with a cured product of a resin composition for forming a matte layer containing the above-described specific wrinkle-forming stabilizer in a specific content. layer to be composed. As mentioned above, by stabilizing the formation of irregular wrinkles on the surface of the matte layer, the matte effect is stably expressed due to the light diffusion effect caused by the shape of the wrinkles, and a smooth touch is also expressed. layer. FIG. 1 is a schematic plan view showing one embodiment of the laminate of the present disclosure, and is a schematic image of the surface of the laminate obtained in the 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.

Irregular wrinkles appearing on at least one surface of the matte layer are defined by the above surface profile, i.e., RSm (mean length of curvilinear element) and Sku (kurtosis) within the above specified numerical range, preferably other Rz (maximum height) and Ra (arithmetic mean roughness) are not particularly limited as long as the surface shape has the above surface shape due to the appearance of irregular wrinkles. Formation is stable, a matte effect is stably exhibited, and a slippery touch is also exhibited.
Regarding irregular wrinkles, at least one surface of the matte layer needs to have an uneven shape composed of irregular wrinkles in order to obtain a good matte effect and a slippery feel. In addition, in order to improve the matte effect and the slippery feel, the irregular wrinkles are formed by a plurality of protrusions formed by a plurality of protrusions and a recess formed by being surrounded by the plurality of protrusions. Preferably, the projections have filamentous projections. As used herein, the term “striated projection” (hereinafter also referred to as “striated projection”) means that the ratio of the length to the width of the projection (length/width) is 3 or more, preferably 5 More preferably, it means 10 or more, and the method for determining the length and width will be described later.
In the present disclosure, the more preferable irregular wrinkles are composed of a plurality of protrusions formed by the plurality of filamentary protrusions and recesses formed by being surrounded by the plurality of filamentary protrusions.

Aspects relating to these irregular wrinkles include, for example, the aspect shown in FIG. In FIG. 1, the surface of the laminate, that is, the surface of the matte layer, has irregular wrinkles in plan view, and the irregular wrinkles are formed by a plurality of curved linear projections. It is configured by including a plurality of protrusions 3 and a recess 2 formed by being surrounded by a plurality of projections (plurality of protrusions 3), and at least a part of the plurality of curved protrusions 3 , each formed by meandering filamentary protrusions, forming a meandering recess 2 surrounded by the meandering filamentary protrusions. The laminate of the present disclosure stably exhibits a matting effect by stabilizing the formation of irregular wrinkles shown in FIG. 1, and also exhibits a slippery feel.

Here, “curved” means having one or more portions in which the extending direction of the continuous filamentary projections 3 is reversed from one side to the other side in plan view. As an example of the 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 protrusion 3 of the filament is ignored (when the planar view shape width is regarded as 0) is approximated by a continuous curve, a form having an inflection point, and the like. In addition, when approximating with a straight line when ignoring the width of the planar view shape of the protrusion 3 of the filament, a form having a portion approximated by two sides sandwiching one vertex of a V-shaped broken line or triangle etc.

In addition, the term "meandering" refers to a portion in which the extending direction of the continuous linear projections 3 is reversed from one side to the other side (hereinafter also referred to as a "reversed portion") at least two times. When the filamentary protrusions 3 are advanced in their extending direction, the filamentary protrusions 3 have a portion where the extending direction of the filamentary protrusions 3 is alternately reversed in two adjacent locations. means that For example, there is a form having a portion approximated by a Roman letter "S" when approximating with a continuous curve when the width of the projection 3 of the filaments in a plan view is ignored. Further, when the linear projections 3 are approximated by a straight line when the width of the projection 3 of the filament in plan view is ignored, there is a form having a portion approximated by the Roman letter "W".

In this specification, the term "irregular" means a shape having a certain rule, or a shape that is arranged according to a certain rule, which cannot be said to be patterned. A typical example of a non-irregular shape, that is, a regular shape is a so-called "lenticular lens (lens)," in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction perpendicular to the longitudinal direction. lenticular lens)”, which are arranged with a certain periodicity in a specific direction. Therefore, the irregular wrinkles in the present disclosure refer to the fact that the shape of one protrusion itself is irregular rather than a shape formed according to a certain rule such as periodicity, and that a plurality of protrusions formed by a plurality of protrusions It includes 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 laminated body of the present disclosure, the shape of one protrusion (one protrusion) itself, the shape and arrangement of each of the plurality of protrusions (plurality of protrusions), and the shape of the recess surrounded by the plurality of protrusions If any one of is irregular, a matte effect and a slippery feel due to having irregular wrinkles can be obtained, but both are preferably irregular. By having irregular wrinkles, the laminate of the present disclosure improves the visibility and texture of the matte effect, stably exhibits an extremely excellent matte effect, and exhibits a slippery feel. become a thing.

As described above, the matte layer has irregular wrinkles on at least one surface thereof. Protrusions and recesses in the uneven shape, for example, using the lightness difference of the image on the surface of the laminate of the present disclosure, the darkest part in the density distribution image has a gradation of 255, and the lightest part in the density distribution image has a gradation of 255. For the gradation 0 to 255, the gradation 0 to 127 can be divided into concave portions, and the gradation 128 to 255 into convex portions by binarization processing.

The surface of the laminate of the present disclosure may have an uneven shape formed by irregular wrinkles on at least a part thereof, and preferably has an uneven shape formed by irregular wrinkles over the entire surface. The place where irregular wrinkles are formed (that is, the place with the matte layer) is not particularly limited as long as it is on the surface of the laminate, and if it exists on at least a part of the surface, formation of irregular wrinkles A matte effect and a slippery feel due to are expressed. For example, an uneven shape (that is, matte layer) formed by irregular wrinkles is formed on a portion corresponding to the pattern of the decoration layer, for example, on the pattern layer, as a portion where the pattern is more matte than the surrounding area. Since it is visible, it is possible to improve the designability. In this case, there are places where the matte layer is provided and places where it is not provided.

