JP7215514B2 - matte goods - Google Patents

Description

The present invention relates to matte articles.

Conventionally, for example, interior members of buildings such as walls, ceilings and floors; In addition to fixtures and fixtures such as malls, general furniture such as wardrobes, shelves, and desks, kitchen furniture such as dining tables and sinks, various types of furniture and components used around water such as kitchens, toilets, bathrooms, and washstands, or BACKGROUND ART So-called decorative materials and decorative sheets are used as articles for decorating and protecting surfaces such as surface decorative boards for cabinets of home electric appliances and OA equipment, interior and exterior members of vehicles, and the like. As such decorative materials and decorative sheets, for example, those having a surface layer having a desired function are used. performance is required.

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

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

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

As a technique for improving the texture by a matting effect, a matting agent (also referred to as a "matting agent") is used as in Patent Document 1, and the light diffusion effect itself is obtained. and a method of forming an uneven shape on the outermost surface by applying embossing as described in Patent Document 2 above.

However, when a matting agent is used as in Patent Document 1, it is necessary to increase the amount of the matting agent to achieve a better matting effect. It falls off from the coating film and damages the coating film, reducing the scratch resistance. The surface properties tend to deteriorate due to the penetration of contaminants and the adsorption of the contaminants to the matting agent itself, which lowers the stain resistance. On the other hand, if the amount used is reduced in order to suppress deterioration of the surface properties, the matting effect tends to be reduced, and the surface properties and the matting effect are in a dichotomy relationship. Therefore, there is a limit to the matte effect using matting agents.
In addition, when embossing is used as in Patent Document 2, preparation of embossing plates takes a lot of time and effort and is not easy. Therefore, it cannot be said that it is a method that can sufficiently respond to the diversity of customer demands.

In addition, as a method for improving the texture of the article by a matting effect, (i) a method of roughening the surface by blasting inorganic particles, (ii) a method of roughening the surface by a decomposition reaction using an alkaline treatment liquid. and (iii) a drum printing system (also referred to as “DPS”), such as those disclosed in Japanese Patent Application Laid-Open Nos. 57-87318 and 7-32476. An uncured liquid material of an ionizing radiation curable resin is applied to the surface of the embossed plate, and irradiated with ionizing radiation in a state where a base sheet made of a resin sheet or the like is superimposed to make the uncured liquid material a cured product, and the curing After adhering an object to a base sheet, it is released from the embossing plate to form a base material consisting of the base sheet and the cured product on the base sheet, thereby embossing the base material. There is also a method of transferring a printing paint using a rough shape plate by . However, in the method (i), blasting the inorganic particles causes deterioration of the physical properties of the article itself, and in the chemical etching (ii), it is necessary to select a resin material that can be used. is low. In addition, common to (i) to (iii), there is also the problem that the production speed is slow, the yield is high, and the productivity is poor.

Accordingly, an object of the present invention is to provide a matte article with excellent matte effect visibility and texture with high productivity.

The present inventors have made intensive studies to solve the above problems, and found that the above problems can be solved by adopting a matte layer having a predetermined irregular shape and a Martens hardness within a predetermined range in a matte article. found a solution. That is, in order to solve the above problems, the present invention provides the following matte article;
A matte article having an uneven shape due to irregular wrinkles on the surface, having a matte layer composed of a cured product of a resin composition, wherein the matte layer has a Martens hardness of 200 N/mm ² or less,
I will provide a.

ADVANTAGE OF THE INVENTION According to this invention, the matte article excellent in the visibility and texture of a matte effect can be provided with high productivity.

BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic diagram in planar view which shows one Embodiment of the matte article of this invention. 1 is a cross-sectional view showing one embodiment of the matte layer of the matte article of the present invention; FIG. 1 is a cross-sectional view showing one embodiment of the matte article of the present invention; FIG. 1 is a cross-sectional view showing one embodiment of the matte article of the present invention; FIG. 2 is an optical microscope image of the surface of the matte article obtained in Example 1. FIG. 2 is an optical microscope image of the surface of the matte article obtained in Example 2. FIG. 4 is an optical microscope image of the surface of the matte article obtained in Example 3. FIG. 4 is an optical microscope image of the surface of the matte article obtained in Example 4. FIG. 2 is an optical microscope image of the surface of the matte article obtained in Example 5. FIG. 4 is an optical microscope image of the surface of the article obtained in Comparative Example 1. FIG. 4 is an optical microscope image of the surface of the article obtained in Comparative Example 2. FIG.

