JP2022048111A - Matte article - Google Patents

Abstract

To provide a matte article that has a matte effect with good visibility and texture and also has a moist feel.SOLUTION: In at least one portion of the surface, the matte article has a surface shape in which skewness (Ssk) is less than 0.00 as defined by ISO 25178-2:2012.SELECTED DRAWING: None

Description

The present disclosure relates to matte articles.

Conventionally, for example, interior members of buildings such as walls, ceilings, and floors; exterior members such as outer walls, eaves ceilings, roofs, walls, and fences; window frames, doors, door frames, handrails, skirting boards, and surrounding edges. , Fittings or building parts such as malls; General furniture such as basins, shelves, desks; Kitchen furniture such as dining tables and sinks; Surface decorative boards such as cabinets for home appliances and OA equipment; Interior or exterior parts of vehicles, etc. As an article for decorating and protecting the surface of the door, so-called decorative materials or decorative sheets are used. As the decorative material, for example, a material having a surface layer having a desired function is used.

For decorative materials used for these purposes, a method of improving the texture by using a matte effect (also referred to as a "matte effect") is widely used in order to improve the design. As a decorative material using a matte effect, for example, Patent Document 1 has a pattern layer and a concealing layer on one side of a base sheet, and a gloss adjusting layer such as a matte layer and a gloss layer on the other side. A decorative sheet 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 by the difference in gloss between the matte layer of the gloss adjusting layer and the gloss layer, and in the embodiment thereof, the mat provided on the entire surface is obtained. For the layer, a matte ink containing 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate, for a total of 50 parts by weight, is used per 100 parts by weight of the resin content.

Further, Patent Document 2 proposes a decorative material in which a printing layer and a transparent resin layer are sequentially provided on a base material, and an embossed pattern is applied to the outermost surface of the transparent resin layer.

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

As a method for improving the texture by the matting effect, a matting agent (also referred to as “matting agent” or “matting agent”) is used as in Patent Document 1 above, and the matting effect itself has a matting effect. A method of obtaining an erasing effect, a method of forming an uneven shape on the outermost surface by embossing as in Patent Document 2 above, and the like are mainly mentioned.
However, when a matting agent is used as in Patent Document 1, it is necessary to increase the amount used in order to improve the matting effect, but as the amount used increases, the matting agent becomes more effective. The scratch resistance is reduced by falling off from the coating film and damaging the coating film, and the scratches become more noticeable due to the change in gloss due to the lack of the matting agent, or the minute gaps at the interface between the matting agent and the resin are contaminated. The surface characteristics tend to be deteriorated due to the permeation of the substance and the deterioration of the stain resistance due to the adsorption of the contaminated substance on the matting agent itself. On the other hand, if the amount used is reduced in order to suppress the deterioration of the surface characteristics, the matting effect tends to decrease, and the surface characteristics and the matting effect have a bilateral relationship. Therefore, there is a limit to the matte effect using a matting agent.
Further, when embossing is used as in Patent Document 2, it is not easy to produce an embossed plate because it requires a great deal of labor, and it is necessary to produce a plate for each desired pattern. Therefore, it cannot be said that the method is sufficiently easy to respond to the diversity of customer demand.

By the way, the variety of customer demands is wide-ranging, and not only the above-mentioned visual matting effect but also the tactile expression is required. For example, when a matting agent as in Patent Document 1 is used, by increasing the amount used, the contour of the matting agent is exposed on the surface of the decorative sheet, and a slightly rough texture is exhibited. May be done. Further, when embossing is used as in Patent Document 2, a tactile sensation due to the uneven shape of the surface formed by the embossed plate may be exhibited. However, in either case, the expression of the tactile sensation is not focused on, and it cannot be said that the expression is sufficient in terms of the tactile sensation. That is, it cannot be said that the conventional decorative sheet and decorative material can achieve both an excellent matting effect and a tactile sensation. In this disclosure, we paid particular attention to the "moist" tactile sensation.

It is an object of the present disclosure to provide a matte article having an excellent visibility and texture of a matte effect and an excellent moist touch feeling.

In order to solve the above problems, this disclosure is
A matte article having a surface shape with a Sk (skewness) of less than 0.00, as defined in ISO 25178-2: 2012, on at least a portion of the surface.
I will provide a.

According to the present disclosure, it is possible to provide a matte article having an excellent visibility and texture of a matte effect and an excellent moist touch feeling.

It is a schematic diagram for demonstrating the surface shape of the matte article of this disclosure. It is a schematic diagram for demonstrating the surface shape of the matte article of this disclosure. It is sectional drawing which shows one Embodiment of the matte article of this disclosure. It is sectional drawing which shows one Embodiment of the matte article of this disclosure. It is sectional drawing which shows one Embodiment of the matte article of this disclosure. It is a schematic diagram in the plan view which shows one Embodiment of the matte article of this disclosure. 6 is an optical microscope image of the surface of the shaped sheet obtained in Example 1. 6 is an optical microscope image of the surface of the shaped sheet obtained in Comparative Example 1. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2.

[Matte goods]
Hereinafter, the matte article of the present disclosure will be described. In addition, in this specification, the numerical values relating to "greater than or equal to", "less than or equal to" and "..." relating to the description of the numerical range are numerical values that can be arbitrarily combined, and the numerical values of Examples are numerical values that can be used for the upper and lower limits of the numerical range. Is.

The matte article of the present disclosure is characterized in that at least a part of the surface has a surface shape having an Sk (skewness) of less than 0.00 as defined in ISO25178-2: 2012.

[About surface shape]
The matte article of the present disclosure will be described from the surface shape (hereinafter, also simply referred to as “surface shape”) that the matte article has on at least a part of the surface thereof.
The surface shape requires Skk (skuneness) to be less than 0.00 as defined in ISO 25178-2: 2012. By having such a surface shape, the matte article of the present disclosure exhibits excellent visibility and texture of a matte effect, and also exhibits a particularly "moist" tactile sensation as a tactile sensation. Here, "the visibility and texture of the matte effect" may be simply referred to as "the matte effect" below.

The "moist" tactile sensation is a sensual expression, but the "moist" in the present specification generally includes all the tactile sensations that are felt as "moist". Specifically, it means the tactile sensation felt when touching a moist and smooth surface with the pad of a finger.

What has a "moist" tactile sensation cannot be unequivocally determined because it can be changed depending on the surface processing and the weaving method of the fabric described later, but for example, silk (silk), tencel (lyocell), etc. Natural fiber fabrics, synthetic fibers such as promix, rayon, cupra, synthetic fiber fabrics such as regenerated fibers, or peach skin processed fabrics of these synthetic fibers (thin with a tactile sensation similar to that of peach fruit epidermis). Examples include fabrics such as brushed fabrics. Also, for example, ceramic materials such as tiles, glass, porcelain, and enamel; stone materials such as marble and mikage stone, especially those with various surface treatments such as mirror treatment; lacquered wood materials; brass, gold, silver, and copper. , Aluminum, steel, stainless steel and other metals, especially those with various surface treatments such as mirror finish; etc. are also mentioned as those that can have a "moist" feel. Some ceramic materials, stone materials, wood-based materials, and metals do not have a "moist" feel depending on the surface processing, but it goes without saying that such processed materials are not included.
Therefore, the matte article of the present disclosure is preferably used for applications such as those for expressing a design such as a fabric, a ceramic material, a stone material, a wood-based material, and a metal surface. In this case, the matte article of the present disclosure preferably has a decorative layer having a pattern such as a fabric, a ceramic material, a stone material, a wood-based material, or a metal surface so as to express a desired design. Details of the decorative layer that the matte article of the present disclosure may have will be described later.

Skk (skewness) is one of the three-dimensional surface texture parameters defined by the above ISO, and is an index showing the degree of deviation of the height distribution from the average plane. When Sk is 0, the surface shape is symmetric with respect to the average surface, and when Sk exceeds 0, the surface shape is biased to the lower side with respect to the average surface, that is, to the side where the height is low, and the convex portion. It is a measured value that can be grasped that the vicinity of the top tends to be sharp and thin. Here, "symmetry with respect to the average plane" can also be referred to as "normal distribution".

On the other hand, when Sk is less than 0, the surface shape is biased to the upper side with respect to the average surface, that is, to the side where the height is high, and it is a measured value that can be grasped that the vicinity of the top of the convex portion tends to be dull and thick. The tendency of the shape exhibited by the surface shape indicated by Sk (skewness) will be described with reference to FIG.
FIG. 1 is a schematic diagram of a case where Sk (skewness) is less than 0 (1-1) and a case where Sk (skuneness) exceeds 0 (1-2). The Sk (skewness) of the surface shape in the present disclosure is less than 0.00, indicating that the surface shape tends to have the shape shown in (1-1). That is, since the surface shape is biased upward with respect to the average surface, the surface shape above the average surface, that is, the surface side of the matte shape of the present disclosure has a wide width with respect to height and a low aspect ratio. It can be said that there are many convex portions whose cross-sectional shape is close to a rectangle (trapezoid), and that the convex portions are closely distributed. Here, in FIGS. 1 and 2, the "average plane" is the average level plane corresponding to the horizontal line, and the "lower side with respect to the average plane" is also the lower side in FIGS. 1 and 2, and the matte article. It can be said that it is on the outer surface side.

Since the surface shape has such a shape, the contact area is large when touched with the pad of the finger, so that a person feels stuck, which leads to the tactile sensation felt when touching a moist and smooth surface. it is conceivable that. Further, it is considered that the presence of such a convex portion further has a concave portion between the convex portion and the convex portion, so that a matte effect is also obtained. Details on the manifestation of the matting effect will be described later.

Skk (skewness) is preferably −0.10 or less, more preferably -0.25 or less, still more preferably -0.45 or less, and the lower limit is preferably −3.00 or more, preferably -2. It is 0.00 or more, more preferably -1.50 or more, and even more preferably -1.30 or more. When Sk (skewness) is within the above range, the matte effect and the moist tactile sensation are improved.

The Sk (skewness) measurement is a measured value measured using a shape analysis laser microscope for a rectangle (1024 μm × 768 μm) at an arbitrary point on the surface shape of the matte article, and the measurement conditions may be adjusted as appropriate. It can be measured, for example, under the conditions described in Examples. Further, Sk (Kurtosis) described later, and Rsm (average length of curve elements), Rz (maximum height) and Ra (arithmetic mean roughness) related to the contour curve can be measured in the same manner.

In the present disclosure, as the surface shape, it is preferable that the Sk (Kurtsis) specified in ISO25178-2: 2012 is 3.00 or more.
Sku (Kurtosis) is one of the three-dimensional surface texture parameters defined by the above ISO, and is an index showing the degree of sharpness of the height distribution from the average plane. When the Sku is 3, the surface shape is symmetric with respect to the average plane (normal distribution), when the Sku exceeds 3, the height distribution has a sharp shape, and when the Sku is less than 3, the height distribution becomes. It is a measured value that can be grasped as having a tendency to have a crushed shape. The tendency of the shape exhibited by the surface shape shown by Sk (Kurtsis) will be described with reference to FIG. FIG. 2 is a schematic diagram of a case where Sk (Kurtsis) exceeds 3.000 (2-1) and a case where it is less than 3.00 (2-2). The fact that the surface shape in the present disclosure has a Sk (Kurtosis) of 3.00 or more means that the surface shape has the shape shown in (2-1), and the height portion before and after the average height is the most, and the average height is the largest. It is shown that the height distribution is such that the portion where the height protrudes more than the halfbeak and the portion where the height drops more than the average height are both small. The tip of the convex portion existing above the average surface has a sharp shape, but it can be said that the number is small.

In the surface shape satisfying the Sk (skewness), when Sk (Kurtosis) is 3.00 or more, the tip-shaped protrusion and the tip-shaped protrusion on the convex region having a low aspect ratio shape having a wide width with respect to the height. A small number of recessed (sharp) recesses with a squeezed bottom will be scattered. Therefore, the contact area when touched with the pad of a finger does not spread over a wide area as in a simple flat surface (mirror surface). Further, by being appropriately divided by the scattered protrusions and recesses and becoming smaller, the degree of catching of the finger pad becomes an appropriate range. As a result, the moist texture is improved and the matte effect is also improved.

The Sku (Kurtosis) is preferably 3.05 or more, more preferably 3.10 or more, still more preferably 3.15 or more, and the upper limit is preferably 5.50 or less, more preferably 5.25 or less, still more preferable. Is 5.00 or less. When the Sk (Kurtosis) is within the above range, the matte effect and the moist tactile sensation are improved.

The surface shape of the matte article is Sk (skewness) within the above-mentioned specific numerical range, preferably Sk (skewness) and Sk (Kurtosis) within the above-mentioned specific numerical range, and Rsm (average of curved elements described later) described later. It is preferable to have a length), Rz (maximum height), Ra (arithmetic mean roughness), and fine wrinkles (wrinkles) visually recognizable in a plan view shown in FIG. 6 described later.

Regarding the surface shape of the matte article of the present disclosure, Sk (skewness), preferably Sk (skewness) and Sk (Kurtosis), etc. are likely to be within a specific numerical range due to having the fine wrinkles (wrinkles), while the other The fine wrinkles (wrinkles) are easily formed by having Sk (skewness) within a specific numerical range, preferably Skk (skewness) and Sku (Kurtosis) within a specific numerical range. As described above, it can be said that Sk (skunes) and preferably Sk (Kurtosis) and the like and minute wrinkles (wrinkles) are inextricably linked to each other. By having such a surface shape, the matte effect is improved as well as the moist touch feeling.