Also, as shown in FIG. 1, it has a plurality of protrusions formed by a plurality of irregular but uniform protrusions and recesses surrounded by the protrusions. is preferred. Therefore, a shape in which the width of one protrusion (protrusion) changes extremely is unlikely to result in the above-described surface shape, and is not a preferable mode for obtaining the visibility and texture of the matte effect, and the surface is slippery. It cannot be said that this is a preferable mode for obtaining such a tactile sensation. Concerning the shapes of protrusions (protrusions) and recesses that form irregular wrinkles, specific aspects that can be advantageous in stably improving the matting effect and improving the slippery touch will be described below. do. When the irregular wrinkles have the following shape, it becomes easier to exhibit the surface shape described above, and the matting effect and smooth touch are improved.

The height of the protrusions (the height of the projections) of the irregular wrinkles formed on at least one surface of the matte layer 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. The width of the protrusion is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, and still more preferably 3 μm. It is below. When the height and width of the protrusions are within the above ranges, the surface shape described above is likely to be exhibited, and in relation to the recesses, the matting effect is stably improved and the slippery feel is improved.
Here, the above dimensions of the protrusions are arbitrary 10 protrusions (protrusions) in arbitrary 10 locations (100 μm square area × 10 locations) of the laminate of the present disclosure, that is, the average value of a total of 100 protrusions is. In addition, as shown in FIG. 1, the width of one protrusion (projection) is not the same, but wide and narrow, so the width of one protrusion (projection) is The average value of the width of any five points in The same applies to the height of the projection (protrusion).

The depth of the concave portion is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is about 10 μm or less. The width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still 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. is. When the depth and width of the concave portions are within the above ranges, the surface shape described above is likely to be 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 recesses are determined in the same manner as the dimensions of the projections.

The distance from the top of the projection to the bottom of the recess, that is, the height difference between the projection and the recess, is preferably 1 μm or more, more preferably 2 μm or more, still more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 2 μm or more. It is preferably 8 μm or less, more preferably 7 μm or less. When the distance is within the above range, the above surface shape is likely to be exhibited, the matting effect is stably improved, and the slippery feel is improved.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The occupancy ratio of the convex portion is preferably 15% or more, more preferably 20% or more, and still more preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, and further preferably 60% or less. is. When the occupancy ratio of the convex portions is within the above range, the above-described surface shape is likely to be exhibited, and in relation to the occupancy ratio of the concave portions surrounded by the convex portions, the matting effect is stably improved and the touch is slippery. improves.
Here, the occupancy ratio of the convex portions is the average value of the occupancy ratio of the convex portions at arbitrary 10 locations (100 μm square area×10 locations) of the laminate of the present disclosure.

The protrusions and recesses may have portions of approximately the same direction and approximately the same width, but considering the improvement of the matting effect and the improvement of the slippery touch, it is preferable that the length is short. Specifically, the length of continuous protrusions and recesses 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. It is more preferably 10 μm or more, still more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, so that the matte effect is stably improved and the slippery feel is improved.
Here, 80% or more of any 10 convex portions and concave portions (that is, a total of 100 convex portions and concave portions) in arbitrary 10 locations (100 μm square area × 10 locations) of the laminate of the present disclosure It preferably satisfies the conditions, more preferably 85% or more, still more preferably 90% or more, and even more preferably 95% or more. In addition, the “substantially” of “substantially the same” in this specification means that they are substantially the same, without branching, meaning a difference within ± 3 ° in the case of direction, and ± 5 in the case of width Means difference within %.

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

FIG. 2 is a cross-sectional view showing one embodiment of the laminate of the present disclosure, and is a cross-sectional view of the laminate 1 cut 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-angled shape as shown in FIG. 2a, a semicircular or semielliptical shape as shown in 2b, or a combination thereof. Alternatively, a shape such as 2c in FIG. 2, in which one convex portion partially has a concave portion, may be used.
On the other hand, as for the shape of the convex portion, as shown in 3a and 3b of FIG. 2, although the width varies, it exhibits a semicircular or semielliptical shape.

The thickness of the matte layer is not particularly limited as long as it is a thickness capable of stably expressing the matting effect and forming the above-mentioned irregular wrinkles to the extent that a slippery feel can be expressed. 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, and even more preferably 5 μm or more, and the upper limit is preferably 300 μm or less. , more preferably 200 μm or less, still more preferably 150 μm or less, and even more preferably 100 μm or less.
In this specification, the thickness of the matte layer is the average value of 20 thicknesses measured from an image taken with a scanning electron microscope (SEM) of the cross section of the laminate. . The acceleration voltage of the SEM is set to 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 surface shape over its entire surface, and since it is sufficient that the laminate of the present disclosure has a surface shape on at least part of the surface, at least part of the surface of the laminate It may be provided on the entire surface.
If the matte layer is provided at a location where consumers can see and touch the laminate, that is, the surface shape is provided at a location where consumers can see and touch the laminate. The effects of the invention, namely, the extinguishing effect and the slippery feel, are obtained.

Further, even when the substrate has the shape of a film, a sheet, or a plate, the matte layer may be provided at a location where consumers can see and touch the laminate. It may be provided on the entire surface of the surface, and from the viewpoint of improving the matte effect and the smooth touch, as shown in FIGS. It is preferable that

(resin)
As the resin for forming the matte layer, a resin composition for forming a matte layer containing a predetermined amount of the wrinkle-forming stabilizer is formed and cured to form a cured product and a resin constituting the matte layer. good. 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. Therefore, in addition to being a resin that easily forms wrinkles due to the wrinkle-forming stabilizer, considering the improvement of usability as a laminate, it expresses surface properties such as processing characteristics, stain resistance, scratch resistance, and weather resistance. It is preferably a resin that is easy to cure, and an ionizing radiation-curable resin is a preferable resin from these points of view. 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 the surface characteristics. .