Hereinafter, a fuel oil composition for an internal combustion engine according to an embodiment of the present invention (hereinafter sometimes simply referred to as "this embodiment") will be specifically described. It should be noted that the present invention is not limited to the following embodiments, and can be arbitrarily modified within the scope that does not impair the effects of the invention.
In addition, in this specification, numerical values related to “greater than”, “less than or equal to” and “to” in describing numerical ranges are numerical values that can be arbitrarily combined. For example, when a numerical range is described as "A to B" and "C to D", numerical ranges such as "A to D" and "C to B" are also included.

[Matte article]
The matte article of the present embodiment has an uneven shape due to irregular wrinkles on the surface, and has a matte layer composed of a cured product of a resin composition, and the matte layer has a Martens hardness of 200 N/mm. ² or less.

[Matte layer]
The matte layer is a layer that has irregular wrinkles on the surface and is composed of a cured product of a resin composition. By having an uneven shape due to irregular wrinkles on the surface, a matte effect and texture are exhibited. In this case, in order to obtain an excellent matte effect and texture, the matte effect is uniformly expressed over the entire surface of the matte article, and partial gloss unevenness is reduced, and a stable matte effect is visually recognized. (Hereinafter, expressions such as "stable visibility of the matte effect" and similar expressions may be used.) In addition, the surface condition due to the stable formation of wrinkles over the entire surface of the matte article. Achieving uniformity (also called "texture") is essential.
In the matte article of the present embodiment, by setting the Martens hardness of the matte layer within a specific range of 200 N/mm ² or less, wrinkles are easily formed on the surface of the matte layer, and excellent matte It can have the visibility and texture of the effect.

(Surface shape of matte layer)
The matte layer has irregular wrinkles on the surface due to having the above-mentioned specific Martens hardness, and expresses excellent visibility and texture of the matte effect due to the light diffusion effect caused by the uneven shape expressed by the wrinkles. layer. In particular, ionizing radiation curable resins such as monomers and oligomers, which will be described later, are selected as resins constituting the matte layer, and irradiated with ultraviolet rays having a short wavelength of 100 nm or more and less than 200 nm, which will be described later, to cause irregular wrinkles on the surface. In a mode employing a manufacturing method for forming an uneven shape, the wrinkles express the visibility and texture of the matte effect excellent in the matte layer.
Here, "wrinkles form" more specifically means the shape of "wrinkles" and their geometric characteristic values (length, width and their ratios, and also statistical indicators such as, for example, Rz (maximum height), Rsm (average length of curvilinear element), Ra (arithmetic mean roughness), Ssk (skewness), Sku (kurtosis), etc. It means that various numerical values and indices such as inner distribution (dispersion σ) converge when the Martens hardness of the matte layer is within the above specific range compared to when it is outside the above specific range. .

As described above, in the prior art such as Patent Document 1, matting agents have been used for matte expression. The matting agent itself exhibits a matting effect due to the light diffusion effect resulting from its physical shape. Specifically, what is generally called a matting agent usually has a refractive index difference between the matting agent particles and the surrounding resin and air, and the light reflection and refraction properties corresponding to the contour shape of the particles The visibility of the matte effect is expressed by the light diffusion effect of the interface. That is, when a matting agent is used, the surface has an uneven shape in which the contour shape of the matting agent stands out in places, and the uneven shape due to irregular wrinkles like the matte article of the present embodiment. will be completely different from

The matting effect of the matte layer in the matte article of the present embodiment is not due to light diffusion due to reflection and refraction of light rays by particles themselves such as matting agents, but to a predetermined Martens hardness of the matte layer. Within the range, wrinkles are formed on the surface of the matte layer, and the visibility of the matte effect is excellent in the matte article due to the light diffusion effect at the interface of the refractive index difference between the surface and air. It is intended to give texture along with. Therefore, the matting effect in the present embodiment is defined by the matting effect by the matting agent that itself expresses the visibility of the matting effect, the mechanism (action) of the matting, and the structure for expressing the matting. etc. are different.

In addition, as a method for improving the texture of the article by the matting effect, as described above, (i) a method of roughening the surface by blasting inorganic particles, (ii) chemical etching, and (iii) transfer However, all of them have the problem that the production speed is slow, the yield is high, and the productivity is poor. In this regard, in the matte article of the present embodiment, irregular wrinkles are formed on the surface simply by setting the Martens hardness of the matte layer within a predetermined range, and the wrinkles provide excellent visibility of the matte effect. And texture can be obtained, so the productivity is extremely excellent.