In the surface shape of the matte article, Sk (skewness) within the above-mentioned specific numerical range, preferably Sk (skewness) and Sk (Kurtosis) within the above-mentioned specific numerical range, and Rsm (average length of curved elements described later) described later. ), Rz (maximum height) and Ra (arithmetic mean roughness)
(1) Forming a fine wrinkle structure on the surface of the matte layer,
Is preferable. Moreover,
(2) Composition of the resin composition for forming a 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 formation stabilizer, and the wrinkles when the wrinkle formation stabilizer is used. Optimize the particle size and content of the forming agent,
(3) The irradiation conditions of the resin composition for matte formation, particularly the wavelength of light having a wavelength of 100 nm or more and 380 nm or less capable of curing and shrinking the surface portion of the matte layer, the integrated consideration, the ultraviolet output density, etc. are optimized.
(4) In addition to the above, optimize the type and thickness of the base material, the thickness of the matte layer, etc.
Is preferable. By optimizing these, regarding the surface shape of the matte article of the present disclosure, Sk (skewness) is set within the above-mentioned specific numerical range, preferably Sk (Kurtosis), and Rsm (average length of curved elements) described later. , Rz (maximum height) and Ra (arithmetic mean roughness) can be easily set within a predetermined numerical range.

In the present disclosure, as the surface shape, it is preferable that Rsm (average length of curve elements), which is a lateral parameter of the contour curve defined in JIS B0601: 2013, is 100.00 μm or less.
Rsm (average length of the curve element) is a lateral parameter of the contour curve and is the average length of the contour curve element at the reference length. The smaller the value of Rsm (average length of curved elements), the narrower the width of the convex portion, and the surface shape is an index indicating that the convex portion tends to have a narrower width. Therefore, when the Rsm (average length of the curved element) is 100.00 μm or less in the surface shape satisfying the Sk (skewness), the width of the convex portion of the surface shape becomes narrower and can be touched by the pad of a finger. By reducing the contact area at the time of contact, the degree of catching becomes appropriate and the moist tactile sensation is improved. It also improves the matte effect.

The Rsm (average length of the curved element) is preferably 90.00 μm or less, more preferably 80.00 μm or less, still more preferably 65.00 μm or less, still more preferably 55.00 μm or less, and the lower limit is preferably 20. It is 0.00 μm or more, more preferably 25.00 μm or more, still more preferably 30.00 μm or more. When RSm (average length of curved elements) is within the above range, the matte effect and the moist tactile sensation are improved.
In measuring Rsm (average length of curved elements) in the present specification, the cutoff value is 0.8 mm.

In the present disclosure, as the surface shape, it is preferable that Rz (maximum height), which is a lateral parameter of the contour curve defined in JIS B0601: 2013, is 3.00 μm or more.
Rz (maximum height) is one of the peaks and height parameters of the contour curve, and 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 value of Rz (maximum height), the more convex portions having a large shape (high) when viewed from the valley exist, and this is an index indicating that many such convex portions tend to exist. Therefore, when the Rz (maximum height) is 3.00 μm or more in the surface shape satisfying the Sk (skunes) and Sk (Kurtosis), the shape is large when touched by the pad of a finger (seeing from the valley). High) The feeling of resistance due to each of the convex parts increases, so the moist feel is improved. It also improves the matte effect.

The Rz (maximum height) is preferably 3.50 μm or more, more preferably 4.00 μm or more, still more preferably 4.50 μm or more, still more preferably 4.80 μm or more, and the upper limit is preferably 15.00 μm or less. , More preferably 13.50 μm or less, still more preferably 11.00 μm or less, still more preferably 10.00 or less. When Rz (maximum height) is within the above range, the matte effect and the moist tactile sensation are improved.
In the measurement of Rz (maximum height) in the present specification, the cutoff value is 0.8 mm.

In the present disclosure, it is preferable that Ra (arithmetic mean roughness), which is a lateral parameter of the contour curve defined in JIS B0601: 2013, is 2.00 μm or less as the surface shape.
Ra (arithmetic mean roughness) is one of the parameters in the height direction of the contour curve, and is the average value of the height difference from the average plane in the contour curve at the reference length. It is an index showing that the smaller the value of Ra (arithmetic mean roughness), the smaller the convex portion in the surface shape and the concave portion formed accordingly, and the smoother and more uniform shape tends to be obtained. Therefore, in the surface shape satisfying the Sk (skewness) and Sk (Kurtosis), when Ra (arithmetic mean roughness) is 2.00 μm or less, the shape of the convex portion of the surface shape becomes more uniform and gentle. Since there will be more of them, the eccentric tactile sensation will be suppressed, and the moist tactile sensation will be improved. It also improves the matte effect.

Ra (arithmetic mean roughness) is preferably 1.95 μm or less, more preferably 1.90 μm or less, still more preferably 1.80 μm or less, and the lower limit is preferably 0.10 μm or more, more preferably 0.40 μm or more. , More preferably 0.60 μm or more. When Ra (arithmetic mean roughness) is within the above range, the matte effect and the moist tactile sensation are improved.
In the measurement of Ra (arithmetic mean roughness) in the present specification, the cutoff value is 0.8 mm.

[Layer structure]
As long as the matte article of the present disclosure has a surface shape defined by the above parameters, the layer structure is not particularly limited, and any layer structure may be adopted.
For example, the simplest layer structure of the matte article of the present disclosure includes a single layer structure as shown in FIG. The article shown in FIG. 3 is, for example, a cured product layer of a resin composition, preferably a cured product layer of a curable resin composition containing a curable resin such as an ionizing radiation curable resin described later, on one side thereof. Examples thereof include an article having the above-mentioned surface shape on the surface, and an article composed of a single layer such as an article in which the surface of a resin molded product is subjected to processing such as embossing to shape the surface shape.

Further, it is shown in FIGS. It is composed of a laminated body in which a plurality of such layers are laminated, for example, a base material, and a laminated body having the above-mentioned surface shape in at least a part thereof, for example, a laminated body having a cured product layer of a resin composition as a matte layer. Goods are also mentioned.
Hereinafter, for each layer constituting the matte article of the present disclosure, for an article composed of a laminated body, which is one of the preferred embodiments, a base material and a cured product layer (glossy) having the above-mentioned surface shape at least a part thereof. (Erasing layer), and the layer constituting the laminated body having the above will be described.

〔Base material〕
The form (or shape) of the base material forming the matte article of the present disclosure is not particularly limited, and may be selected from various shapes such as a film, a sheet or a plate, a polyhedron, a polygonal prism, a cylinder, a sphere, and a spheroid. It can be preferably adopted. Here, the film, the sheet and the plate are referred to as a film, a sheet and a plate from the one having a relatively thin thickness, but in the present specification, there is no particular significance in strictly distinguishing these three, and the film. , Sheets and boards shall not cause any difference in the interpretation of the rights of this disclosure. Therefore, in the present specification, the film, the sheet and the plate may be collectively referred to as "sheet", "sheet-like" and the like.
When the matte article of the present disclosure is composed of a laminated body, the shape of the base material is preferably a sheet. When the base material is in the form of a film, it is easy to provide a matte layer, which will be described later, so that the manufacturing suitability is improved, and for example, it is easy to be integrated with a resin molded product by sticking or the like, so that the post-processing suitability is improved.

The constituent material of the base material is not particularly limited, and various materials such as resin, metal, non-metal inorganic material, fibrous material, and wood-based material can be appropriately selected depending on the intended use. The base material composed of these various materials can be used as one layer, or as a plurality of layers in which two or more layers of the base materials composed of these various materials are combined. In the case of a plurality of layers, two or more layers of different materials can be laminated and integrated, and various functions of the materials of each layer can complement each other.

When a multi-layered base material is adopted, a laminate formed by laminating each layer constituting the plurality of layers, for example, a layer composed of the material A and a layer composed of the material B, is referred to as "A / B". When notation;
(1) Resin / wood-based material (2) Resin / metal (3) Resin / fibrous material (4) Resin / non-metal inorganic material (5) Resin 1 / resin 2 (for example, "olefin resin / acrylic resin" etc. When having multiple layers composed of different resins)
(6) Metal / wood-based material (7) Metal / non-metal inorganic material (8) Metal / fibrous material (9) Metal 1 / Metal 2 (for example, a plurality composed of different metals such as "copper / chromium") If you have a layer of)
(10) Aspects such as a non-metal inorganic material / fibrous material are preferably mentioned.
Further, when the base material has a plurality of layers, the adhesive layer, the pressure-sensitive adhesive layer, and the primer layer (anchor layer and the easy-adhesion layer) are used as layers for improving the adhesiveness of the adjacent layers between the layers of the plurality of layers. It may be further referred to.).

Examples of the resin that can be used as the base material include various synthetic resins and natural resins. Examples of the synthetic resin include a thermoplastic resin and a curable resin, and the thermoplastic resin is preferable in consideration of manufacturing suitability, handling suitability, post-processing suitability, and the like of the matte article.

Examples of the thermoplastic resin include olefin resins such as polyethylene, polypropylene, polymethylpentene, ionomer, 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-based thermoplastic elastomer; methyl poly (meth) acrylate, ethyl poly (meth) acrylate, poly ( Acrylic resins such as butyl acrylate and methyl (meth) butyl acrylate-polypolymer resins such as nylon 6 and nylon 66; celluloses such as cellulose triacetate, cellophane and celluloid. Resin: Styrene resin such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer (ABS resin); polovinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin , Polyallylate resin, polyimide resin and the like are preferable.
As the natural resin, natural rubber, pine fat, amber and the like are preferably mentioned.
Further, as the curable resin, a thermosetting resin, an ionizing radiation curable resin and the like exemplified as a constituent material of the matte layer described later are preferably mentioned.

Metals that can be used as the base material include, for example, aluminum or aluminum alloys such as aluminum and duralumin; iron or iron alloys such as iron, carbon steel and stainless steel; copper or copper alloys such as copper, brass and bronze; gold and silver. , Chromium, nickel, cobalt, tin, titanium and the like are preferable. Further, as the base material composed of metal, those obtained by applying these metals to the surface by plating or the like are also preferable.

Non-metal inorganic materials that can be used for the base material include non-ceramic ceramic materials such as cement, ALC (lightweight cellular concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramics such as ceramics, earthenware, glass, and amber. Materials: Natural stones such as limestone (including marble), granite, and Anshan rock are preferably mentioned.

Fibrous materials that can be used as the base material include, for example, thin leaf paper, kraft paper, high-quality paper, Japanese paper, titanium paper, linter paper, sulfate paper, paraffin paper, parchment paper, glassin paper, wallpaper backing paper, board paper, and plaster board. Paper such as base paper for use; preferably, woven cloth or non-woven fabric made of protein such as polyester resin fiber, acrylic resin fiber, silk, cotton, linen or cellulose-based natural fiber, glass fiber, carbon fiber or the like is preferable. Among these materials, acrylic resin, in order to improve the interlayer 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. Various resins such as styrene-butadiene rubber, melamine resin, and urethane resin may be added (impregnated with these resins after fabrication or internally filled at the time of fabrication). As the paper to which the resin is added, for example, inter-paper reinforced paper, resin-impregnated paper and the like are preferably mentioned.
Further, as a laminate formed by laminating a layer made of a fibrous material and a layer made of a resin, a vinyl chloride resin layer and an olefin resin are formed on the surface of a backing paper for wallpaper, which is widely used in the field of building materials. A wallpaper raw fabric or the like in which layers composed of various resins such as a layer and an acrylic resin layer are laminated is preferable.

Wood-based materials that can be used as the base material include veneer, plywood, and laminated wood made of various types of wood such as cedar, cypress, pine, zelkova, 楢, oak, walnut, lauan, teak, and rubber wood. Particle board, medium density fiberboard (MDF) and the like are preferably mentioned.

As the base material, a base material composed of the above-mentioned materials can be used without limitation, and may be appropriately selected depending on desired properties and the like. From the viewpoint of improving the matte effect and the moist texture, a base material made of a resin and a base material made of a fibrous material are preferable, and a base material made of a resin is more preferable. Among the resins, olefin resin, vinyl chloride resin, polyester resin and acrylic resin are preferable, olefin resin, vinyl chloride resin and polyester resin are more preferable, polyethylene and polypropylene are preferable as olefin resin, and polyvinyl chloride is preferable as vinyl chloride resin. As the polyester resin, polyethylene terephthalate is preferable. Among these, polyester resin is preferable as the resin used for the base material, and polyethylene terephthalate is particularly preferable. Further, among the fibrous materials, paper is preferable. By using a base material composed of these materials, it is particularly easy to obtain the above-mentioned surface shape, and it is easy to improve the moist tactile sensation.

The shape and dimensions of the base material made of a single layer or a laminated body are not particularly limited and may be appropriately selected in consideration of the intended use, desired various performances, post-processing suitability and the like.
When the shapes of films, sheets and plates are adopted, the thickness is a typical design dimension of the matte article, but the thickness is not particularly limited, and the manufacturing suitability, use handling suitability, post-processing suitability and mechanical Considering strength, economy, etc., it is preferable to select from a range of 10 μm or more and 10 cm or less. When the shape of the film or sheet is adopted, it is preferably selected from the range of 20 μm or more and 300 μm or less, and when the shape of the plate is adopted, it is preferably selected from the range of 1 mm or more and 2 cm or less.