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. A functional group having an ethylenic double bond such as an allyl group is preferred. In addition, in this specification, a (meth)acryloyl group shows an acryloyl group or a methacryloyl group. Moreover, in this specification, (meth)acrylate indicates acrylate or methacrylate.
In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing and/or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are 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 curable resins. Considering stabilizing the formation of wrinkles by the wrinkle-forming stabilizer, stably improving the matting effect, and improving the slippery feel, an ultraviolet curable resin is preferred.
Specifically, the ionizing radiation-curable resin can be appropriately selected and used from polymerizable monomers and polymerizable oligomers 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 having at least a (meth)acryloyl group as the ionizing radiation-curable functional group. be done.

Stabilize the formation of wrinkles, stably improve the matting effect, improve the smooth touch, and further improve 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. Moreover, when it is the said number of functional groups, said surface shape is especially easy to obtain, and it becomes easy to improve a slippery touch.
These polyfunctional (meth)acrylates may be used alone or in combination.

In addition, it is preferable to use a monofunctional monomer in combination with the polyfunctional monomer, in order to particularly improve the slippery touch. As a 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 polymerizable oligomers include polyfunctional oligomers having two or more ionizing radiation-curable functional groups in the molecule, preferably polyfunctional (meth) having at least (meth)acryloyl groups as ionizing radiation-curable functional groups. Acrylate oligomers are mentioned. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, and the like.
Furthermore, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. , aminoplast resins modified with aminoplast resins having many reactive groups in small molecules (meth)acrylate oligomers, novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers having cationic polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination.
As the polymerizable oligomer, among the above, urethane (meth)acrylate oligomer, epoxy (meth)acrylate oligomer, polyester (meth)acrylate oligomer, polyether (meth)acrylate oligomer, polycarbonate (meth)acrylate oligomer, acrylic (meth) 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. When these polymerizable oligomers are used, the formation of wrinkles can be stabilized, the matting effect can be stably improved, the slippery touch can be improved, and furthermore, post-processing properties, scratch resistance, and Surface properties such as weather resistance can be improved.

The number of functional groups of 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 touch can be improved, and further processing characteristics, scratch resistance and Surface properties such as weather resistance can be improved.
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, 1,400 or more and 2,900 or less are even more preferable. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

In the present disclosure, it is preferable to use a combination of the polymerizable oligomer and the polymerizable monomer as the resin forming the matte layer. In this case, the polymerizable oligomer is preferably a polyfunctional urethane (meth)acrylate oligomer, more preferably a polyfunctional urethane acrylate oligomer. In addition, as the polymerizable monomer, it is preferable to use at least a monofunctional monomer, and it is more preferable to use 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 in combination with. It can stabilize the formation of wrinkles, stably improve the matting effect, improve the slippery feel, and further improve surface properties such as processing properties, scratch resistance, and weather resistance. .
When used in combination, for the same reason, the content of the polymerizable oligomer with respect to the total 100 parts by mass 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 further It is preferably 20 parts by mass or more, 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, and even more preferably 35 parts by mass. It is below.

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

When the resin is an ultraviolet curable resin that is cured by ultraviolet rays, 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 light (without using ionizing radiation), and practical surface properties can be obtained.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, thioxanthones and the like.
In addition, the photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. One or more selected types can be mentioned.

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 having weather resistance. For example, it may contain various weather resistance agents such as ultraviolet absorbers and light stabilizers. preferable.
As the UV absorber, any UV absorber that is commonly used for cosmetic materials, decorative sheets, etc. can be used without particular limitation. Examples include triazine-based ultraviolet absorbers. As the light stabilizer, any light stabilizer commonly used for 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. Moreover, 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.
Weather resistance agents such as these ultraviolet absorbers and light stabilizers can be used alone or in combination.

[60° gloss value and 85° gloss value]
The laminate of the present disclosure is a laminate with excellent matte effect visibility and texture. In the present specification, "matte" means that the gloss is difficult to see, and it cannot be said unconditionally because it changes 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 example, in laminates exhibiting black or other dark colors, even with the use of a matting agent, it has been possible to obtain excellent visibility of the matting effect with a 60° gloss value of 20.0 or less, preferably 10.0 or less. Then it was. Here, the term “dark color” means low lightness, for example, CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* L ^* value in the 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, making it difficult to manufacture easily, and the surface characteristics are lowered. In addition, for example, for a laminate exhibiting a color tone other than black or other dark colors, even if a matting agent is used, there is a lower limit to the numerical value of the 60° gloss value, and it is the same as a laminate exhibiting black. It was not possible to easily obtain a laminate that is excellent in both the visibility of the matte effect and the texture. Such a tendency becomes more remarkable as the 60° gloss value becomes smaller.

In the laminate of the present disclosure, by using a combination of wrinkle-forming stabilizers having a predetermined average particle size and reducing the content thereof to a small amount as described above, a stable and extremely excellent matting effect can be visually recognized. Not only are the properties and textures obtained, but also a slippery feel is obtained. In addition, by suppressing the amount of the 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. It naturally has surface properties such as stain resistance, scratch resistance, and weather resistance.

Although the laminate of the present disclosure changes depending on the color tone as described above, it cannot be defined unconditionally. 7.5 or less, 5.0 or less, 4.0 or less, and 3.5 or less, and the visibility of the extremely excellent matting effect can be expressed.