FIG. 1 is a schematic plan view showing one embodiment of the matte article of the present embodiment, which is a schematic image of the surface of the matte article obtained in the example. FIG. 1 shows that the matte article of this embodiment has wrinkles on its surface, ie, the surface of the matte layer.

A matte article has an irregular shape formed by irregular wrinkles on its surface. Such an uneven shape due to wrinkles is formed when the matte layer has a predetermined Martens hardness, and the wrinkles express excellent visibility and texture of the matte effect. In particular, ionizing radiation curable resins such as monomers and oligomers, which will be described later, are selected as resins constituting the matte layer, and irradiated with ultraviolet rays having a short wavelength of 100 nm or more and less than 200 nm, which will be described later, to cause irregular wrinkles on the surface. In a mode employing a manufacturing method for forming an uneven shape, the wrinkles are suitable for expressing the visibility and texture of the matte effect excellent in the matte layer.

In addition, the irregular wrinkles are preferably composed of a plurality of protrusions formed by a plurality of protrusions and a recess formed by being surrounded by the plurality of protrusions, and the protrusions are filamentous. It is preferable to have projections. In the present specification, the term "protrusion of filament" (hereinafter also referred to as "filament projection") means that the ratio of the length and width of the protrusion (length/width) is 3 or more, preferably It means 5 or more, more preferably 10 or more, and the method for determining the length and width will be described later.
In the present embodiment, the more preferable irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary protrusions and recesses formed by being surrounded by the plurality of filamentary protrusions. .

Aspects related to these wrinkles include, for example, the aspect shown in FIG. FIG. 1 shows that the surface of the matte article, that is, the surface of the matte layer, has irregular wrinkles in a plan view, and the irregular wrinkles are formed by a plurality of curved filamentary protrusions. and a recess 2 formed by being surrounded by a plurality of protrusions (plurality of protrusions 3), and at least part of the plurality of protrusions 3 that are curved. are formed by meandering linear protrusions, and meandering concave portions 2 are formed so as to be surrounded by the meandering linear protrusions. The matte article of this embodiment has irregular wrinkles as shown in FIG. 1, and the wrinkles provide excellent visibility and texture of the matte effect.

Here, “curved” means having one or more portions in which the extending direction of the continuous filamentary projections 3 is reversed from one side to the other side in plan view. As an example of the portion where the extending direction is reversed from one side to the other side, for example, when the width of the planar view shape of the protrusion 3 of the filament is ignored (when the width is considered to be 0), a continuous curve Examples of approximation include a form having an inflection point. In addition, when approximating with a straight line when ignoring the width of the planar view shape of the protrusion 3 of the filament, a form having a portion approximated by two sides sandwiching one vertex of a V-shaped broken line or triangle etc.
In addition, the term "meandering" refers to a portion where the extending direction of the continuous linear projections 3 is reversed from one side to the other side (hereinafter also referred to as a "reversed portion") at least two times. There are at least two portions where the extension direction of the filament projections 3 is alternately reversed at two locations adjacent to each other when the filament projections 3 are advanced in their extending direction. means to have For example, when approximating with a continuous curve when ignoring the width of the projection 3 of the filaments in plan view, there is a form having a portion approximated by the Roman letter "S". Further, when the linear projections 3 are approximated by a straight line when the width of the projection 3 of the filament in plan view is ignored, there is a form having a portion approximated by the Roman letter "W".

In this specification, the term "irregular" means a shape having a certain rule, or a shape that is arranged according to a certain rule, which cannot be said to be patterned. A typical example of a non-irregular shape (regular shape) is a so-called "lenticular lens ( lenticular lens)”, which are arranged with a certain periodicity in a specific direction. Therefore, the irregular wrinkles in the present embodiment are defined by the fact that the shape of one protrusion itself is irregular rather than a shape formed according to a certain rule such as periodicity, and that the shape of a plurality of protrusions formed by a plurality of protrusions is irregular. It includes that the shape of the protrusions is not formed and arranged according to a certain rule but is irregular, and that the shape of the recesses surrounded by such a plurality of protrusions is also irregular. be.
In the matte article, any of the shape of one protrusion (one protrusion) itself, the shape and arrangement of each of a plurality of protrusions (plurality of protrusions), and the shape of a recess surrounded by a plurality of protrusions Both are preferably irregular, although if they are irregular, the visibility and texture of the matte effect can be obtained by having irregular wrinkles. The matte article has irregular wrinkles to facilitate the visibility and texture of the matte effect.