The base material is used from the viewpoint of improving the adhesion to other layers such as the matte layer, which will be described later, which constitutes the matte article, and the adhesion to the adherend such as the resin molded product in which the matte article is laminated. At least one surface thereof can be subjected to physical surface treatment such as acid value method and unevenness method, and surface treatment for improving easy adhesion such as chemical surface treatment.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method and the like, and examples of the unevenness method include sandblasting method and solvent treatment method. These surface treatments may be appropriately selected according to the type of the base material, and the corona discharge treatment method is preferable from the viewpoints of the effect of improving the adhesiveness of the surface treatment and the workability.

The base material may be colored or may not be colored (may be transparent), and when it is colored, the mode of coloring is not particularly limited and may be transparently colored. It may be opaque coloring (concealed coloring), and these may be arbitrarily selected.

When the base material is colored, the colorant includes, for example, a white pigment such as titanium white, an inorganic pigment such as iron black, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. Organic pigments or dyes such as isoindolinone yellow, phthalocyanine blue, nickel-azo complex, azomethine azo black pigment, perylene black pigment; metal pigment consisting of scaly foil pieces such as aluminum and brass; titanium dioxide coated mica, base Examples thereof include colorants such as pearl luster (pearl) pigments made of scaly foil pieces such as lead carbonate. For example, when the surface hue of an adherend such as a resin molded product on which matte articles are 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. May use an inorganic pigment such as a white pigment.

When coloring the base material with resin, either means such as adding a colorant to the resin (kneading, kneading) or applying a coating film of a paint containing the resin and the colorant should be adopted. Can be done. When a base material made of a fibrous material such as paper, woven fabric, or non-woven fabric is colored, it can be carried out by any means such as mixed extraction with pulp or fibrous material, formation of a coating film, or a combination thereof.
When the base material is colored with a wood-based material, it can be dyed with a dye, formed with a coating film, or used in combination thereof. When coloring a base material with a metal, in addition to forming a coating film, an electrolytic coloring method for forming a metal oxide film on the surface by using an anodizing method or the like can be adopted. Further, when the base material is colored with a non-metal 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 thereof.

Additives may be added to the base material, if necessary. In the case of mainly resins, the additives include, for example, calcium carbonate, inorganic substances such as clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, antioxidants, ultraviolet absorbers, and light stabilizers. And so on. The blending amount of the additive 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, etc.

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

In the present disclosure, the above-mentioned base materials may be used alone or in combination of two or more. It may be a combination of a plurality of paper base materials, a paper base material and a fiber base material, a paper base material and a resin base material, a fiber base material and a resin base material, and a paper base material and a fiber base material and a resin base material. It may be a combination with a material. Further, the resin base material may be composed of either a single layer of the above resin base material or a plurality of layers made of the same type or different kinds of resin.

The thickness of the base material is as described above, but when the base material is a film or sheet of the above resin, it is preferably 20 μm or more, and the upper limit is preferably 300 μm or less. Considering mechanical strength, economy and the like, 40 μm or more is more preferable, 200 μm or less is more preferable as an upper limit, and 100 μm or less is further preferable.
For the same reason, when the base material is paper, the basis weight is usually preferably 20 to 150 g / m ² , more preferably 30 to 100 g / m ² .

[Matte layer]
The matte layer in the matte article of the present disclosure is a layer provided on at least a part of the above-mentioned base material and having the above-mentioned surface shape, that is, a surface shape having an Sk (skewness) of less than 0.00. Further, as shown in FIG. 4, the layer is provided so that the surface having the surface shape is the surface opposite to the base material side.
Therefore, it is preferable that the matte article of the present disclosure has a matte layer and the surface shape is formed by the surface of the matte layer, and in consideration of mechanical strength, manufacturing suitability, etc., the matte article is matte. The layer is preferably a layer composed of a cured product of the resin composition, preferably a cured product of the curable resin composition containing the cured product resin.

As the resin composition for forming the matte layer, a resin composition containing a resin and a wrinkle formation stabilizer (considering that a matte article having an excellent matting effect and an excellent moist texture can be obtained). Hereinafter, it may be referred to as "resin composition for forming a matte layer"). That is, in the present disclosure, the matte layer is preferably a layer containing a resin and a wrinkle formation stabilizer.

(Wrinkle formation stabilizer)
The wrinkle-forming stabilizer stabilizes the formation of wrinkles on at least one surface of the matte layer, thereby uniformly matting over the entire surface of the matte layer forming the surface shape of at least a part of the surface of the matte article. The visibility of the effect is expressed, the unevenness of partial gloss is reduced, the visibility of the stable matte effect, and the uniformity of the surface condition due to the stable formation of wrinkles over the entire surface of the matte layer. It has a function of imparting. The wrinkles formed on the matte layer also greatly contribute to the development of a moist tactile sensation. In the present specification, with respect to "visibility of stable matting effect", an expression such as "visibility of stable matting effect" or an expression equivalent thereto may be used below. Further, "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 are both matting mechanisms (actions) even when their constituent substances and average particle diameters are the same. , The structure for developing matte and the amount used are different from each other in the relationship between the degree of gloss (gloss value) on the surface. It is also different from the "matte agent" in that it expresses a moist tactile sensation by forming wrinkles.

In the prior art such as Patent Document 1, the matting agent used for matting expression itself exhibits the visibility of the matting effect due to the light diffusion effect caused by the physical shape. Is. Specifically, what is generally called a matting agent generally has a difference in refractive index between the matting agent particles and the surrounding resin and air, and the reflection and refractive index of light rays corresponding to the contour shape of the particles. The visibility of the matte effect is exhibited by the light diffusion effect of the interface. On the other hand, in the matte article of the present disclosure, the wrinkle-forming stabilizer is caused by the wrinkle-forming stabilizer, in which the reflection of light rays by the particles themselves and the light diffusion by refraction do not exhibit the visibility of the matte effect. By stabilizing the formation of wrinkles on the surface of the matte layer, the light diffusion effect at the interface between the surface and the air with a refractive index difference gives the matte article a stable texture with the visibility of the matte effect. It is a thing. Therefore, the wrinkle-forming stabilizer used in the present disclosure is different from the matting agent that itself exhibits the visibility of the matting effect, even if the constituent substances and the average particle size of both are the same. The matting mechanism and action of the above, the structure for expressing the matting, and the like are different.
Further, the "wrinkle formation stabilizer" and the "matte agent" are also different in the relationship between the content and the gloss (gloss value) of the surface. 60 ° gloss value G _{60 °} ^AW (C) of the surface when the same substance A is used as a wrinkle formation initiator AW (W: wrinkle, wrinkle) and contained in a specific amount C to form wrinkles on the surface. Is clearly lower than the 60 ° gloss value G _{60 °} ^AM (C) on the surface when the same substance A is used as a mere matting agent AM and is contained in a specific amount C but no wrinkles are formed on the surface. .. That is, the following relational expression holds.
G _{60 °} ^AW (C) <G _{60 °} ^AM (C)

The matte layer in the matte article of the present disclosure may contain an agent conventionally used as a matting agent, but an extremely excellent matting effect that cannot be obtained even if a matting agent is used is stably obtained. Considering the characteristic of the effect of the invention that the obtained and moist tactile sensation can be obtained, it is preferable not to contain a matting agent. As described above, the matte article of the present disclosure has extremely excellent visibility and texture of the matte effect even if it does not substantially contain the matting agent conventionally used for obtaining the visibility of the matte effect. It can be said that it has. Here, "does not contain a matting agent" means that, in addition to not containing the matting agent at all, even if it is contained, it does not have the visibility of the matting effect based on the action 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 with respect to 100 parts by mass of the resin. ..
In the specification of the present application, the "matte agent" is specifically a layer in which the matte agent can be contained, that is, the thickness of the matte layer, from the viewpoint of forming a convex portion by the effect of cueing as described above. It means a particle having an average particle diameter whose lower limit is the smaller of more than 100% and more than 30 μm.

In the present disclosure, the wrinkle formation stabilizer is particularly limited as long as it is not a matting agent and the average particle size is 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. Can be used without.
Considering that the matte effect and the moist texture are improved, the average particles of the wrinkle formation stabilizer whose average particle diameter is 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller, is the upper limit. It is preferred to use at least one of the two wrinkle-forming stabilizers distinguished by diameter. Specifically, the two types of wrinkle formation stabilizers are wrinkle formation stabilizers having an average particle diameter of 1 μm or more and an upper limit of 100% or less or 30 μm or less of the thickness of the matte layer, whichever is smaller. , And a wrinkle-forming stabilizer 2 having an average particle size of less than 1 μm.

In the present disclosure, if at least one of the two types of wrinkle formation stabilizers is used, wrinkle formation is stable, a stable and excellent matting effect can be obtained, and a moist texture can also be obtained. Considering that the matting effect and the moist touch are improved, it is more preferable to use the wrinkle formation stabilizer 2 alone or in combination with the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2.

As the wrinkle formation stabilizer, for example, organic particles and inorganic particles can be used.
The organic substances constituting the organic particles include polymethylmethacrylate, acrylic-styrene copolymer resin, melamine resin, polycarbonate, polystyrene, polyvinyl chloride resin, benzoguanamine-melamine-formaldehyde condensate, silicone, fluororesin and polyester resin. And so on.
Examples of the inorganic substance constituting the inorganic particles include silica, alumina, calcium carbonate, aluminosilicate, barium sulfate and the like, and among these, silica having excellent transparency is preferable.

The shape of the wrinkle formation stabilizer is not particularly limited, and examples thereof include a spherical shape, a polyhedron, a scaly shape, and an amorphous shape.

The average particle size of the wrinkle formation stabilizer 1 is 1 μm or more, and the upper limit is 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller. Considering that the matting effect is stably improved and the moist texture is improved, the average particle size of the wrinkle forming stabilizer 1 is preferably 1.3 μm or more, more preferably 1.5 μm or more, still more preferably. It 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, and further, with respect to the thickness of the matte layer. The thickness of the matte layer is preferably 70% or less, and the absolute value is preferably 20 μm or less, more preferably 10 μm or less, still more preferably 8 μm or less, still more preferably 7 μm or less, and the matte layer. Any combination of the upper limit of the thickness and the upper limit of the absolute value may be used, whichever is smaller. For example, the upper limit may be 90% or less of the thickness of the matte layer or 20 μm or less, whichever is smaller, or 90% or less or 10 μm or less of the thickness of the matte layer, whichever is smaller. You can also. The thickness of the matte layer will be described later.

The average particle size of the wrinkle formation stabilizer 2 is less than 1 μm. Considering that it stabilizes the formation of wrinkles, stably improves the matting effect, and improves the moist texture, the average particle size of the wrinkle formation stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more. It is more preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm or less, still more preferably 500 nm or less.
In the present specification, the average particle size of the wrinkle formation stabilizer is measured as the mass average value d50 in the particle size distribution measurement by the laser light diffraction method.

Considering that the wrinkle formation stabilizer stabilizes the formation of wrinkles, stably improves the matting effect, and improves the moist texture, the wrinkle formation stabilizer (wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2) The content of (the total content of these when used in combination with) is preferably 0.5 parts by mass or more, more preferably 0.75 parts by mass or more, based on 100 parts by mass of the resin forming the matte layer. It is more preferably 1.0 part by mass or more, and even more preferably 1.2 parts by mass or more. On the other hand, the upper limit is preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, further preferably 10.0 parts by mass or less, still more preferably 7.5 parts by mass or less, and particularly preferably 6 parts. It is 0.0 parts by mass or less. The upper limit is not particularly limited in terms of improving the stable matte effect and improving the moist texture, but if the upper limit is within the above range, for example, the applicability of the resin composition for forming a matte layer The productivity of the decorative material is improved, and the visibility and texture of the matte effect are efficiently improved.

When the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 are used in combination, the content of each of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 is not particularly limited as long as the total content is within the above range. However, the content of the wrinkle formation stabilizer 2 is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and further preferably 1.0 part 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, still more preferably 3.5 parts by mass or less. The blending ratio of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is preferably 0.05 to 0.95 as the blending amount of the wrinkle-forming stabilizer 1 when the total amount thereof is 100 parts by mass. It is by mass, more preferably 0.10 to 0.90 parts by mass, still more preferably 0.20 to 0.80 parts by mass, and even more preferably 0.30 to 0.70 parts by mass.

As the wrinkle formation stabilizer, organic particles and inorganic particles can be used as described above, but the types of these particles themselves can be said to include those conventionally used as a matting agent, for example, the above-mentioned patent documents. A matting agent such as spherical alumina or calcium carbonate is used for the matte layer of the decorative sheet according to 1. As described in Patent Document 1, in order for a matting agent such as spherical alumina or calcium carbonate to exhibit the visibility of the matting effect by itself due to the light diffusion effect caused by the physical shape, as described in Patent Document 1. It is necessary to use it in a total content of about 50 parts by weight of 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate per 100 parts by weight of the resin content. However, in the present disclosure, even if the content is small as described above, that is, the content necessary for exhibiting the visibility of the matte effect itself due to the light diffusion effect due to the physical shape. Even with a smaller content, an extremely excellent matting effect is obtained as compared with the effect obtained by the matting agent, and a moist feeling is also obtained. Therefore, although the matte article of the present disclosure does not substantially contain a matte agent, wrinkles are stably formed on the surface thereof, so that the matte article is more excellent than the case where the matte agent is used. It can be said that the visibility of the defoaming effect is stably obtained, the texture is also obtained, and the moist touch is also obtained.