Also, a laminate exhibiting a color tone other than black or other dark colors can have the above 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 it further has other layers. , the 60° gloss value of the surface of the matte layer. In addition, when another layer is provided and another layer is provided on the surface side from the matte layer, the 60 ° gloss value means the 60 ° gloss value of the other layer, but the laminate of the present disclosure has a particular 60° gloss value substantially due to the composition of the matte layer.
In this specification, the 60° gloss value on the matte layer side is the 60° specular gloss measured in accordance with JIS K 5600-4-7: 1999, and a gloss meter or the like is measured at arbitrary 10 points. is the average value of the values that can be measured from the matte layer side using

In addition, the laminate of the present disclosure preferably has an 85° gloss value of 25.0 or less, more preferably 20.0 or less, and can be treated as "matte" from this point as well. In addition, when the 85 ° gloss of the laminate of the present disclosure is extremely low, for example, less than about 7.0, in addition to the uneven shape of the matte layer composed of irregular wrinkles, for example, macro unevenness (yuzu skin, There is a tendency to form a satin-like texture, etc.). Therefore, it goes without saying that a lower value is not necessarily more preferable in order to achieve a good slippery feel in the laminate of the present disclosure, and there is a substantial lower limit value.
As described above, the laminate of the present disclosure varies depending on the color tone, so it cannot be defined unconditionally. It is 25.0 or less, 20.0 or less, and further 15.0 or less, so that the visibility of the extremely excellent matting effect can be expressed. In addition, as with the 60° gloss value, regarding the 85° gloss value, a laminate exhibiting a color tone other than black or other dark colors can also have the above 85° gloss value.
The 85° gloss value, like the 60° gloss value, is an 85° specular gloss measured in accordance with JIS K 5600-4-7: 1999, and is matted using a gloss meter or the like at arbitrary 10 points. It is the average value of the values that can be measured from the layer side.

[Decoration layer]
The laminate of the present disclosure has a decorative layer in order to improve designability. The decorative layer is a layer provided between the substrate and the matte layer. Moreover, when a transparent resin layer, which will be described later, is provided, the base material, the decorative layer, the transparent resin layer, and the matte layer may be provided in this order.

The decoration 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 referred to as the "solid colored layer" and is the layer indicated by "6a" in FIGS. 6b''. Moreover, as shown in FIGS. 2 and 3, a solid colored layer and a pattern layer may be combined.

The pattern (pattern) of the pattern layer is not particularly limited, and any desired pattern may be adopted. Examples include texture patterns on the surface of fabric, grain patterns on the surface of leather, geometric patterns, letters, figures, and combinations thereof.
In addition, patterns such as texture patterns, metal surface processing patterns such as hairlines, leather grain patterns, etc., which are patterns of fabrics, metal surfaces, and baby skins, which are exemplified as those having a "slippery feel", are also preferable. be done. A more realistic design can be expressed by combining the "slippery feel" of the laminate of the present disclosure and the pattern of the object having the "slippery feel".

The ink used for the decorative layer is a mixture of a binder resin and a coloring agent such as a pigment or dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, etc. used.
The binder resin for the decorative layer is not particularly limited, and examples include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and vinyl chloride-vinyl acetate copolymers. Resins such as coalesced resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins and cellulose acetate resins can be used. Moreover, various types of resins can be used, such as a one-liquid curable resin and a two-liquid curable resin with a curing agent such as an isocyanate compound.

As the coloring agent, pigments having excellent hiding properties and weather resistance are preferred. Pigments similar to those exemplified as pigments that can be used in the substrate 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 with respect to 100 parts by mass of the resin constituting the decoration layer. More preferred are:

The decorative layer may contain additives such as ultraviolet absorbers, weathering agents such as light stabilizers, and colorants.
The thickness of the decorative layer may be appropriately selected according to the desired pattern, and is preferably 0.5 μm or more and 20 μm or less, preferably 1 μm, in consideration of concealing the background color of the adherend and improving the design. 10 μm or less is more preferable, and 2 μm or more and 5 μm or less is even more preferable.

[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 later, and the like, and is used for applications such as exterior members and interior members. It is what you get. Considering that the substrate has the decorative layer described later, and that it is used for the above applications, 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, still more preferably 10% or less.
In this specification, the total light transmittance of the laminate is the total light transmittance measured according to JIS K7361-1:1997, and is the average value of the measurements at 10 arbitrary points.

[Other layers]
The laminate of the present disclosure may optionally have other layers such as a primer layer, a transparent resin layer, an adhesive layer, etc., in addition to the base material, the matte layer, and the decorative layer. A cross-sectional view showing one embodiment of a laminate of the present disclosure having these layers is shown in FIG. FIG. 3 is a cross-sectional view showing one embodiment of the laminate of the present disclosure, and is a cross-sectional view of the laminate 1 cut 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 has a substrate 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 multiple layers, it may have a primer layer in order to improve the interlayer adhesion of the multiple layers.
For example, a primer layer can be provided between the matte layer and the substrate, 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 ultraviolet absorbers and light stabilizers, 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 (carbonate bonds in the main chain of the polymer). urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the end and side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer Resins such as coalescent resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins are preferred, and these can be used alone or in combination.
The binder resin may be obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins, followed by cross-linking and curing. Among these, a polyol resin such as an acrylic polyol resin is preferably crosslinked and cured with an isocyanate curing agent, and more preferably an acrylic polyol resin is crosslinked and cured with an isocyanate curing agent.

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 substrate for the purpose of improving adhesion to an adherend such as a resin molded product, a primer is added to the side opposite to the side of the substrate on which the matte layer is provided. It can also have a layer (also called a "back primer layer").

(Transparent resin layer)
The laminate of the present disclosure may have a transparent resin layer in order to increase its strength and from the viewpoint of protecting 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 resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, and the like. Among these, polyolefin resins and vinyl chloride resins are preferred from the viewpoint of suitability for post-processing. Also, two or more of these various resins may be laminated or mixed for use.

The transparent resin layer may be transparent enough to allow the decoration layer to be visually recognized, and may be colorless and transparent, colored transparent, and translucent. That is, in the present specification, "transparency" means colorless transparency, as well as colored transparency and semi-transparency.

The transparent resin layer may contain additives such as ultraviolet absorbers, light stabilizers and other weather resistance agents, and colorants and the like.
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, in consideration of the protection of the decorative layer and post-processing suitability.