As described above, the matte layer has wrinkles, ie, unevenness on at least one surface thereof. The median value of the height distribution in the uneven shape is used as a reference for the protrusions and recesses in the uneven shape, and a region having a height exceeding the median value is defined as a protrusion, and a region having a height equal to or less than the median value is defined as a recess. For example, using the density difference (i.e., lightness difference) of an image having a density corresponding to the height of the surface of the matte article and 1:1, the darkest part of the density distribution image is set to gradation 255, and the density distribution image is the highest. With the light part as gradation 0 (the median density value for the median height value is 127), the gradation 0 to 255 is defined as a concave portion, and the gradation 128 to 255 as a convex portion. It suffices to classify them by binarizing them.

Irregular wrinkles are preferably formed on at least a part of the surface of the matte article, and more preferably irregular wrinkles are formed over the entire surface. In the matte article of the present embodiment, the matte layer has a predetermined Martens hardness, so that irregular wrinkles are easily formed over the front surface.
The place where the wrinkles are formed is not particularly limited as long as it is the surface of the matte article, for example, it is not limited to the place corresponding to the pattern described later (on the pattern), and if it is at least part of the surface, wrinkles The visibility and texture of the matte effect due to formation are expressed. For example, in the case where there is a pattern layer to be described later and irregular wrinkles are formed in part, if the wrinkles are formed in a place (for example, on the pattern) according to the pattern of the pattern layer, the pattern will be more prominent than the surroundings. Since it is visually recognized as a matted portion, it is possible to improve the design.

Also, as shown in FIG. 1, it has a plurality of protrusions formed by a plurality of protrusions that are irregular but have a certain degree of homogeneity, and recesses surrounded by the protrusions. is preferred. Therefore, a shape in which the width and height of one protrusion (protrusion) change drastically is not preferable for obtaining the visibility and texture of the matte effect. Regarding the shape of the protrusions (protrusions) and recesses that form irregular wrinkles, the formation of wrinkles can be advantageous in improving the visibility and texture of the excellent matte effect. It is explained below.

Regarding the shape of the wrinkles formed on at least one surface of the matte layer, the height of the projections (the height of the protrusions) is preferably 0.5 µm or more, more preferably 1 µm or more, and still more preferably 2 µm or more. and the upper limit is about 10 μm or less. The width of the protrusion is preferably 0.1 μm or more, more preferably 0.3 μm or more, and still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, and still more preferably 3 μm. It is below. When the height and width of the protrusions are within the above ranges, the visibility and texture of the matte effect are improved in relation to the recesses.
Here, the above dimensions of the protrusions are arbitrary 10 protrusions (protrusions) in arbitrary 10 locations (100 μm square area × 10 locations) of the matte article of the present embodiment, that is, a total of 100 protrusions Average value. In addition, as shown in FIG. 1, the width of one protrusion (projection) is not the same but has a wide width, so the width of one protrusion (projection) is ) shall be the average value of the widths of any five locations. The same applies to the height of the projection (protrusion).

The depth of the concave portion is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more, and the upper limit is about 10 μm or less. The width of the recess is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more, and the upper limit is preferably 10 μm or less, more preferably 3 μm or less, and still more preferably 2 μm or less. is. When the depth and width of the concave portions are within the above ranges, the visibility and texture of the matte effect are improved in relation to the convex portions.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The distance from the top of the projection to the bottom of the recess (height difference between the projection and the recess) is preferably 1 μm or more, more preferably 2 μm or more, and even more preferably 4 μm or more, and the upper limit is preferably 20 μm or less, more preferably 2 μm or more. It is preferably 8 μm or less, more preferably 7 μm or less. When the distance is within the above range, the visibility and texture of the matte effect are improved.
Here, the dimensions of the recesses are determined in the same manner as the dimensions of the projections.

The occupancy ratio of the convex portion is preferably 15% or more, more preferably 20% or more, and still more preferably 30% or more, and the upper limit is preferably 80% or less, more preferably 70% or less, and further preferably 60% or less. is. When the occupancy ratio of the projections is within the above range, the visibility and texture of the matte effect are improved in relation to the occupancy ratio of the recesses surrounded by the projections.
Here, the occupancy ratio of the convex portions is the average value of the occupancy ratio of the convex portions at arbitrary 10 locations (100 μm square area×10 locations) on the matte article.