(Surface shape of matte layer)
The matte layer in the matte article of the present disclosure is a layer having the above-mentioned surface shape, and is preferably a cured product of a resin composition for forming a matte layer containing the above-mentioned specific wrinkle-forming stabilizer in a specific content. It is a layer composed of. As described above, the stable formation of wrinkles on the surface of the matte layer makes it a layer that stably develops a matte effect due to the light diffusion effect caused by the shape of the wrinkles and also develops a moist tactile sensation. .. FIG. 6 is a schematic view showing an embodiment of the matte article of the present disclosure in a plan view, and is a schematic image of the surface of the matte article obtained in the examples. FIG. 6 shows that the matte article of the present disclosure has wrinkles formed on its surface, that is, on the surface of the matte layer. Here, "planar view" means to see the surface of the matte article from the positive direction of the Z axis in the XYZ coordinate system shown in FIGS. 3 to 6.

The wrinkles appearing on at least one surface of the matte layer are the surface shape, that is, Sk (skunes), preferably Sk (skunes) and Sku (Kurtosis), and other Rsm (curves) within the above specific numerical range. There is no particular limitation as long as it has a surface shape having (average length of element), Rz (maximum height), and Ra (arithmetic mean roughness), and it has the above surface shape due to the appearance of wrinkles. The wrinkle formation stabilizer stabilizes the formation, stably develops a matting effect, and also develops a moist tactile sensation.
With respect to wrinkles, at least one surface of the matte layer has an uneven shape composed of irregular wrinkles from the viewpoint of expressing the above-mentioned surface shape, improving the matte effect, and improving the moist tactile sensation. It is preferable that the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions, and the protrusions are linear. It is preferable to have a protrusion. In the present specification, the “streak protrusion” (hereinafter, also referred to as “streak protrusion”) means that the ratio (length / width) of the length and width of the protrusion is 3 or more, preferably 5. As described above, it means that it is more preferably 10 or more, and the method for determining the length and width is as described later.
In the present disclosure, a more preferable irregular wrinkle is one composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions.

Examples of the aspect relating to these wrinkles include the aspect shown in FIG. In FIG. 6, the surface of the matte article, that is, the surface of the matte layer, has irregular wrinkles in a plan view, and irregular wrinkles are formed by a plurality of curved streaks. It is configured by including a plurality of convex portions 3 and a concave portion 2 formed by being surrounded by a plurality of convex portions (plurality of convex portions 3), and at least a part of the plurality of curved convex portions 3. However, it is also shown that each of the meandering linear protrusions is formed, and the meandering concave portion 2 is formed so as to be surrounded by the meandering linear protrusions. The matte article of the present disclosure stably exhibits a matte effect due to the stable formation of wrinkles shown in FIG. 6, and also exhibits a moist tactile sensation.

Here, "curvature" means having one or more portions in which the extending direction of the convex portion 3 of the continuous line is reversed from one side to the other side in a plan view. As an example of the part where the extending direction is reversed from one side to the other side, for example, when the width of the convex portion 3 of the line is ignored (when the width of the plan view shape is regarded as 0). When approximated by a continuous curve, a form having an inflection point and the like can be mentioned. Further, when the width of the convex portion 3 of the streak is ignored and the width is approximated by a straight line, the shape has a V-shaped polygonal line or a portion approximated by two sides sandwiching one vertex of the triangle. And so on.
Further, "meandering" refers to a portion (hereinafter, also referred to as "reversed portion") in which the extending direction of the convex portion 3 of the continuous streak is reversed from one side to the other side in a plan view. It has more than one place, and when the convex part 3 of the streak is advanced in its extending direction, it has a part in which the extending direction of the convex part 3 of the streak is alternately reversed in two places adjacent to each other. Meanders that. For example, when the width of the convex portion 3 of the streak is ignored and the width is approximated by a continuous curve, a form having a portion approximated by the Roman character "S" can be mentioned. Further, when the width of the convex portion 3 of the streak is ignored and the width is approximated by a straight line, a form having a portion approximated by the Roman character “W” can be mentioned.

In the present specification, irregularity means that a shape having a certain rule and an arrangement having a certain rule, that is, a so-called patterning, cannot be said. A typical example of a non-irregular shape, that is, a regular shape, is a so-called "lenticular lens" in which a plurality of cylindrical unit lenses are arranged adjacent to each other in a direction orthogonal to the longitudinal direction thereof. Examples thereof include shapes arranged with a certain periodicity in a specific direction, such as “lenticular lens)”. Therefore, the irregular wrinkles in the present disclosure are irregular in that the shape of one protrusion itself is not a shape formed by a certain rule such as periodicity, and a plurality of protrusions formed by a plurality of protrusions. It includes that the shape of the portion is not formed and arranged according to a certain rule but is irregular, and that the shape of the concave portion surrounded by such a plurality of protrusions is also irregular. ..
In the matte article of the present disclosure, the shape of one protrusion (one convex portion) itself, the shape and arrangement of each of the plurality of protrusions (plurality of protrusions), and the concave portion surrounded by the plurality of protrusions. If any of the shapes is irregular, a matte effect due to having irregular wrinkles and a moist tactile sensation can be obtained, but it is preferable that all of them are irregular. The matte article of the present disclosure has irregular wrinkles, so that the visibility and texture of the matte effect are improved, an extremely excellent matte effect is stably exhibited, and a moist tactile sensation is exhibited. It will be a thing.

As described above, the matte layer has wrinkles, that is, uneven shapes, on at least one surface thereof. For the convex and concave portions in the uneven shape, for example, by utilizing the difference in brightness of the image on the surface of the decorative material of the present disclosure, the darkest part in the density distribution image is set to gradation 255, and the lightest part in the density distribution image is gradation. As 0, the gradations 0 to 255 may be classified by binarizing the gradations 0 to 127 into concave portions and the gradations 128 to 255 into convex portions.

The surface of the matte article of the present disclosure preferably has irregular wrinkles formed at least in a part thereof, and more preferably irregular wrinkles are formed over the entire surface. The place where wrinkles are formed is not particularly limited as long as it is the surface of the matte article. A matte effect and a moist tactile sensation are exhibited. For example, when it has a decorative layer described later and irregular wrinkles are formed in a part of the wrinkles, when the wrinkles are formed on a part corresponding to the pattern of the decorative layer, for example, on the pattern, the pattern becomes more matte than the surroundings. Since it is visually recognized as a wrinkled part, it is possible to improve the design.
Further, as shown in FIG. 6, it has a plurality of protrusions formed by a plurality of protrusions having a certain degree of homogeneity although irregular, and a recess surrounded by the protrusions. Is preferable. Therefore, the shape in which the width of the convex portion (projection portion) of 1 is extremely changed is unlikely to be the above-mentioned surface shape, and is not a preferable mode for obtaining the visibility and texture of the matte effect, and is moist. It cannot be said that it is a preferable mode to obtain a good tactile sensation. The specific aspects of the shapes of the convex portions (projections) and concave portions that form irregular wrinkles, which can be advantageous in stably improving the matting effect and improving the moist tactile sensation, will be described below. .. When the wrinkles have the following shapes, the surface shape is easily exhibited, and the matte effect and the moist tactile sensation are improved.

Regarding the shape of the wrinkles formed on at least one surface of the matte layer, the height of the convex portion (height of the protrusion) is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more. Yes, the upper limit is about 10 μm or less. The width of the convex portion is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, still more preferably 3 μm. It is as follows. When the height and width of the convex portion are within the above range, the surface shape is likely to be exhibited, the matting effect is stably improved in relation to the concave portion, and the moist tactile sensation is improved.
Here, the above-mentioned dimensions of the convex portion are the average of any 10 convex portions (projections) in any 10 locations (100 μm square area × 10 locations) of the matte article of the present disclosure, that is, a total of 100 convex portions. The value. Further, as shown in FIG. 6, since the widths of the convex portions (projections) of 1 are not the same and are wide and narrow, the width of the convex portions (projections) of 1 is the convex portions (projections) of 1. It is the average value of the widths of any 5 points in. The same applies to the height of the convex portion (projection portion).

The depth of the recess 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, still more preferably 0.3 μm or more, and the upper limit is preferably 10 μm or less, more preferably 3 μm or less, still more preferably 2 μm or less. Is. When the depth and width of the concave portion are within the above range, the surface shape is likely to be exhibited, the matting effect is stably improved in relation to the convex portion, and the moist tactile sensation is improved.
Here, the dimensions of the concave portion are determined in the same manner as the dimensions of the convex portion described above.

The distance from the top of the convex portion to the bottom of the concave portion, that is, the height difference between the convex portion and the concave portion is preferably 1 μm or more, more preferably 2 μm or more, further preferably 4 μm or more, and the upper limit is preferably 20 μm or less. It is preferably 8 μm or less, more preferably 7 μm or less. When the distance is within the above range, the surface shape is likely to be exhibited, the matting effect is stably improved, and the moist tactile sensation is improved.
Here, the dimensions of the concave portion are determined in the same manner as the dimensions of the convex portion described above.

The occupancy ratio of the convex portion is preferably 15% or more, more preferably 20% or more, further preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, still more preferably 60% or less. Is. When the occupancy ratio of the convex portion is within the above range, the surface shape is likely to be exhibited, and in relation to the occupancy ratio of the concave portion surrounded by the convex portion, the matte effect is stably improved and the moist texture is obtained. improves.
Here, the occupancy ratio of the convex portion is an average value of the occupancy ratio of the convex portion at any 10 locations (100 μm square region × 10 locations) of the matte article of the present disclosure.

The convex portion and the concave portion may have portions in substantially the same direction and having substantially the same width, but the length thereof is preferably short in consideration of the improvement of the matte effect and the improvement of the moist tactile sensation. Specifically, the continuous length of the convex portions and concave portions having substantially the same direction and substantially the same width is preferably 95 μm or less, more preferably 80 μm or less, still 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, wrinkles become more irregular, so that the matte effect is stably improved and the moist touch is improved.
Here, 80% or more of any 10 convex portions and concave portions (that is, 100 convex portions and concave portions in total) in any 10 locations (100 μm square area × 10 locations) of the matte article of the present disclosure are described above. It is preferable that the conditions of the above conditions are satisfied, more preferably 85% or more, still more preferably 90% or more, still more preferably 95% or more. In addition, "abbreviation" of "substantially the same" in the present specification means that they are almost the same, meaning a difference within ± 3 ° in the case of direction without branching, and ± 5 in the case of width. Means a difference within%.

The number of protrusions (projections) in a 100 μm square region is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and the upper limit is preferably 200 or less, more preferably 100 or less, and further. It is preferably 70 or less. When the number of convex portions is within the above range, the matting effect is stably improved and the moist tactile sensation is improved.
The number of convex portions is an average value of the number of convex portions in 10 locations (100 μm square region × 10 locations) of the matte article of the present disclosure.

FIG. 3 is a cross-sectional view showing an embodiment of the matte article of the present disclosure, and is a cross-sectional view of the matte article 1 cut along a plane parallel to the thickness direction thereof. The thickness direction of the matte article 1 is the Z direction in FIG.
The shape of the concave portion may be, for example, an acute-angled shape as shown in 2a of FIG. 3, a semicircular or semi-elliptical shape as shown in 2b, or a combination thereof. Further, the shape as shown in 2c of FIG. 3 may be obtained, in which one convex portion has a concave portion in a part thereof.
On the other hand, as the shape of the convex portion, although the width is wide and narrow as shown in 3a and 3b of FIG. 3, it exhibits a semicircular or semi-elliptical shape.

The thickness of the matte layer is not particularly limited as long as it can stably exhibit the matte effect and can form the above-mentioned wrinkles to the extent that a moist tactile sensation can be exhibited. Considering ease of use and the like, it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, still more preferably 5 μm or more, and the upper limit is preferably 300 μm or less, more preferably. It is 200 μm or less, more preferably 150 μm or less, still more preferably 100 μm or less.
In the present specification, the thickness of the matte layer is the average value of the values of 20 points obtained by measuring the thickness of 20 points from the image taken by a scanning electron microscope (SEM) with respect to the cross section of the matte article. do. 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 thickness of other layers.

The matte layer is a layer having the above-mentioned surface shape on the entire surface thereof, and since the matte article of the present disclosure has a surface shape on at least a part of the surface, at least a part of the surface of the matte article. It may be provided on the entire surface thereof. When the matte article of the present disclosure has the above-mentioned base material and the matte layer, it may be provided on at least a part of the surface of the base material, or may be provided on the entire surface thereof.
If the matte layer is provided at a place where the consumer can see and touch the matte article, that is, if the surface shape is provided at a place where the consumer can see and touch the matte article. The effects of the invention, such as a matte effect and a moist tactile sensation, can be obtained.

Further, even when the base material exhibits the shape of a film, a sheet, or a plate, the matte layer may be provided at a place where the consumer can see and touch the matte article, and at least one of the surfaces thereof. It may be provided on a part of the surface, or may be provided on the entire surface thereof. From the viewpoint of improving the matte effect and the moist tactile sensation, it may be provided on the entire surface of one surface as shown in FIGS. 4 to 6. It is preferable that the film is used.