(glue)
When the laminate of the present disclosure has a base material and a transparent resin layer, it may have an adhesive layer between the base material and the transparent resin layer in order to improve adhesion between the two layers.
Further, the positional relationship between the adhesive layer and the decorative layer is not particularly limited. It may have an adhesive layer, a decoration layer and a transparent resin layer in this order from the side closer to the material.

The adhesive layer can be composed of, for example, an adhesive such as a urethane-based adhesive, an acrylic adhesive, an epoxy-based adhesive, or a rubber-based adhesive. Among these adhesives, urethane-based adhesives are preferable in terms of adhesive strength.
Examples of urethane-based adhesives include adhesives using two-liquid curing urethane resins containing various polyol compounds such as polyether polyols, polyester polyols and acrylic polyols, and curing agents such as isocyanate compounds.

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, in order to efficiently obtain a desired adhesive strength.

[Laminate production method]
A first method for producing a laminate of the present disclosure includes a decorative layer forming step of providing a decorative layer on a substrate, and a resin composition for forming a matte layer containing a curable resin and a wrinkle stabilizer on the decorative layer. It is characterized by comprising a matte layer forming step of applying a substance 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 production method, for example, as shown in FIG. 2, it has a base material, a decorative layer and a matte layer in order, and the surface of the matte layer opposite to the decorative layer is composed of irregular wrinkles. Laminates can be produced that have a rugged topography and have specific RSm (mean length of curvilinear element) and Sku (kurtosis).

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

By irradiating the resin composition for forming the matte layer with such a low-wavelength ultraviolet ray, wrinkles are formed on at least one surface of the matte layer, and a matting effect and a slippery feel are exhibited. Although the details of this are unknown, it is presumed to be due to the following mechanism.

When a low-wavelength ultraviolet ray is applied to a coating layer in which a resin composition for forming a matte layer is applied to a predetermined thickness, the energy of the ultraviolet ray permeates only the surface portion, and the energy does not reach the lower layer. , only the surface portion of the resin composition begins to harden. Therefore, it is considered that only the surface undergoes curing shrinkage and irregular wrinkles are formed. Thus, the formation of irregular wrinkles is considered to occur when the resin composition for forming the matte layer is cured only in a certain thickness direction from the surface by irradiation with low-wavelength ultraviolet rays.

In addition, from the comparison of the examples and comparative examples described later, when the wrinkle-forming stabilizer is not included, the formation of irregular wrinkles becomes unstable, and the visibility and texture of the matte effect are stable over the entire surface of the matte layer. As a result, it does not develop to a sufficient degree and does not sufficiently develop a slippery feel. From this, the stable expression of the matte effect and the slippery feel cannot be explained only by the curing of only the surface portion by the low wavelength ultraviolet rays. In other words, the inclusion of a wrinkle-forming stabilizer is essential for the laminate of the present disclosure to stably have irregular wrinkles to exhibit a matte effect and slippery feel.
Considering that a stable matte effect and a slippery feel due to irregular wrinkle formation were not obtained when wrinkle stabilizers were not included, the wrinkle stabilizers did not contribute to the formation of wrinkle-triggering nuclei. Around the nucleus, the resin on the surface of the resin composition gathers to form wrinkle protrusions (protrusions) and recesses along with the formation of the protrusions (protrusions). As a result, the formation of irregular wrinkles is stabilized, and it is believed that a matte effect and a slippery feel are stably exhibited.

The wrinkle-forming stabilizer and the resin composition for forming a matte layer containing the wrinkle-forming stabilizer used in the production method of the present disclosure include the wrinkle-forming stabilizer and the matte layer-forming resin composition that can be used in the laminate of the present disclosure. The contents are the same as those described for the resin composition for

In the production method of the present disclosure, the resin composition for forming the matte layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. Due to this irradiation, the energy of the ultraviolet rays penetrates only the surface portion as described above, and the energy does not reach the lower layer, so that only the surface portion of the resin composition begins to cure. Therefore, curing shrinkage occurs only on the surface, which stabilizes the formation of irregular wrinkles, and the surface layer of the resin composition becomes a cured product to form a matte layer. Then, after that, 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 the entire thickness of the resin composition, In addition, the matte layer exhibits a light diffusion effect on the surface and has irregular wrinkles that exhibit a slippery feel. In order to accelerate 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.

The light having a wavelength of at least 100 nm or more and 380 nm or less includes, for example, rare gases such as Ar, Kr, Xe, and Ne, halogen halides of rare gases such as F, Cl, I, and Br, or mixed gases thereof. Preferred is "excimer light," which includes light in the ultraviolet wavelength region from excited dimers, or excimers, formed by the discharge. The wavelength of the excimer light and the excimer serving as the light source include, for example, light with a wavelength of 126 nm emitted from the excimer of Ar ₂ (hereinafter abbreviated as “126 nm (Ar ₂ )”), 146 nm (Kr ₂ ), and 157 nm. Wavelength light such as (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), 351 nm (XeF) can be preferably employed. As the excimer light, either spontaneous emission light or laser light with high coherence due to stimulated emission can be used, but the use of spontaneous emission light is usually sufficient. A discharge lamp that emits light (ultraviolet rays) is also called an “excimer lamp”.
The excimer light has a single wavelength peak and is characterized by a narrow half width of the wavelength compared to ordinary ultraviolet rays (for example, ultraviolet rays 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 touch is also improved.

The wavelength is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, in order to stabilize the formation of irregular wrinkles, stably improve the matting effect, and improve the smooth touch. It is more preferably 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, still more preferably 200 nm or less, and most preferably 172 nm (Xe ₂ ). Thus, in the present disclosure, in order to stably improve the matting effect and improve the smooth touch, it is preferable to use light with a shorter wavelength, medium wavelength ultraviolet rays (wavelength: 280 to 320 nm), It can be said that short wavelength ultraviolet rays (wavelength: 280 nm or less) are more preferable, and short wavelength ultraviolet rays are even more preferable.