The protrusions and recesses may have portions of approximately the same direction and approximately the same width, but from the viewpoint of improving the visibility and texture of the matting effect, the lengths thereof are preferably short. Specifically, the length of continuous protrusions and recesses having approximately the same direction and approximately the same width is preferably 95 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less, and the lower limit is preferably 5 μm or more. It is more preferably 10 μm or more, still more preferably 15 μm or more. When the length is within the above range, the wrinkles become more irregular, thereby improving the visibility and texture of the matte effect.
Here, 80% or more of the arbitrary 10 convex portions and concave portions (that is, a total of 100 convex portions and concave portions) in arbitrary 10 locations (100 μm square area × 10 locations) of the matte article meet the above conditions. It preferably satisfies the requirement, more preferably 85% or more, still more preferably 90% or more, and even more preferably 95% or more. In addition, the “substantially” of “substantially the same” in this specification means that they are substantially the same, without branching, meaning a difference within ± 3 ° in the case of direction, and ± 5 in the case of width Means difference within %.

In addition, the number of protrusions (protrusions) in a 100 μm square area is preferably 10 or more, more preferably 20 or more, and still more preferably 30 or more, and the upper limit is preferably 200 or less, more preferably 100 or less, and further. Preferably it is 70 or less. When the number of protrusions is within the above range, the visibility and texture of the matte effect are improved.
The number of protrusions is the average number of protrusions at 10 locations (100 μm square area×10 locations) on the matte article.

FIG. 2 is a cross-sectional view showing one embodiment of the matte article, taken along a plane parallel to its thickness direction (the Z direction in FIG. 2).
The shape of the recess may be, for example, an acute-angled shape as shown in FIG. 2a, a semicircular or semielliptical shape as shown in 2b, or a combination thereof. Alternatively, a shape such as 2c in FIG. 2, in which one convex portion partially has a concave portion, may be used.
On the other hand, as for the shape of the convex portion, as shown in 3a and 3b of FIG. 2, although the width varies, it exhibits a semicircular or semielliptical shape.

The thickness of the matte layer is not particularly limited as long as it can form the above-mentioned wrinkles to the extent that the visibility and texture of the matte effect can be expressed, but the ease of production etc. is also taken into consideration. Then, it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, still more preferably 4 μm or more, and even more preferably 5 μm or more, and the upper limit is preferably 300 μm or less, more preferably 200 μm or less, and still more preferably It is 150 μm or less, more preferably 100 μm or less.
In this specification, the thickness of the matte layer is the average value of the 20 thicknesses measured from the image of the cross section of the matte article taken using a scanning electron microscope (SEM). 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 thicknesses of other layers.

The matte layer may be partially provided or may be provided over the entire surface, but from the viewpoint of improving the visibility and texture of the matte effect, it is provided over the entire surface. is preferred.
When the matte layer is partially provided, the matte article of the present embodiment preferably has a base material described later as a layer other than the matte layer.

(Martens hardness)
In the matte article of the present embodiment, the matte layer should have a Martens hardness of 200 N/mm ² or less. If the Martens hardness exceeds 200 N/mm ² , it becomes difficult to form irregular wrinkles on the surface of the matte layer, and excellent visibility and texture of the matte effect cannot be obtained.
The lower the Martens hardness of the matte layer, the lower the 60° gloss value, preferably 190 N/mm ² or less, more preferably 180 N/mm ² or less, and even more preferably 175 N/mm ² . Below, more preferably 160 N/mm ² or less, particularly preferably 140 N/mm ² or less, and most preferably 50 N/mm ² or less. The lower limit is not particularly limited, but is usually 1 N/mm ² or more in consideration of the mechanical strength required for the matte layer and the properties of the resin itself constituting the matte layer. When the Martens hardness of the matte layer is within the above range, irregular wrinkles are likely to form on the surface of the matte layer, so that better visibility and texture of the matte effect can be obtained.

The method for adjusting the Martens hardness of the matte layer will be described later. etc. can be adjusted.