(resin)
The resin for forming the matte layer is a resin that forms a resin composition for forming a matte layer containing the above wrinkle formation stabilizer in a predetermined amount and is cured to become a cured product and constitutes the matte layer. good. Examples of such a resin include an ionizing radiation curable resin. The matte layer is a layer that can be provided on the outermost surface of the matte article of the present disclosure, as shown in FIGS. 4 to 6. Therefore, in addition to being a resin that easily forms wrinkles with a wrinkle-forming stabilizer, surface properties such as processing characteristics, stain resistance, scratch resistance, and weather resistance are exhibited in consideration of improving usability as a matte article. A resin that is easy to use is preferable, and an ionizing radiation curable resin is a preferable resin from these viewpoints. Since the matte article of the present disclosure contains an extremely small amount of the wrinkle formation stabilizer contained in the matte layer, the performance of the resin forming the matte layer is more directly exhibited as its surface characteristics. Become.

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, for example, (meth) acryloyl group, vinyl group, and the like. A functional group having an ethylenic double bond such as an allyl group is preferable. In addition, in this specification, a (meth) acryloyl group means an acryloyl group or a metachloroyl group. Further, in the present specification, (meth) acrylate means acrylate or methacrylate.
Further, ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing and / or cross-linking a molecule, and usually ultraviolet (UV) or electron beam (EB) is used. In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion rays are also included.

Examples of the ionizing radiation curable resin include an electron beam curable resin and an ultraviolet curable resin. An ultraviolet curable resin is preferable in consideration of stabilizing the formation of wrinkles by the wrinkle formation stabilizer, stably improving the matting effect, and improving the moist touch feeling.
Specifically, the ionizing radiation curable resin can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. Here, "(meth) acrylate" means "acrylate or methacrylate".
Examples of the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group.

Considering that it stabilizes the formation of wrinkles, stably improves the matting effect, improves the moist tactile sensation, and further improves the surface characteristics such as post-processing characteristics, 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, and more preferably 2 or more and 6 or less. Further, when the number of functional groups is the above, the above-mentioned surface shape is particularly easy to be obtained, and the moist tactile sensation is easily improved.
These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

Examples of the polymerizable oligomer include (meth) acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional groups. Examples thereof 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.
Further, as the polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group on the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond on the main chain. In molecules such as aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resin having many reactive groups in small molecules, novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether and the like. There are oligomers and the like having cationically polymerizable functional groups.

These polymerizable oligomers may be used alone or in combination of two or more.
Among the above, the polymerizable oligomers include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, polycarbonate (meth) acrylate oligomers, and acrylic (meth) oligomers. The acrylate oligomer is preferable, the urethane (meth) acrylate oligomer and the polycarbonate (meth) acrylate oligomer are more preferable, and the urethane (meth) acrylate oligomer is further preferable. When these polymerizable oligomers are used, the formation of wrinkles can be stabilized, the matting effect can be stably improved, the moist texture can be improved, and the post-processing characteristics, scratch resistance and weather resistance can be improved. Surface properties such as weathering 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. 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 moist tactile sensation can be improved, and the processing characteristics, scratch resistance and weather resistance can be improved. Surface properties such as weathering 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 preferred. Is more preferable. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

In the present disclosure, as the resin forming the matte layer, it is preferable to use the above-mentioned polymerizable oligomer and the polymerizable monomer in combination. As the polymerizable oligomer, a polyfunctional urethane (meth) acrylate oligomer is preferable, a polyfunctional urethane acrylate oligomer is more preferable, and as a polymerizable monomer, a polyfunctional polymerizable monomer is preferable, and a polyfunctional (meth) acrylate is preferable. Monomers are more preferred, and polyfunctional acrylate monomers are even more preferred. It is possible to stabilize the formation of wrinkles, stably improve the matting effect, improve the moist tactile sensation, and further improve the surface characteristics such as processing characteristics, scratch resistance and weather resistance.
When used in combination, for the same reason, the content of the polymerizable oligomer with respect to a total of 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, and further. It is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, and the upper limit is preferably 98 parts by mass or less, more preferably 95 parts by mass or less, still more preferably 92 parts by mass or less. Is.

(Resin composition)
The matte layer is preferably composed of a cured product of a resin composition containing the wrinkle formation stabilizer in a predetermined content, and the resin composition preferably contains the resin and the wrinkle formation stabilizer in a predetermined content. It is included in. The resin composition used in the present disclosure may contain other components in addition to the above-mentioned wrinkle formation stabilizer and resin, depending on desired performance and the like.
The resin composition for forming the matte layer may contain a monofunctional (meth) acrylate for the purpose of lowering the viscosity thereof, for example. These monofunctional (meth) acrylates may be used alone or in combination of two or more.

When the resin is an ultraviolet curable resin that is cured by ultraviolet rays, it is preferable to contain additives such as a photopolymerization initiator and a photopolymerization accelerator. By including these additives, the resin can be cured even when ultraviolet rays are used (without using ionizing radiation), and surface properties that contribute to practical use can be obtained.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, thioxanthones and the like.
Further, the photopolymerization accelerator can reduce the polymerization inhibition due to air at the time of curing and accelerate the curing rate. For example, from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like. One or more selected species can be mentioned.

Since the matte layer is a layer that can be provided on the outermost surface of the matte article of the present disclosure, it is preferably a layer having weather resistance, and includes various weather resistant agents such as an ultraviolet absorber and a light stabilizer. Is preferable.
As the ultraviolet absorber, an ultraviolet absorber widely used for cosmetic materials, decorative sheets and the like can be used without particular limitation. For example, a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, a triazine-based ultraviolet absorber, and a hydroxyphenyl can be used. Examples thereof include triazine-based ultraviolet absorbers. As the light stabilizer, a light stabilizer widely used for decorative materials, decorative sheets and the like can be used without particular limitation, and examples thereof include hindered amine-based light stabilizers such as piperidinyl sebacate-based light stabilizers. Further, these ultraviolet absorbers and light stabilizers may have reactive functional groups having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group and an allyl group in the molecule.
These weather resistant agents such as ultraviolet absorbers and light stabilizers can be used alone or in combination of two or more.

[60 ° gloss value]
The matte article of the present disclosure is an article having excellent visibility and texture of a matte effect. In the present specification, "matte" means that it is difficult to visually recognize the gloss, and it cannot be said unconditionally because it changes depending on the color tone, pattern, etc. of the article, but for example, the 60 ° gloss value is 20.0 or less, preferably 10. If it is about 0 or less, it is generally treated as "matte".

So far, for example, in a matte article exhibiting a black color or other dark color, it is possible to obtain excellent visibility of a matte effect having a 60 ° gloss value of 20.0 or less, preferably 10.0 or less even if a matting agent is used. It was possible. Here, "dark color" means a CIE (International Commission on Illumination) L ^* a ^* b ^* L ^* value in a color system (hereinafter referred to as "dark color"), which has a low brightness and is measured according to, for example, JIS Z8781-4: 2013. It may be simply referred to as "L ^* value"), which means that it is usually about 40 or less, preferably 30 or less.
However, since a large amount of matting agent is used, it is not easy to manufacture because streaks and unevenness occur at the time of layer formation, and the surface characteristics are deteriorated. Further, for example, for a matte article exhibiting a color tone other than black or other dark colors, there is a lower limit to the numerical value of the 60 ° gloss value even when a matte agent is used, which is the same as that of a matte article exhibiting black color, and in any case, the surface surface. It was not possible to easily obtain a matte article having excellent characteristics and excellent visibility and texture of the matte effect. Such a tendency becomes more remarkable as the 60 ° gloss value is made smaller.

In the matte article of the present disclosure, two kinds of wrinkle formation stabilizers having a predetermined average particle size are used in combination, and the content thereof is as small as described above, so that the gloss is stable and extremely excellent. Not only the visibility and texture of the erasing effect have been obtained, but also a moist tactile sensation has been obtained. Further, by suppressing the amount of the wrinkle formation stabilizer to be used to an extremely small amount, it is possible to suppress a significant increase in the viscosity of the resin composition, which facilitates layer formation and is excellent according to the characteristics of the resin used for the matte layer. It naturally has surface characteristics such as stain resistance, scratch resistance, and weather resistance.

The matte article of the present disclosure cannot be unconditionally defined because it changes according to the color tone as described above. However, for example, in the case of exhibiting black or other dark colors, the 60 ° gloss value on the matte layer side is 10. It is possible to exhibit extremely excellent visibility of a matte effect of 0 or less, 7.5 or less, 5.0 or less, 4.0 or less, 3.6 or less, and 2.0 or less.

Further, a matte article exhibiting a color tone other than black or other dark colors can also have the above 60 ° gloss value. The 60 ° gloss value on the matte layer side of the matte article 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 matte article, and further has another layer. Unless otherwise, it will be a 60 ° gloss value on the surface of the matte layer. Further, when another layer is provided and another layer is provided on the surface side of the matte layer, the 60 ° gloss value means the 60 ° gloss value of the other layer, but the matteness of the present disclosure is disclosed. It is substantially due to the composition of the matte layer that the article has a particular 60 ° gloss value.
In the present specification, the 60 ° gloss value on the matte layer side is a 60 ° mirror surface gloss measured in accordance with JIS K 5600-4-7: 1999, and a gloss meter or the like at any 10 points is used. It is an average value of values that can be measured from the matte layer side using.

[Total light transmittance]
As described above, the matte article of the present disclosure may employ a base material made of a non-transparent material, a decorative layer described later, and the like, and may be used for exterior members, interior members, and the like. It is possible. Considering the case where the above-mentioned base material, the decorative layer described later, etc. are adopted, and the case where it is used for the above-mentioned application, the total light transmittance of the matte article of the present disclosure is measured in accordance with JIS K7361-1: 1997. The rate is preferably 20% or less, more preferably 15% or less, still more preferably 10% or less.
In the present specification, the total light transmittance of the matte article is the total light transmittance measured in accordance with JIS K7361-1: 1997, and is an average value of measurements at any 10 points.

[Other layers]
The matte article of the present disclosure may have, for example, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer and the like as other layers in addition to the matte layer and the base material. 4 and 5 show cross-sectional views showing an embodiment of the matte article of the present disclosure having these layers. 4 and 5 are cross-sectional views showing an embodiment of the matte article of the present disclosure, which is a cross-sectional view of the matte article 1 cut along a plane parallel to the thickness direction thereof. Here, the "thickness direction" means the Z direction in FIGS. 4 and 5.
The matte decorative material 1 shown in FIG. 4 has a base material 5 and a matte layer 4 in this order, and the matte article 1 shown in FIG. 5 has a base material 5, a decorative layer 6, and an adhesive layer 7. It has a transparent resin layer 8, a primer layer 9, and a matte layer 4 in this order.

(Primer layer)
When the matte article of the present disclosure is composed of, for example, a plurality of layers, it may have a primer layer in order to improve the interlayer adhesion of the plurality of layers.
When the matte article of the present disclosure has a layer other than the matte layer, for example, when it has a matte layer and a base material, a primer layer is provided between the matte layer and the base material in order to improve the interlayer adhesion. Can be provided.

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

As the binder resin, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, polycarbonate-based urethane-acrylic copolymer (carbonate bond to the polymer main chain). Urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the terminal and side chains), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic co-weight Resins such as a coalesced resin, a chlorinated propylene resin, a nitrocellulose resin (nitrated cotton), and a cellulose acetate resin are preferably mentioned, and these can be used alone or in combination of two or more.
Further, the binder resin may be one obtained by cross-linking and curing these resins by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent. Among these, a polyol resin such as an acrylic polyol resin is preferably cross-linked and cured with an isocyanate-based curing agent, and a acrylic polyol resin is more preferably cross-linked and cured with an isocyanate-based 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 further preferably 2 μm or more and 6 μm or less.

The matte article of the present disclosure is based on the matte layer on the side opposite to the wrinkled surface of at least one of the matte layers for the purpose of improving the adhesiveness with an adherend such as a resin molded product on which the articles are laminated. When the material is provided, a primer layer (also referred to as "backside primer layer") may be provided on the side opposite to the side on which the matte layer of the base material is provided.

(Transparent resin layer)
The matte article of the present disclosure may have a transparent resin layer in order to increase its strength and, in the case of having a decorative layer described later, from the viewpoint of protecting the decorative layer and the like. When the transparent resin layer has a base material, it may be provided between the base material and the matte layer, and when it has a decorative layer, the decorative layer and the matte layer are provided in order to protect the decorative layer. It may be provided in between.

Examples of the resin constituting the transparent resin layer include a polyolefin resin, a polyester resin, a polycarbonate resin, an acrylonitrile-butadiene-styrene resin (hereinafter, also referred to as “ABS resin”), an acrylic resin, and a vinyl chloride resin. Among these, a polyolefin resin and a vinyl chloride resin are preferable from the viewpoint of post-processing suitability and the like. Further, two or more kinds of these various resins may be laminated or mixed and used.

The transparent resin layer may be transparent to the extent that the substrate side can be visually recognized from the transparent resin layer, and if it has a decorative layer, it may be transparent to the extent that the decorative layer can be visually recognized. , Colored transparent and translucent. That is, in the present disclosure, "transparency" means not only colorless and transparent but also colored transparent and translucent.

The transparent resin layer may contain a weathering agent such as an ultraviolet absorber and a light stabilizer, and an additive such as a colorant.
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 further preferably 60 μm or more and 100 μm or less, in consideration of protection of the decorative layer and post-processing suitability.