In the present disclosure, the integrated amount of light of the above wavelength 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, and even more preferably 50 mJ/cm ² or more. The upper limit is not particularly limited, and considering productivity such as reducing the number of lamps required for irradiating wavelength light and improving production efficiency, it is preferably 1,000 mJ/cm ² or less, more preferably 500 mJ/cm 2 or less. cm ² or less, more preferably 300 mJ/cm ² or less. For the same reason, the ultraviolet power density is preferably 0.001 W/cm or more, more preferably 0.01 W/cm or more, still more preferably 0.03 W/cm, and the upper limit is preferably 10 W/cm or less. , more preferably 5 W/cm or less, and still more preferably 3 W/cm or less.
Further, the oxygen concentration at the time of irradiation with light of the above wavelength is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

In the matte layer forming step in the method for producing a laminate of the present disclosure, in addition to the irradiation with light having 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 can go
For example, in order to stabilize the formation of irregular wrinkles due to the difference in the degree of hardening progress between the surface portion and the deep portion distant from the surface in the depth direction, and to promote the progress of hardening to the deep portion, After previously irradiating with light having a wavelength of more than 380 nm, preferably with light having a wavelength of about 385 nm or more and 400 nm or less to pre-cure the entire resin composition for forming the matte layer, irradiating with light having a wavelength of 100 nm or more and 380 nm or less. Alternatively, after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, post-curing may be performed to further cure the resin composition. Pre-curing and post-curing may be appropriately determined depending on desired properties such as processing properties and surface properties such as stain resistance required for the matte layer. Moreover, although the above wavelength light belongs to ultraviolet rays, it is possible to use not only ultraviolet rays but also other ionizing radiation such as electron beams. For example, in post-curing, an electron beam 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 formed by applying a resin composition for forming a matte layer to 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, or the like. In particular, in order to improve the slippery feeling, the coating layer (uncured resin layer) coated by the inkjet method or the gravure printing method should be formed by irradiating 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 production method of the present disclosure has other layers such as a transparent resin layer in addition to the base material and the decorative layer described as the 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 the composition for forming each layer by the known method described above, and drying and curing as necessary. Moreover, when forming a transparent resin layer, a resin film forming the transparent resin layer can be formed by dry lamination or the like.

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

Moreover, the laminate of the present disclosure can also be used as a shaping sheet and a transfer sheet. When used as a shaping sheet, it can be used as an embossing plate used for embossing, a shaping sheet, or the like, whereby the 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.

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

In the case of having an adherend, the decorative member has the adherend and the laminate of the present disclosure described above. Specifically, the surface of the adherend requiring decoration and the base material of the laminate are laminated facing each other. In the case of having an adherend, the laminate of the present disclosure preferably has a film or sheet form in consideration of ease of lamination.

(Substrate)
Examples of the adherend include flat plates of various materials, plate materials such as curved plates, three-dimensional shaped articles such as cylinders and polygonal prisms, sheets (or films), and the like. For example, it is used as a plate material such as a wood veneer made of various woods such as cedar, cypress, pine, lauan, wood plywood, laminated lumber, particle board, and wood fiberboard such as MDF (medium density fiberboard), and as a three-dimensional article. Wood members used as plate materials, three-dimensional articles, or sheets made of metals such as iron, aluminum, copper, and alloys containing one or more of these metals; Glass, ceramics such as ceramics, gypsum, cement , ALC (lightweight cellular concrete), ceramic materials used as plates and three-dimensional articles made of non-ceramic ceramic materials such as calcium silicate; acrylic resins, polyester resins, polystyrene resins, polyolefin resins such as polypropylene, ABS (acrylonitrile -butadiene-styrene copolymer) resins, phenolic resins, vinyl chloride resins, cellulose resins, resin members used as resins such as rubber plates, three-dimensional articles, and sheets. Moreover, these members can be used individually or in combination of multiple types.

The adherend may be appropriately selected from the above according to the application, and may be used as interior members of buildings such as walls, ceilings, and floors, or exterior members such as outer walls, roofs, eaves, fences, gates, and windows. When used as fittings or fixtures such as frames, doors, handrails, baseboards, rims, moldings, etc., it is preferably made of at least one member selected from wooden members, metal members and resin members, such as entrance doors. When it is used as fittings such as exterior members, window frames, and doors, it is preferably made of at least one member selected from metal members and resin members.

The thickness of the adherend may be appropriately selected depending on the application 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 or less, and still more preferably 0.5 mm or more and 3 mm or less.

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

The adhesive used for the adhesive layer is not particularly limited, and known adhesives can be used, and may be appropriately selected according to the application. For example, adhesives such as moisture-curable adhesives, anaerobic-curable adhesives, dry-curable adhesives, UV-curable adhesives, heat-sensitive adhesives (e.g., hot-melt adhesives), and pressure-sensitive adhesives are preferred. be done.

Examples of resins used for 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. In addition, a two-liquid curing type urethane-based adhesive or an ester-based adhesive using an isocyanate compound or the like as a curing agent can also be applied.
A pressure-sensitive adhesive can also be used for the adhesive layer. As the adhesive, various adhesives such as acrylic, urethane, silicone, and rubber can be appropriately selected and used.

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

[Total light transmittance]
The decorative member using the laminate of the present disclosure includes a substrate, a decorative layer, etc., made of a material that is not transparent as described above, and an adherend made of a material that is not transparent. may be adopted, and may 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 according to JIS K7361-1:1997, is preferably 20% or less, more preferably 15% or less, and even more preferably. is 10% or less.

(Manufacturing method of decorative member)
The decorative member can be manufactured through a step 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, and the surface of the adherend requiring decoration and the surface of the laminate of the present disclosure on the substrate side are laminated so as to face each other. . As a method for laminating the adherend and the laminate, for example, there is a lamination method in which the laminate is laminated by applying pressure to the plate-like adherend 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, depending on the type of resin constituting the adhesive. A temperature of 100° C. or higher and 130° C. or lower is preferable for a heat-resistant hot-melt adhesive. In the case of vacuum forming, it is generally carried out while heating, and the temperature is preferably 80° C. or higher and 130° C. or lower, more preferably 90° C. or higher and 120° C. or lower.