In this specification, Martens hardness is specifically a value measured using an ultra-micro hardness tester, and at room temperature (23 ° C.), a pyramid-shaped diamond indenter is sampled while the load is continuously increased. (the surface of the surface protective layer), the surface area A (mm ² ) was calculated from the length of the diagonal of the pyramid-shaped depression formed on the surface, and the test load F (N ) by the surface area A. As the ultra-micro hardness tester, for example, a micro-hardness tester "Picodenter HM-500" (manufactured by Fisher Instruments) may be used.

(wrinkle-forming stabilizer)
In the matte article of this embodiment, the matte layer may contain a wrinkle stabilizer. By setting the Martens hardness of the matte layer within a predetermined range, the formation of irregular wrinkles can be promoted and stabilized, so that excellent visibility and texture of the matte effect can be easily obtained. Further, as will be described later, the use of a wrinkle-forming stabilizer makes it easier to adjust the Martens hardness of the matte layer within the predetermined range.

As the wrinkle-forming stabilizer, as will be described later, organic particles, inorganic particles, etc. having a predetermined average particle size can be employed. The "matting agent" that has been used is the mechanism (action) of both matting, the structure for expressing matting, and the amount used, even if the constituent substances and the average particle size are the same. , differ in relation to the degree of surface luster (gloss value).

As described above, the "matting agent" itself exhibits a matting effect due to the light diffusion effect resulting from its physical shape.
On the other hand, the wrinkle-forming stabilizer does not express the visibility of the matte effect by light diffusion due to reflection and refraction of light rays by the particles themselves, but by setting the Martens hardness of the matte layer to a predetermined range. It stabilizes the formation of irregular wrinkles. That is, the wrinkle-forming stabilizer has the property of facilitating the adjustment of the Martens hardness of the matte layer within a predetermined range, and as a result promotes the formation of irregular wrinkles in the matte layer, further stabilizing the wrinkles. It can also be said that it has the performance of making it easy to obtain excellent visibility and texture of the matte effect.
Thus, when a wrinkle stabilizer is used in this embodiment, the wrinkle stabilizer is functionally different from a "matting agent."

In addition, regarding the difference between the "wrinkle-forming stabilizer" and the "matting agent", there is also a difference in the relationship between the content and surface luster (gloss value). The same substance A is used as a wrinkle-forming initiator AW (W: abbreviation for wrinkle), and when this is contained in a specific amount C to form wrinkles on the surface, the 60° gloss value G _60° ^AW ( C) is the 60 ° gloss value G of the surface when the same substance A is used as a simple matting agent AM (M: matte, abbreviation for matte), and wrinkles are not formed on the surface even when this is contained in the specific amount C Clearly lower than _60° ^AM (C). That is, the following relational expression holds.
G _60° ^AW (C) < G _60° ^AM (C)
This is because, in the matte article of the present embodiment, the visibility and texture of the matte effect expressed by stabilizing the formation of wrinkles is mainly due to the Martens hardness of the matte layer, and the wrinkle-forming stabilizer is It can be said that this is due to the fact that it is used to promote the formation of wrinkles and make them more stable.

The matting layer may contain an agent that has been conventionally used as a matting agent, but it is said that it is easy to obtain an extremely excellent matting effect visibility and texture that cannot be obtained even by using a matting agent. Considering the effect characteristics of the invention, it is preferable not to contain matting agents. As described above, the matte article has extremely excellent visibility and texture of the matte effect even if it does not substantially contain a matting agent that has been conventionally used to obtain the visibility of the matte effect. It can be said that there is. Therefore, when a matting agent is included (added), it is only to the extent that it reinforces the matting effect due to wrinkles on the surface of the matte layer. Here, "does not contain a matting agent" means not containing a matting agent at all, and even if it does contain a matting agent, it does not have the visibility of the matting effect based on the action and effect of the matting agent itself. Specifically, it means that the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, more preferably 3.0 parts by mass or less per 100 parts by mass of the resin. .
In the specification of the present application, the term "matting agent" is used specifically from the viewpoint of expressing the visibility of the matting effect due to the reflection of light rays corresponding to the contour shape of the particles and the light diffusion effect due to the refractive interface, as described above. Specifically, it means a layer in which the matting agent can be contained, that is, particles having an average particle size whose lower limit is more than 100% of the thickness of the matting layer or more than 30 μm, whichever is smaller.

The wrinkle-forming stabilizer, which is not a matting agent as described above, has an average particle size of 100% or less of the matte layer thickness or 30 μm or less, whichever is smaller. , inorganic particles, and the like.