(Decorative layer)
The matte article of the present disclosure may have a decorative layer in order to improve the design. The decorative layer may be provided on a surface opposite to at least one surface having wrinkles of the matte layer, and if a base material is provided, a transparent resin layer may be provided between the base material and the matte layer. If it is present, it may be provided in the order of a decorative layer, a transparent resin layer, and a matte layer.

The decorative layer may be, for example, a colored layer that covers the entire surface, or may be 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 a "solid colored layer" and is a layer indicated by "6a" in FIG. 5, and the "picture layer" is indicated by "6b" in FIG. Is done. Further, as shown in FIG. 5, a solid coloring layer and a pattern layer may be combined.

As the pattern (pattern) of the pattern layer, a pattern as desired may be adopted without particular limitation. For example, a wood grain pattern such as an annual ring or a conduit groove on the surface of a wood board, a stone pattern on a stone board surface such as marble or granite, etc. Examples include a texture pattern on the surface of a cloth, a textured pattern on a leather surface, a geometric pattern, characters, figures, and a combination thereof.
Further, a pattern such as a pattern such as a cloth, a ceramic material, a stone material, a wood-based material, or a metal surface, which is exemplified as having a "moist" tactile sensation, is also preferably mentioned. A more realistic design can be expressed by combining the "moist" tactile sensation of the matte article of the present disclosure and the design of the object having the "moist" tactile sensation.

The ink used for the decorative layer is a binder resin mixed with a pigment, a colorant such as a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, and the like. used.
The binder resin of the decorative layer is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate copolymer weight. Examples thereof include a coalesced resin, a vinyl chloride-vinyl acetate-acrylic copolymer resin, a chlorinated propylene resin, a nitrocellulose resin, and a cellulose acetate resin. Further, various types of resins such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound can be used.

As the colorant, a pigment having excellent hiding power and weather resistance is preferable. As the pigment, the same pigments as those exemplified as the pigments that can be used for 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 decorative layer. The following is more preferable.

The decorative layer may contain an ultraviolet absorber, a weather resistant agent such as a light stabilizer, and an additive such as a colorant.
The thickness of the decorative layer may be appropriately selected according to the desired pattern, but is preferably 0.5 μm or more and 20 μm or less, preferably 1 μm or more and 10 μm in order to conceal the ground color of the adherend and improve the design. The following is more preferable, and 2 μm or more and 5 μm or less is further preferable.

(glue)
When the matte article of the present disclosure has a base material and a transparent resin layer, an adhesive layer may be provided between the base material and the transparent resin layer in order to improve the adhesion between the two layers. ..
When a decorative layer is further provided between the base material and the transparent resin layer, the positional relationship between the adhesive layer and the decorative layer is not particularly limited, and specifically, the decorative layer and the adhesive layer are formed from the side closer to the base material. And the transparent resin layer may be provided in this order, or the adhesive layer, the decorative layer and the transparent resin layer may be provided in this order from the side closer to the base material.

The adhesive layer can be composed of, for example, an adhesive such as a urethane-based adhesive, an acrylic-based 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 the urethane-based adhesive include an adhesive using a two-component curable urethane resin containing various polyol compounds such as a polyether polyol, a polyester polyol, and an acrylic polyol, and a curing agent such as an isocyanate compound.

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 further preferably 2 μm or more and 10 μm or less in order to efficiently obtain a desired adhesive force.

[Manufacturing method of matte articles]
In the first method for producing a matte article of the present disclosure, a matte layer is formed, and a layer of a resin composition for forming a matte layer containing the above-mentioned resin and a wrinkle forming stabilizer is formed. It is characterized by comprising a matte layer forming step of forming by irradiating with.
By the first production method, for example, as shown in FIGS. 4 and 5, a laminate having a substrate and at least a part thereof having the above-mentioned surface shape, for example, a cured product layer of a resin composition as a matte layer. As described above, it is possible to manufacture a matte article having a structure of a laminated body in which a plurality of layers are laminated. For example, if the above-mentioned resin composition for forming a matte layer is applied onto a base material, a layer of the resin composition is formed on the base material, and the above-mentioned irradiation is performed to form a matte layer, the base material is formed. A matte article having a matte layer and a matte layer can be manufactured. By making the matte article have the above-mentioned surface shape by the matte layer, the surface on the matte layer side can be made to have the above-mentioned surface shape. Therefore, the first manufacturing method has a matte effect that the 60 ° gloss value on the matte layer side is 20.0 or less, 10.0 or less, or even less, and has a moist tactile sensation. It is a suitable manufacturing method in the case of manufacturing.

According to the method for producing the matte article of the present disclosure, the matte article of the present disclosure described above can be easily obtained. Specifically, in forming the matte layer, by irradiating a resin composition for matte formation containing a wrinkle formation stabilizer that forms the matte layer with ultraviolet rays having a low wavelength of at least 100 nm or more and 380 nm or less. Wrinkles can be formed on at least one surface of the matte layer, and it is possible to impart a matte effect and a moist touch to the matte article (matte layer).

Regarding the mechanism by which wrinkles are formed on at least one surface of the matte layer and a matte effect and a moist tactile sensation are exhibited by irradiating the resin composition for forming the matte layer with such low-wavelength ultraviolet rays. Details are unknown, but it is presumed to be due to the following mechanism.

When a coating layer coated with a resin composition for forming a matte layer to a predetermined thickness is irradiated with low-wavelength ultraviolet rays, the energy of the ultraviolet rays permeates only the surface portion, and the energy does not reach the lower layer. , Only the surface portion of the resin composition begins to cure. Therefore, it is considered that only the surface undergoes curing shrinkage and wrinkles are formed. As described above, it is considered that the formation of wrinkles occurs in a state where only a certain thickness direction from the surface of the resin composition for forming a matte layer is cured by irradiation with ultraviolet rays having a low wavelength.

Further, as a comparison between Examples and Comparative Examples described later, wrinkle formation becomes unstable when the wrinkle formation stabilizer is not contained, and the visibility and texture of the matte effect are stable over the entire surface of the matte layer. It does not develop to a sufficient extent, and it does not sufficiently develop a moist tactile sensation. From this, the stable expression of the matte effect and the moist tactile sensation cannot be explained only by the curing of only the surface portion by the low wavelength ultraviolet rays. That is, in order for the matte article of the present disclosure to stably have wrinkles to exhibit a matte effect and a moist tactile sensation, it is indispensable to include a wrinkle formation stabilizer.

Considering that the stable matting effect due to the formation of wrinkles and the moist touch are not obtained when the wrinkle formation stabilizer is not contained, the wrinkle formation stabilizer has a function like a nucleus that triggers the formation of wrinkles. The resin on the surface portion of the resin composition gathers around the nucleus to form a convex portion (projection portion) of a wrinkle and a concave portion together with the formation of the convex portion (projection portion). As a result, it is considered that the formation of wrinkles is stable, and a matte effect and a moist tactile sensation are stably exhibited.

The resin composition for forming a matte layer containing a wrinkle-forming stabilizer and a wrinkle-forming stabilizer used in the production method of the present disclosure is a wrinkle-forming stabilizer and matte that can be used in the above-mentioned matte cosmetic material of the present disclosure. It is the same as the content described as the resin composition for layer formation.

In the production method of the present disclosure, the resin composition for forming a matte layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. By this irradiation, as described above, the energy of ultraviolet rays permeates only the surface portion, and the energy does not reach the lower layer, so that only the surface portion of the resin composition begins to cure. Therefore, the formation of wrinkles is stabilized by causing curing shrinkage only on the surface, and the surface layer of the resin composition becomes a cured product, which constitutes a matte layer. After that, the curing progresses from the portion near the surface where the curing progresses slowly to the deep portion separated in the depth direction, the layer of the resin composition becomes a cured product, and thus the resin composition is cured over the entire thickness. Moreover, it constitutes a matte layer having wrinkles that exerts a light diffusing effect on the surface and develops a moist tactile sensation. In order to promote the progress of curing to the deep part, it is preferable to perform another irradiation treatment after irradiating with light having a wavelength of 100 nm or more and 380 nm or less, as will be described later.

Examples of the wavelength light having a wavelength of at least 100 nm or more and 380 nm or less include a rare gas such as Ar, Kr, Xe, and Ne, a halide of a rare gas such as F, Cl, I, and Br, or a mixed gas thereof. An excited state dimer formed by electric discharge, that is, "excimer light" containing light in the ultraviolet wavelength range from an excimer is preferable. The wavelength of the excimer light and the excimer used as the light source include, for example, light having a wavelength of 126 nm radiated from the excimer of Ar ₂ (hereinafter abbreviated as “126 nm (Ar ₂ )”), 146 nm (Kr ₂ ), and 157 nm. Wavelength light of (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF), 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), 351 nm (XeF) and the like can be preferably adopted. As the excimer light, either naturally emitted light or laser light having high coherence (coherence) due to stimulated emission can be used, but it is usually sufficient to use naturally emitted light. A discharge lamp that emits light (ultraviolet rays) is also referred to as an "excimer lamp".
Excimer light has a single wavelength peak, and is characterized by having a narrower half-width of wavelength than ordinary ultraviolet rays (for example, ultraviolet rays emitted from a metal halide lamp, a mercury lamp, or the like). By using such excimer light, the formation of wrinkles is stabilized, the matting effect is stably improved, and the moist 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, still more preferably 150 nm or more, in order to stabilize the formation of wrinkles, stably improve the matting effect, and improve the moist tactile sensation. It is 155 nm or more, and the upper limit is preferably 320 nm or less, more preferably 300 nm or less, further preferably 250 nm or less, still more preferably 200 nm or less, and most preferably 172 nm (Xe ₂ ). As described above, in the present disclosure, in order to stably improve the matting effect and improve the moist tactile sensation, it is preferable to use wavelength light having a shorter wavelength, and medium wavelength ultraviolet rays (wavelength: 280 to 320 nm) and short wavelengths. It can be said that wavelength ultraviolet rays (wavelength: 280 nm or less) are more preferable, and short wavelength ultraviolet rays are further preferable.

In the present disclosure, the integrated light amount of the wavelength light is preferably 1 mJ / cm ² or more, more preferably 1 mJ / cm 2 or more, from the viewpoint of stabilizing the formation of wrinkles, stably improving the matting effect, and improving the moist tactile sensation. It is 10 mJ / cm ² or more, 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 is preferably 1,000 mJ / cm ² or less, more preferably 500 mJ /, in consideration of productivity such as reduction of the number of lamps required for irradiation of wavelength light and improvement of production efficiency. It is cm ² or less, more preferably 300 mJ / cm ² or less. For the same reason, the ultraviolet output density is preferably 0.001 W / cm or more, more preferably 0.01 W / cm or more, still more preferably 0.03 W / cm or more, and the upper limit is preferably 10 W / cm. It is cm or less, more preferably 5 W / cm or less, still more preferably 3 W / cm or less.
Further, the oxygen concentration when irradiating the wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, still more preferably 500 ppm or less, still more preferably 300 ppm or less.

In the matte layer forming step in the method for producing a matte article of the present disclosure, in addition to the above-mentioned irradiation with wavelength light of at least 100 nm or more and 380 nm or less, other treatments that contribute to the curing of the resin composition for forming the matte layer are performed. May be done.
For example, in order to stabilize the formation of wrinkles due to the difference in the degree of progress of curing between the above-mentioned surface portion and the deep portion separated from the surface in the depth direction, and to promote the progress of curing to the deep portion, for example, it exceeds 380 nm. The resin composition for forming a matte layer may be pre-cured by pre-irradiating with wavelength light, preferably 385 nm or more and 400 nm or less, and then irradiated with 100 nm or more and 380 nm or less. Further, after irradiation with light having a wavelength of 100 nm or more and 380 nm or less, post-curing may be performed in order to further cure the resin composition. For pre-curing and post-curing, it may be appropriate to determine whether or not to adopt the matte layer according to desired properties such as processing characteristics, surface characteristics such as stain resistance, and the like. Further, although the above-mentioned wavelength light belongs to ultraviolet rays, it is also possible to use not only ultraviolet rays but also other ionizing radiations such as electron beams. For example, in post-curing, an electron beam can be preferably used from the viewpoint of improving the surface characteristics of the matte layer.

In the manufacturing method of the present disclosure, the matte layer is coated with a resin composition for forming a matte layer by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method, and a comma coating method. The coated coating layer (uncured resin layer) can be formed by irradiating it with light having a wavelength of at least 100 nm or more and 380 nm or less.

Further, the matte article obtained by the manufacturing method of the present disclosure may have other layers such as a transparent resin layer in addition to the base material described as the layer that can be adopted in the matte article of the present disclosure. ..
For example, the decorative layer, the adhesive layer and the primer layer can be formed by applying a coating liquid containing the composition forming each layer by the above-mentioned known method, and drying and curing as necessary. When forming the transparent resin layer, the resin film forming the transparent resin layer can be formed by dry laminating or the like.

Among the matte articles of the present disclosure, an article composed of a single layer as shown in FIG. 3, for example, a matte product having a cured product of a resin composition and having the above-mentioned surface shape on the surface on one side thereof. The article can be manufactured by the following second manufacturing method.
The second manufacturing method is a step of applying a resin composition for forming a matte article containing a resin and a wrinkle forming stabilizer on the release layer of a support sheet having a release layer to form a coating layer. It is characterized by having a step of irradiating the coating layer with light having a wavelength of at least 100 nm or more and 380 nm or less, and a step of peeling off the support sheet.