The decorative member obtained as described above can be arbitrarily cut, and the surface and the butt end portion can be arbitrarily decorated such as grooving and chamfering using a cutting machine such as a router and a cutter. And various uses, for example, interior members of buildings such as walls, ceilings and floors; exterior members such as outer walls, eaves, roofs, fences and fences; Fittings or fixtures such as rims and malls; General furniture such as chests, shelves, desks; Kitchen furniture such as dining tables and sinks; It is suitably used as a member or the like.

In addition to the above-described decorative members used in buildings and the like, the laminate of the present disclosure can be packaged as a single unit, or in a form in which the laminate is laminated, combined, or combined with another material (adherend). Materials, whiteboards or blackboards, credit cards, cash cards, telephone cards, various cards such as various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (window glass, etc.), artificial leather, etc. can be used for In these applications, it is preferable that the laminate of the present disclosure, which usually exhibits a matte effect and a slippery feel, is arranged on the outermost surface, but depending on the application, purpose of use, etc., other uses Of course, it is also possible to have a form.

(Laminate 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 that order,
The surface of the matte layer on the side opposite to the decorative layer has an uneven shape composed of irregular wrinkles,
In the measurement image when the measurement area (length 204 μm × width 272 μm) on the surface is measured with a laser microscope (50x objective lens),
RSm (average length of curvilinear element) 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 1 above, wherein Rz (maximum height), which is the peak and height parameter of the profile 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 profile curve, is 3.00 μm or less on the measurement screen.
4. Any one of the above 1 to 3, wherein the irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary protrusions and a recess formed by being surrounded by the plurality of filamentary protrusions. The laminate according to .
5. The matte layer is composed of a cured resin composition containing a resin and a wrinkle stabilizer, and the wrinkle stabilizer is 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 of the upper limit and contains 0.5 parts by mass or more of the wrinkle-forming stabilizer with respect to 100 parts by mass of the resin.
6. 6. The laminate according to any one of 1 to 5 above, wherein the substrate 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 surface of the base material.
8. 8. The laminate according to any one of 1 to 7 above, wherein the 60° gloss value of the surface shape is 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 according to JIS K7361-1:1997.
10. 10. The laminate according to any one of 1 to 9 above, which is used as a decorative sheet.

EXAMPLES Next, the present disclosure will be described in more detail with reference to examples, but the present disclosure is not limited by these examples.

(Measurement of surface texture)
RSm (average length of curvilinear element), Sku (kurtosis), Rz (maximum height) and Ra (arithmetic mean roughness) of the laminates obtained in Examples and Comparative Examples are the surface shape of the laminate. For a total of 9 measurement areas (one measurement area is 204 μm in length × 272 μm in width), one arbitrary location and eight surrounding locations, a shape analysis laser microscope (“VK-X150 (control unit) / VK- X160 (measurement part)", 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) is 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 curve element), Rz (maximum height) and Ra (arithmetic mean roughness) are measured corresponding to the one measurement area. On 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 9 arbitrary points. Then, the average value of the surface textures at the 9 points was taken as various surface textures of the laminate.
The cutoff values of RSm (average length of curvilinear element), Rz (maximum height) and Ra (arithmetic mean roughness) were set to 0.8 mm.

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

(Evaluation of texture (uniformity of surface condition))
The laminates obtained in Examples and Comparative Examples were evaluated for surface texture (uniformity of surface condition) by arbitrary 20 adults according to the following criteria.
A: 18 or more people evaluated that the surface condition was uniform and the visibility of the matte effect was high.
B: 15 or more and 17 or less evaluated that the surface condition was uniform and the visibility of the matte effect was high.
C: 14 or less evaluated that the surface condition was uniform and the visibility of the matte effect was high.

(Evaluation of slippery touch)
For the laminates obtained in Examples and Comparative Examples, a plain satin fabric without embroidery, background pattern, etc. was used as a reference for a slippery touch, and the feel of the surface was tested by 20 random adults. Evaluation was made according to the following criteria.
A: More than 18 people evaluated that the tactile sensation was close to the standard, and that the tactile sensation was slippery without being caught on a flat surface with respect to hand movements.
B: 15 or more and 17 or less evaluated that the tactile sensation was close to the reference, and that the tactile sensation was slippery without being caught on a flat surface with respect to hand movements.
C: 14 or less people evaluated that the tactile sensation was close to the reference, and that the tactile sensation was slippery without being caught on a flat surface with respect to hand movements.

[Example 1]
A corona discharge-treated polypropylene sheet (thickness: 60 μm) is used as the base material, and printing ink (binder resin: two-liquid curing acrylic-urethane resin) is applied to one side of the base material by the gravure method for coloring. 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 coating a resin composition containing a two-component curing type acrylic-urethane resin on the decorative layer, and a primer On the layer, a resin composition for forming a matte layer (polyfunctional urethane acrylate oligomer 1 (average functional group number: 3, average molecular weight: 2400) 30 parts by mass, multifunctional acrylate monomer 1 (bifunctional, molecular weight: 296): 40 parts by mass, monofunctional acrylate monomer (molecular weight: 226): 30 parts by mass, wrinkle-forming stabilizer 1 (silica particles, average particle size: 4 μm): 5.0 parts by mass, photoinitiator (benzophenone system): 0 .8 parts by mass) was applied to the entire surface by a gravure method (coating amount: 5 g/m ² (dry), matte layer thickness: 5 μm).
Next, ultraviolet rays are irradiated using a UV irradiation device composed of LEDs (wavelength: 395 nm, amount of ultraviolet rays: 6 W/cm ² ), and ultraviolet rays are irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), Ultraviolet power density: 1 W/cm, cumulative light intensity: 10 to 100 mJ/cm ² , nitrogen atmosphere (oxygen concentration of 200 ppm or less)), and further irradiation using a high-pressure mercury lamp (ultraviolet power density: 200 W/cm) to form a matte layer. was provided to obtain a laminate having a substrate, a decorative layer, a primer layer and a matte layer in that order. 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 texture was measured and the texture and touch were evaluated by the above methods. These results are shown in Table 1.