As the wrinkle-forming stabilizer used in matte articles, particles that are not matting agents and have an average particle size of 100% or less of the thickness of the matte layer can be used without particular limitation. wrinkle-forming stabilizer 1 having a particle diameter of 1 μm or more and having an upper limit of 100% or less of the thickness of the matte layer or 30 μm or less, whichever is smaller; and wrinkle-forming stabilizer 2 having an average particle diameter of less than 1 μm. It is preferable to use In this embodiment, as the wrinkle-forming stabilizer, one or more wrinkle-forming stabilizers 1 may be used, one or more wrinkle-forming stabilizers 2 may be used, or one or more wrinkle-forming stabilizers 2 may be used. The wrinkle-forming stabilizer 1 and one or more wrinkle-forming stabilizers 2 may be used in combination.

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

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

The average particle size of the wrinkle-forming stabilizer is selected from the viewpoint of ease of adjustment of the Martens hardness of the matte layer, and also promotes and stabilizes the formation of wrinkles to obtain excellent visibility and texture of the matte effect. From the viewpoint of making it easier to wear, the upper limit of the thickness of the matte layer 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 still more preferably is 70% or less of the thickness of the matte layer, and the absolute value is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 8 μm or less, and even more preferably 7 μm or less. Any combination of the upper limit for the height and the upper limit for the absolute value may be set to the smaller one. For example, the upper limit may be 90% or less of the matte layer thickness or 20 μm or less, whichever is smaller, or the smaller one of 90% or less and 10 μm or less of the matte layer thickness may be the upper limit. can also The thickness of the matte layer will be described later. The lower limit is preferably 1 nm or more, more preferably 3 nm or more, and still more preferably 5 nm or more.

As described above, when wrinkle-forming stabilizers 1 and 2 are used separately, the average particle size of wrinkle-forming stabilizer 1 is adjusted from the viewpoint of ease of adjustment of the Martens hardness of the matte layer and promotes the formation of wrinkles. However, from the viewpoint of making it more stable and easily obtaining excellent visibility and texture of the matte effect, it is preferably 1.3 μm or more, more preferably 1.5 μm or more, and still more preferably 1.8 μm or more, The upper limit is as described above.
From the same point of view, the average particle size of the wrinkle-forming stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, still more preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm. 500 nm or less, more preferably 500 nm or less.
In the present specification, the average particle size of the wrinkle-forming stabilizer is measured as the mass average value d50 in particle size distribution measurement by laser light diffraction method.

The content of the wrinkle-forming stabilizer, and when wrinkle-forming stabilizers 1 and 2 are used together, the total content of these is 0.5 per 100 parts by mass of the resin forming the matte layer. It is preferably at least 6.0 parts by mass. Within the above range, it is easy to adjust the Martens hardness of the matte layer, and the effect of using the wrinkle-forming stabilizer, ie, the formation of wrinkles, is promoted, and the visibility and texture of the matte effect can be easily obtained.

From the viewpoint of ease of adjustment of the Martens hardness of the matte layer, and from the viewpoint of promoting the formation of wrinkles by the wrinkle-forming stabilizer and making it easier to obtain excellent visibility and texture of the matting effect, wrinkle-formation stabilization The total content of agent 1 and wrinkle-forming stabilizer 2 is preferably 0.75 parts by mass or more, more preferably 1.0 parts by mass or more, and still more preferably 100 parts by mass of the resin forming the matte layer. is 1.2 parts by mass or more, and the upper limit is not particularly limited as long as it is 6.0 parts by mass or less from the viewpoint of easily obtaining excellent visibility of the matting effect.

The content of each of the wrinkle-forming stabilizer 1 and the wrinkle-forming stabilizer 2 is not particularly limited as long as the total content is within the above range, but the content of the wrinkle-forming stabilizer 2 is 100 mass of the resin. parts, preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, and the upper limit is 6.0 parts by mass or less, preferably 5 parts by mass. 0 parts by mass or less, more preferably 3.5 parts by mass or less, and even more preferably 3.0 parts by mass or less. Further, the mixing ratio of wrinkle-forming stabilizer 1 and wrinkle-forming stabilizer 2 (wrinkle-forming stabilizer 1/wrinkle-forming stabilizer 2) is preferably 0.05 to 0.95, more preferably 0.10 to 0.90, more preferably 0.20 to 0.80, still more preferably 0.30 to 0.70.