The support sheet may be appropriately selected from those exemplified as those that can be used as the above-mentioned base material, and a base material made of, for example, a fibrous material, preferably paper such as wood-free paper may be used. After the resin composition is made into a matte article, it is easier to peel off than the matte article, is easy to handle, and is economical.

The peeling layer is a layer provided to facilitate peeling of the support sheet from the matte article after the resin composition is made into a matte article. Examples of the peeling layer include acrylic resins, vinyl chloride-vinyl acetate, olefin resins, silicone resins, fluororesins, silicones, and various resins modified with fluorine, which are excellent in peelability, and waxes as needed. Can be mixed.
Examples of waxes include microcrystallin wax, carnauba wax, paraffin wax, fisher tropus wax, various low molecular weight polyethylenes, wood wax, beeswax, whale wax, ibota wax, wool wax, celac wax, candelilla wax, petrolactam, and some. Various waxes such as modified waxes, fatty acid esters and fatty acid amides are preferably mentioned.

The resin composition for forming a matte article containing a resin and a wrinkle formation stabilizer can be adopted from among the resins and wrinkle formation stabilizers that can be used and exemplified in the resin composition for forming a matte layer. be. Further, the content of the wrinkle formation stabilizer and the like are the same as those of the resin composition for forming the matte layer.

The application of the resin composition for forming a matte article can be performed in the same manner as the application of the resin composition for forming a matte layer, and the coated layer is irradiated with light having a wavelength of at least 100 nm or more and 380 nm or less. The method is also the same as the irradiation of the layer of the resin composition for forming the matte layer.
Further, the thickness of the coating layer is the thickness of the matte article obtained as it is. The thickness of the coating layer may be determined according to the desired thickness, and is not particularly limited, and may be selected from the widest range of 1 μm or more and 10 cm or less among the thicknesses of the above-mentioned base materials. Considering manufacturing suitability, handling suitability, etc., the thickness of the coating layer is preferably 3 μm or more, more preferably 5 μm or more, and the upper limit is preferably 300 μm or less, more preferably 200 μm or less.

Further, a decorative layer may be provided for improving the design before forming the coating layer of the resin composition for forming the matte article. Therefore, when composed of a single layer as shown in FIG. 3, the matte article may further have a decorative layer. The decorative layer may have the same structure as the decorative layer described as the layer that the matte article having the above-mentioned base material and the matte layer can have.

By irradiating the coating layer of the resin composition for forming a matte article with the above-mentioned wavelength light, the formation of wrinkles is stabilized by causing curing shrinkage only on the surface as in the above-mentioned matte layer, and the resin composition. The surface layer of the material becomes a cured product having the above-mentioned surface shape, and the curing progresses from the surface layer where the curing progresses slowly to a deep portion away from the surface layer in the depth direction, and the resin composition is cured as a whole, so that at least a part of the surface is cured. It is a matte article having the above-mentioned surface shape.
Further, regarding irradiation, post-curing may be performed in order to promote curing to a deep portion, or pre-curing may be performed.

After irradiating the above-mentioned predetermined wavelength light to cure the coating layer of the resin composition for forming a matte article, the support sheet is peeled off to have a gloss having the above-mentioned surface shape on at least a part of the surface. An erasable item is obtained.

Further, among the matte articles of the present disclosure, an article composed of a single layer as shown in FIG. 3, for example, a matte article having the above-mentioned surface shape on at least a part of the surface of a resin article such as a resin molded article. Can be manufactured by the following third manufacturing method.
The third manufacturing method is characterized by having a step of embossing at least a part of the surface of the resin molded product with an embossing plate, a molding sheet, or the like to give the surface shape.

The embossed plate and the shaped sheet can be used without particular limitation as long as they can impart the above-mentioned surface shape. The surface shape of the embossed plate and the shaped sheet and the surface shape formed by these have the opposite shapes. Specifically, Sk (skunes) and Sk (Kurtsis) have a shape in which Sk (skunes) and Sk (skunes) of the shaped sheet exhibit target numerical values with a normal distribution of 0 and 3, respectively. Therefore, as the shaping sheet used to obtain the matte article of the present disclosure, an embossed plate, a shaping sheet or the like having a surface shape having a Sk (skewness) of more than 0 may be used. For example, when an embossed plate having a Sk (skewness) of 0.50 and a shaped sheet are used, a matte article having a surface shape having a Sk (skewness) of −0.50 can be obtained. Further, for example, when an embossed version having a Sk (skewness) of 0.50 and a Sk (Kurtosis) of 2.50, and a fixed sheet, the Sk (skewness) is −0.50 and Sk (skewness) is −0.50. A matte article having a surface shape with a Kurtsis) of 3.50 is obtained. It should be noted that the numerical values relating to the surface shapes of the shaped sheet and the matte article are only theoretical values, and it goes without saying that some errors may occur.

Further, as the matte article of the present disclosure, for example, thermosetting such as high pressure melamine resin decorative board, low pressure melamine resin decorative board, diallyl phthalate (DAP) resin decorative board, polyester decorative board, guanamine resin decorative board, phenol resin decorative board and the like. A resin resin veneer can also be mentioned. The thermosetting resin decorative board is a liquid state of a thermosetting resin on a fibrous material, for example, a woven fabric or a non-woven fabric made of paper, which has been described as a base material that can be adopted as a base material for the above-mentioned matte article. Using a material impregnated with the uncured material, it can be subjected to pressure molding or thermosetting, for example, heating temperature: 100 to 200 ° C., pressure: 0.1 to 9.8 MPa, molding time: 10 seconds to 120. It is a decorative board obtained by applying it under the conditions of minutes. When pressure molding or heat pressure molding is performed, the base material, the embossed plate, and the shaping sheet are arranged so as to be laminated and molded to obtain a decorative plate as a matte article having the above surface shape. Is obtained.

In this case, examples of the thermosetting resin impregnated in the substrate include melamine resin, urea resin, melamine-urea resin, guanamine resin, diallyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, and silicon resin. , Polysiloxane resin and the like are preferably mentioned, and thermosetting resins such as melamine resin, urea resin, melamine-urea resin, guanamine resin and sulfonamide resin are preferably mentioned, among which melamine resin, melamine-urea resin and phenol resin are preferable. Preferred, especially melamine resin is preferred.

(Use)
The matte article of the present disclosure can be used as a decorative member as described later.

Further, the matte article of the present disclosure can also be used as a shaping sheet. When used as a shaping sheet, it can be used as an embossing plate used for embossing in the second manufacturing method, the third manufacturing method, a shaping sheet, or the like, whereby the article composed of the above-mentioned single layer. , A thermosetting resin decorative board can be obtained.
As described above, the surface shape of the shaped object (article composed of a single layer, thermosetting resin decorative board, etc.) is the surface shape of the shaped sheet which is the matte article of the present disclosure. The shape is the opposite. Therefore, an object composed of a single layer, a thermosetting resin decorative board, or the like has a Sk (skewness) of 0.00 or more, has a moist or slippery feel, and has a matte effect. Will have.

[Cosmetic material]
The matte article of the present disclosure can be used as a decorative member as it is, or can be used as a decorative member by laminating, compounding, or combining with an adherend. Which one to use may be determined as desired. When the matte article of the present disclosure is used for a decorative member, it is preferable that the matte article has a decorative layer.

When having an adherend, the decorative member has the adherend and the above-mentioned matte article of the present disclosure, and specifically, the surface of the adherend that requires decoration and the gloss of the matte article. It is a laminated layer in which wrinkles of the matte layer are formed and a surface opposite to one surface that exhibits a matte effect and a moist tactile sensation is opposed to each other. Further, in the case of having an adherend, it is preferable that the matte article of the present disclosure has a film or sheet form in consideration of ease of laminating.

On the other hand, the matte article of the present disclosure is suitable when the article composed of a single layer shown in FIG. 3 is used as it is as a decorative member, and above all, the above-mentioned is applied to at least a part of the surface of a resin article such as a resin molded article. Matte articles having the surface shape of are particularly suitable. When the matte article of the present disclosure is used as it is as a decorative member, it is preferably used as a decorative member constituting the surface of, for example, a building, various furniture, a vehicle, a home electric appliance, or the like.
Further, among the articles composed of the single layer shown in FIG. 3, the matte article composed of the cured product of the resin composition for forming the matte article obtained by the above-mentioned second production method is made up as it is. It can be used as a member, or it can be used in combination with an adherend depending on the thickness.

(Applied material)
Examples of the adherend include flat plates of various materials, plate materials such as curved plates, three-dimensional articles such as cylinders and polygonal columns, and sheets (or films). For example, it is used as a board material such as wood single board made of various woods such as cedar, cypress, pine, and lauan, wood plywood, laminated wood, particle board, wood fiber board such as MDF (medium density fiber board), and three-dimensional shaped articles. Wood members; Metal members used as plates, three-dimensional shaped articles, sheets, etc. made of metals such as iron, aluminum, copper, and alloys containing one or more of these metals; Ceramics such as glass and ceramics, gypsum, cement , ALC (lightweight bubble concrete), ceramic members used as plate materials made of non-ceramic ceramic materials such as calcium silicate and three-dimensional shaped articles; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile) -Butadiene-styrene copolymer) Resins, phenolic resins, vinyl chloride resins, cellulose resins, plates made of resins such as rubber, three-dimensionally shaped articles, resin members used as sheets and the like can be mentioned. In addition, these members can be used alone or in combination of two or more.

The adherend may be appropriately selected from the above depending on the intended use, and may be used as an interior member of a building such as a wall, a ceiling, or a floor, or an exterior member such as an outer wall, a roof, an eaves ceiling, a fence, or a gate, or a window. When fittings or building members such as frames, doors, handrails, skirting boards, surrounding edges, and moldings are used, those made of at least one member selected from wood members, metal members, and resin members are preferable, and entrance doors and the like. When fittings such as exterior members, window frames, and doors are used, those made of at least one member selected from metal members and resin members are preferable.

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

(Adhesive layer)
The adherend and the matte article are preferably adhered via an adhesive layer in order to obtain excellent adhesiveness.

The adhesive used for the adhesive layer is not particularly limited, and a known adhesive can be used and may be appropriately selected depending on the intended use. For example, adhesives such as moisture-curable adhesives, anaerobic-curable adhesives, dry-curable adhesives, UV-curable adhesives, heat-sensitive adhesives (for example, hot-melt adhesives), and pressure-sensitive adhesives are preferable. Be done.

Examples of the resin used for these adhesives include acrylic resin, urethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, polyester resin, and amide resin. Examples thereof include cyanoacrylate resin and epoxy resin, and these can be used alone or in combination of two or more. Further, a two-component 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.
Further, an adhesive may be used for the adhesive layer. As the pressure-sensitive adhesive, various pressure-sensitive adhesives such as acrylic, urethane, silicone, and rubber can be appropriately selected and used.

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

[Total light transmittance]
As described above, the decorative member using the matte article of the present disclosure includes a base material, a decorative layer, etc. made of a non-transparent material, and a cover made of a non-transparent material. There are cases where a landing material is used, and it can also be used for applications such as exterior members and interior members. In consideration of the above, the total light transmittance of the decorative member using the matte article of the present disclosure measured in accordance with JIS K7361-1: 1997 is preferably 20% or less, more preferably 15% or less, and further. It is preferably 10% or less.

(Manufacturing method of decorative parts)
The decorative member can be manufactured through a step of laminating the matte article of the present disclosure and the adherend.
This step is a step of laminating the adherend and the matte article of the present disclosure, and wrinkles are formed on the surface of the adherend that requires decoration and the matte layer of the matte article of the present disclosure. When the matte article of the present disclosure has a base material, the surface on the side opposite to one side that exhibits the effect and the moist tactile sensation and the surface on the base material side are opposed to each other and laminated. Examples of the method of laminating the adherend and the matte article include a laminating method in which the matte article is pressurized and laminated on the plate-shaped adherend with a pressure roller via an adhesive layer.

When a hot melt adhesive (also referred to as "heat-sensitive adhesive") is used as the adhesive, the heating temperature is preferably 160 ° C. or higher and 200 ° C. or lower, although it depends on the type of resin constituting the adhesive. The temperature of 100 ° C. or higher and 130 ° C. or lower is preferable for the hot melt adhesive. Further, in the case of vacuum forming, it is generally performed while heating, and it is preferably 80 ° C. or higher and 130 ° C. or lower, and 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 end of the wood can be arbitrarily decorated by grooving, chamfering, etc. using a cutting machine such as a router or a cutter. And various uses, for example, interior members of buildings such as walls, ceilings, floors; exterior members such as outer walls, eaves ceilings, roofs, walls, fences; window frames, doors, door frames, handrails, skirts, etc. Fittings or building members such as peripheral edges and moldings; general furniture such as tans, shelves and desks; kitchen furniture such as dining tables and sinks; surface decorative boards such as cabinets for home appliances and OA equipment; for vehicle interiors or exteriors It is suitably used as a member or the like.

Further, in addition to the decorative members used for the above-mentioned buildings and the like, the matte article of the present disclosure is used as it is, or the matte article is laminated, composited, or combined with another material (adhesive material). , Packaging materials, whiteboards or blackboards, credit cards, cash cards, telephone cards, various cards such as various certificates, various keyboard keys, windows, doors, transparent plates such as partitions (window glass, etc.), artificial It can be used for leather and the like. In these uses, it is usually preferable that the matte article of the present disclosure is arranged on the outermost surface, which exhibits a matte effect and a moist tactile sensation. Of course, it is also possible to make it into a form.