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

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

[Comparative Example 1]
In Example 1, the resin components contained in the resin composition for forming the 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, the amount of wrinkle-forming stabilizer used is 0 parts by mass, that is, no wrinkle-forming stabilizer is used, and 10 parts by mass of matting agent (average particle size: 8.0 μm) is used instead. A laminate was obtained in the same manner as in Example 1, except for using only 1 part.
With respect to the obtained laminate, the 60° gloss value, 85° gloss value, and surface properties of the matte layer side were measured by the methods described above, and the texture and tactile sensation were also evaluated. These results are shown in Table 1.

[Comparative Example 2]
In Example 1, the resin components contained in the resin composition for forming the 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, the average molecular weight: 3000) was 20 parts by mass, and the polyfunctional acrylate monomer 1 (difunctional, molecular weight: 296) was 30 parts by mass. .
With respect to the obtained laminate, the 60° gloss value, 85° gloss value, and surface properties of the matte layer side were measured by the methods described above, and the texture and tactile sensation were also 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 on the matte layer side of 1.5 to 2.2, 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 the slippery feel was also excellent. In addition, the laminate of Example 1, which has a matte layer on at least a part of its surface, has excellent visibility and texture of the matte effect, and has an excellent slippery touch. It was confirmed that
On the other hand, the laminate of Comparative Example 1, which does not contain a wrinkle-forming stabilizer, has an irregular surface even if it contains 10.0 parts by mass of the matting agent, which is higher than the content of the wrinkle-forming stabilizer in the examples. It was confirmed that the surface had a large Sku (kurtosis) and lacked a slippery feel. Moreover, the tactile sensation of the laminate of Comparative Example 1 lacked a slippery tactile sensation and was rather a rough tactile sensation. It was confirmed that the laminate of Comparative Example 2 also had a particularly large Sku (kurtosis) and therefore lacked a slippery feel and was inferior in texture.

4 to 6 are measurement screens of the laminates of Examples 1 and 2 and Comparative Example 1, respectively, in one measurement area (204 μm long×272 μm wide) measured by a shape analysis laser microscope.
As shown in FIGS. 4 and 5, the surface shapes of the laminates of Examples 1 and 2 were found to be uneven due to irregular wrinkles, and it was found that the laminates had a slippery feel.

On the other hand, as for the surface shape of the laminate of Comparative Example 1, as shown in FIG. Because it was too much, it did not have a slippery touch.
In this way, even from the measurement screen, the laminate of the present disclosure has an uneven shape due to irregular wrinkles on its surface, and due to this uneven shape, it has an excellent matte effect visibility and texture, In addition, it was confirmed that the effect of providing an excellent slippery touch was exhibited.

In addition, FIGS. 7 to 9 show nine measurement regions of the laminates of Examples 1 and 2 and Comparative Example 1 (one measurement region is 204 μm long × 272 μm wide.) Measurement by a shape analysis laser microscope. The screens are connected (because there is a partial overlap, the connected measurement screen corresponds to a measurement area of 545 μm in length×743 μm in width). By observing the measurement screens connected in this way, it is possible to get a bird's-eye view of the uneven shape of the laminate obtained in each example due to irregular wrinkles. Regarding this measurement screen, various surface textures measured in the same manner as the 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 shown in Table 1 above. It was almost the same as the numerical value of the surface texture used. Therefore, it can be said that the method of connecting the measurement screens of the nine measurement regions is effective in grasping the uneven shape due to irregular wrinkles of the laminate and in measuring the surface properties.

The laminate of the present disclosure has an excellent matte effect visibility and texture, and is excellent in slipping touch, so it can be used for various purposes, such as interior members of buildings such as walls, ceilings, and floors. Exterior materials such as exterior walls, eaves, roofs, fences, and fences; Fittings or fixtures such as window frames, doors, door frames, handrails, baseboards, rims, and malls; Chests, shelves, desks, etc. general furniture; kitchen furniture such as dining tables and sinks; surface decorative boards for cabinets such as household appliances and OA equipment; decorative members for various members such as interior and exterior members for vehicles.
In addition to the above-described decorative members used in buildings and the like, the laminate of the present disclosure can be packaged as a single unit, or in a form in which the laminate is laminated, combined, or combined with another material (adherend). Materials, whiteboards or blackboards, credit cards, cash cards, telephone cards, various cards such as various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (window glass, etc.), artificial leather, etc. Also preferably used as.

1: Laminate 2: Concave portion 3: Convex portion (protruding portion)
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 that order,
The surface of the matte layer on the side opposite to the decorative layer has an uneven shape composed of irregular wrinkles,
In the measurement image when the measurement area (length 204 μm × width 272 μm) on the surface is measured with a laser microscope (50x objective lens),
RSm (average length of curvilinear element) 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. The laminate according to claim 1, wherein Rz (maximum height), which is a peak and height parameter of the contour curve, is 5.00 [mu]m or more on the measurement screen. 3. The laminate according to claim 1, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve, is 3.00 [mu]m or less on the measurement screen. Any one of claims 1 to 3, wherein the irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary protrusions and a recess formed by being surrounded by the plurality of filamentary protrusions. The laminate according to item 1. The matte layer is composed of a cured resin composition containing a resin and a wrinkle stabilizer, and the wrinkle stabilizer is 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 0.5 parts by mass or more of the wrinkle-forming stabilizer with respect to 100 parts by mass of the resin. 6. 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 surface of the substrate. 8. The laminate according to any one of claims 1 to 7, wherein the surface shape has a 60° gloss value of 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 according to JIS K7361-1:1997. The laminate according to any one of claims 1 to 9, which is used as a decorative sheet.

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