Next, the present disclosure will be described in more detail by way of examples, but the present disclosure is not limited to this example.

(Measurement of surface shape)
Sk (skunes), Sk (Kurtosis), Rsm (average length of curved elements), Rz (maximum height) and Ra (arithmetic mean roughness) of the articles obtained in Examples and Comparative Examples are the articles. A shape analysis laser microscope (“VK-X150 (control unit) / VK-X160 (measurement unit)”, manufactured by Keyence Co., Ltd.) was used for a rectangular shape (1024 μm × 768 μm) at an arbitrary surface shape, and an objective lens: 50. Double, laser wavelength: 658 nm, measurement mode: surface shape mode, measurement pitch: 0.13 μm, measurement quality: high-speed mode.
The cutoff values of Rsm (average length of curved elements), Rz (maximum height) and Ra (arithmetic mean roughness) were set to 0.8 mm.

(Evaluation method: 60 ° gloss value)
For the articles obtained in Examples and Comparative Examples, a gloss meter (“Micro Gloss (model name)”, manufactured by BYK Gardner) was used to achieve 60 ° mirror gloss according to K 5600-4-7: 1999. Was measured.

(Evaluation of texture (uniformity of surface condition))
The articles obtained in Examples and Comparative Examples were evaluated by any 20 adults regarding the surface texture (uniformity of surface condition) according to the following criteria.
A: More than 18 people evaluated that the surface condition was uniform and the matte effect was highly visible.
B: 15 or more and 17 or less evaluated that the surface condition was uniform and the matte effect was highly visible.
C: 14 or less evaluated that the surface condition was uniform and the matte effect was highly visible.

(Evaluation of moist texture)
For the articles obtained in Examples and Comparative Examples, silk fabric was used as a standard for moist tactile sensation, and 20 adults were allowed to evaluate the tactile sensation on the surface according to the following criteria. evaluated.
A: More than 18 people evaluated that the tactile sensation was close to the standard and the tactile sensation was moist.
B: 15 or more and 17 or less were evaluated as having a tactile sensation close to the standard and a moist tactile sensation.
C: 14 or less were evaluated as having a tactile sensation close to the standard and a moist tactile sensation.

[Example 1]
A PET sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method to color it. A layer (thickness: 3 μm) is provided, a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm), and the primer layer is matted. Resin composition for layer formation (polyfunctional urethane (meth) acrylate oligomer (tetrafunctional, average molecular weight: 1800): 65 parts by mass, polyfunctional acrylate monomer (bifunctional, molecular weight: 400): 35 parts by mass, wrinkle formation stable Agent 1 (silica particles, average particle size: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): (0.8 parts by mass) is applied by the gravure method (application amount: 5 g / m ² (when dried)), and then ultraviolet rays are irradiated using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet amount). : 6 W / cm ² ), then irradiate with ultraviolet rays using an excima light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen). (Concentration 200 ppm or less))), and then further irradiated with a high-pressure mercury lamp (ultraviolet output density: 200 W / cm) to provide a matte layer on the substrate to obtain a shaped sheet having the substrate and the matte layer. rice field.

Next, phenol-impregnated kraft paper (manufactured by Ota Sangyo Co., Ltd., obtained by impregnating kraft paper weighing 200 g / m ² with 30% by mass of phenol resin) and black titanium paper as a decorative layer (weighing 80 g / m ² ). ), Overlay paper (obtained by impregnating 300% by mass of methylol melamine resin (manufactured by Cymel) on paper weighing 22 g / m ² (manufactured by Meade)), phenol-impregnated kraft paper, black titanium. The paper and the overlay paper are stacked in this order, and the overlay paper and the surface having the surface shape of the shaping sheet are overlapped so as to be in contact with each other, and then sandwiched between the end plates, and the pressure is 7.8 MPa (80 kg / cm ² ). It was heat-processed and molded at a temperature of 145 ° C. for 30 minutes, and the resin was permeated, cured, and integrated to obtain a thermosetting resin decorative board (high-pressure melamine decorative board) as a matte article.
The gloss value of the obtained matte article was measured at 60 ° from the matte layer side and found to be 1.5. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 1.

[Example 2]
In Example 1, the resin contained in the resin composition for forming a matte layer was applied in the same manner as in Example 1 except that the polyfunctional urethane acrylate oligomer: 90 parts by mass and the monofunctional acrylate monomer: 10 parts by mass. Obtained a mold sheet. The obtained shaped sheet itself was used as the matte article of Example 2. When the 60 ° gloss value of the obtained matte article was measured from the matte layer side, it was 1.6. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 1.

[Comparative Example 1]
In Example 1, the same as in Example 1 except that the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, that is, the wrinkle formation stabilizer was not used. , Obtained a shaped sheet. The obtained shaped sheet itself was used as the article of Comparative Example 1, and the 60 ° gloss value, surface shape measurement, texture and tactile sensation of the article were evaluated by the above method. These results are shown in Table 1.

[Comparative Example 2]
In Example 1, the amount of the wrinkle forming stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, and 15.0 parts by mass of the matting agent (average particle size: 8.0 μm) was used instead. Then, a shaped sheet was obtained in the same manner as in Example 1 except that only an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) was irradiated. The obtained shaped sheet itself was used as the article of Comparative Example 2, and the 60 ° gloss value, surface shape measurement, texture and tactile sensation of the article were evaluated by the above method. These results are shown in Table 1.

[Comparative Example 3]
A polypropylene sheet (thickness: 100 μm) that has been subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by the gravure method to color it. A layer (thickness: 3 μm) is provided, a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm), and the primer layer is matted. Resin composition for layer formation (polyfunctional urethane acrylate oligomer (tetrafunctional, average molecular weight: 1800): 65 parts by mass, polyfunctional acrylate monomer (bifunctional, molecular weight: 400): 35 parts by mass, wrinkle formation stabilizer 1 ( Silica particles, average particle size: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 (Mass part) is applied by the gravure method (application amount: 5 g / m ² (when dried)), and then ultraviolet rays are irradiated using an excima light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W. / Cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), then further irradiated with a high-pressure mercury lamp (ultraviolet output density: 200 W / cm), and a matte layer on the substrate. A matte article having a base material and a matte layer was obtained. The gloss value of the obtained matte article was measured at 60 ° from the matte layer side and found to be 1.6. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 2.

[Comparative Example 4]
A matte article was obtained in the same manner as in Comparative Example 3 except that a paper substrate (thickness: 30 μm) was used as the substrate in Comparative Example 3. Table 2 shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 2.

[Comparative Example 5]
In Comparative Example 3, a matte article was obtained in the same manner as in Comparative Example 3 except that only the polyfunctional acrylate monomer (bifunctional) was used as the resin in the resin composition for forming the matte layer. Table 2 shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 2.

[Comparative Example 6]
A polypropylene sheet (thickness: 100 μm) that has been subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by the gravure method to color it. A layer (thickness: 3 μm) is provided, a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm), and the primer layer is matted. Resin composition for layer formation (polyfunctional urethane acrylate oligomer 1 (tetrafunctional, average molecular weight: 1800): 65 parts by mass, polyfunctional acrylate monomer (bifunctional, molecular weight: 400): 35 parts by mass, wrinkle formation stabilizer 1 (Silica particles, average particle size: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0. (8 parts by mass) is applied by the gravure method (application amount: 5 g / m ² (when dried)), and then ultraviolet rays are irradiated using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet amount: 6 W). / Cm ² ), then irradiate with ultraviolet rays using an excima light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm). The following)) was then further irradiated with a high-pressure mercury lamp (ultraviolet output density: 200 W / cm) to provide a matte layer on the substrate to obtain a matte article having the substrate and the matte layer. The 60 ° gloss value of the obtained matte article was measured from the matte layer side and found to be 1.4. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 3.

[Comparative Examples 7 to 11]
In Comparative Example 6, the wrinkle formation stabilizer in the resin composition for forming the matte layer was compared except that the amount used as shown in Table 3, the resin composition for forming the matte layer to be used, and the base material were used. A matte article was obtained in the same manner as in Example 6. The polyfunctional urethane acrylate oligomer 2 used in Comparative Examples 10 and 11 is an oligomer having 3 functional groups. Table 3 shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side. In addition, the surface shape was measured and the texture and tactile sensation were evaluated by the above method. These results are shown in Table 3.

From the results in Table 1, the matte articles disclosed in the present disclosure have 60 ° gloss values of 1.5 and 1.6 on the matte layer side, and are extremely excellent in visibility of the matte effect. It was confirmed that the texture was excellent. It was also confirmed that it was excellent in moist texture.
On the other hand, in the article of Comparative Example 1 containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface, stable visibility of the matting effect could not be obtained, and the gloss value was partially implemented. The same part as in the example existed, but there was a part with high gloss and the surface condition was unstable (not uniform), and it could not be said that the texture was excellent. In addition, the articles of Comparative Examples 1 and 2 lacked a moist tactile sensation, but rather had a rough tactile sensation.

FIG. 7 is an optical microscope image of the matte article of Example 1 (the width of the image corresponds to 272.0 μm, and the same applies to the image of Comparative Example 2). According to the optical microscope image (FIG. 7) of the matte article of Example 1, it can be confirmed that the surface thereof has irregular wrinkles. On the other hand, according to the optical microscope image (FIG. 8) of Comparative Example 1, as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 9) of Comparative Example 2, wrinkles like the matte article of the example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed, and the surface was confirmed. The condition was unstable (not uniform), and the texture was not excellent.
From the above results, the matte article of the present disclosure exhibits a specific surface shape due to wrinkles on the surface thereof, and due to the surface shape, the matte article has an extremely excellent visibility and texture of the matte effect. It was confirmed that the moist texture was excellent.

The articles of Comparative Examples 3 to 5 have a 60 ° gloss value of 1.4 to 1.6 on the matte layer side, are extremely excellent in visibility of the matte effect, and are also excellent in texture. It was confirmed that it was a thing. However, it did not have a moist texture, but rather a rough texture.

The articles of Comparative Examples 6 to 11 have a 60 ° gloss value of 1.4 on the matte layer side, are extremely excellent in visibility of the matte effect, and are also excellent in texture. Was confirmed. However, it did not have a moist feel, but rather a silky feel.

The matte article of the present disclosure has excellent visibility and texture of a matte effect, and has an excellent moist touch. Therefore, it is used for various purposes, for example, interior members of buildings such as walls, ceilings, and floors. Exterior walls, eaves ceilings, roofs, walls, fences, and other exterior materials; window frames, doors, door frames, handrails, skirts, surrounding edges, moldings, and other fittings or building materials; General furniture; Kitchen furniture such as dining tables and sinks; Surface decorative plates for cabinets such as home appliances and OA equipment; Decorative members for various members such as interior or exterior members of vehicles.
Further, in addition to the decorative members used for the above-mentioned buildings and the like, the matte article of the present disclosure is used as it is, or the matte article is laminated, composited, or combined with another material (adhesive material). , Packaging materials, whiteboards or blackboards, credit cards, cash cards, telephone cards, various cards such as various certificates, various keyboard keys, windows, doors, transparent plates such as partitions (window glass, etc.), artificial It is also suitably used as leather and the like.

1: Matte article 2: Concave part 3: Convex part (protrusion part)
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 (15)

A matte article having a surface shape having a Sk (skewness) of less than 0.00, as defined in ISO 25178-2: 2012, on at least a portion of the surface. The matte article according to claim 1, which has a surface shape and has a Sk (Kurtsis) of 3.00 or more as defined in ISO 25178-2: 2012. The matte article according to claim 1 or 2, wherein Rsm (average length of curved elements), which is a lateral parameter of the contour curve defined in JIS B0601: 2013, of the surface shape is 100.00 μm or less. .. 13. Matte goods. The invention according to any one of claims 1 to 4, wherein Ra (arithmetic mean roughness), which is a parameter in the height direction of the contour curve defined in JIS B0601: 2013, of the surface shape is 2.00 μm or less. Matte goods. The matte article according to any one of claims 1 to 5, which comprises a matte layer and whose surface shape is formed by the surface of the matte layer. The matte article according to claim 6, wherein the surface of the matte layer forming the surface shape has an uneven shape composed of irregular wrinkles. The matte according to claim 7, wherein the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions. Goods. The matte layer is composed of a cured product of a resin composition containing a resin and a wrinkle formation stabilizer, and the wrinkle formation stabilizer is 100% or less or 30 μm or less of the thickness of the matte layer, whichever is smaller. The matte article according to any one of claims 6 to 8, which has an average particle size as an upper limit and contains the wrinkle-forming stabilizer in an amount of 0.5 parts by mass or more with respect to 100 parts by mass of the resin. .. The matte article according to any one of claims 1 to 9, which has a base material. The matte article according to claim 10, wherein the base material is in the form of a sheet. The matte article according to claim 11, wherein the matte layer is provided over the entire surface of one surface of the base material. The matte article according to any one of claims 1 to 12, which has a decorative layer. The matte article according to any one of claims 1 to 13, wherein the surface shape has a 60 ° gloss value of 10.0 or less. The matte article according to any one of claims 1 to 14, wherein the total light transmittance measured in accordance with JIS K7361-1: 1997 is 20% or less.

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