Organic particles and inorganic particles can be used as the wrinkle-forming stabilizer as described above, and it can be said that the types of these particles themselves include those conventionally used as matting agents. For example, matting agents such as spherical alumina and calcium carbonate are used in the mat layer of the decorative sheet described in Patent Document 1 above. In order for matting agents such as spherical alumina and calcium carbonate to express the visibility of the matting effect themselves due to the light diffusion effect resulting from their physical shape, as described in Patent Document 1, It is necessary to use 10 parts by weight of spherical alumina and 40 parts by weight of calcium carbonate in a total amount of about 50 parts by weight per 100 parts by weight of resin. However, in the matte article, as described above, even a small content is necessary for expressing the visibility and texture of the matte effect itself due to the light diffusion effect caused by the physical shape. Even if the content is less than the above content, the visibility and texture of the matting effect are extremely excellent compared to the effect obtained by the matting agent.
Therefore, even though the matte article does not substantially contain a matting agent, the martens hardness of the matte layer is set within a predetermined range to form wrinkles on the surface. By promoting the formation of wrinkles on the surface using the stabilizer, it can be said that the visibility and texture of the matting effect are more excellent than when the matting agent is used.

Further, by setting the Martens hardness of the matte layer within a predetermined range, obtaining the visibility and texture of the matte effect has the following merits in terms of improving the surface characteristics.
In general, when the surface of a resin layer containing particles such as "matting agent" comes into contact with another object and is rubbed, the particles in the vicinity of the surface tend to come off. Therefore, if the specifications are such that the luster of the layer surface is reduced solely by the addition of a "matting agent", the detachment of such particles will cause a change in luster upon contact or friction with other objects. The change in luster due to such a mechanism becomes more pronounced in low-gloss specifications with a higher content of matting agent. In particular, when a surface with a ₆₀ ° gloss value G60 of 5.0 or less is achieved by adding a "matting agent", 100 parts by mass of the resin (regardless of the dispersion form of the resin and the type of matting agent) Although it depends on the circumstances, it is necessary to add about 50 parts by mass or more, and the gloss change due to the detachment of the matting agent during contact with other objects or rubbing becomes large.
In the matte layer of the matte article of the present embodiment, as demonstrated in the examples and comparative examples described later, when a surface with a 60° gloss value G ₆₀ of 5.0 or less is realized by adding a matte agent However, the content of the wrinkle-forming stabilizer with respect to 100 parts by mass of the resin is only about 3.0 parts by mass. For example, in the examples of the present invention, the total content of the wrinkle-forming stabilizer is up to 3 parts by mass, and the ₆₀ ° gloss value G60 is 5.0 or less, and further 3.7 or less. . As will be described later, in this specification, a 60° gloss value of 5.0 or less is treated as "matte".
Therefore, in the matte article, as demonstrated in Examples and Comparative Examples described later, when realizing the same low gloss surface, the 60 ° gloss value G ₆₀ is 10 or less, and further 5.0 or less. In this case, since the particle content is greatly reduced compared to conventional matte articles, there is little change in luster due to detachment of the matting agent during contact with other objects or rubbing.

(resin)
As the resin for forming the matte layer, any resin may be used as long as it is a resin that forms a cured product by curing and can set the Martens hardness of the matte layer within the above-described predetermined range.
Such resins include ionizing radiation-curable resins. Since the matte layer is a layer that can be provided on the outermost surface of the matte article, it is a resin that easily forms wrinkles. , surface properties such as weather resistance, and processing properties are preferred, and ionizing radiation-curable resins are preferred resins from these points of view. In particular, an ionizing radiation curable resin such as a monomer or oligomer described later is selected as the resin constituting the matte layer, and irradiated with ultraviolet rays having a short wavelength of 100 nm or more and less than 200 nm, which will be described later. When a manufacturing method for forming a shape is employed, the matte article of the present embodiment, for example, even when using particles such as the wrinkle-forming stabilizer described above, uses an extremely small amount of the particles. As a surface characteristic, the performance of the resin forming the matte layer is more directly exhibited.

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 cross-linked and cured by irradiation with ionizing radiation. A functional group having an ethylenic double bond such as an allyl group is preferred. In addition, in this specification, a (meth)acryloyl group shows an acryloyl group or a methacryloyl group. Moreover, in this specification, (meth)acrylate indicates acrylate or methacrylate.
In addition, ionizing radiation means, among electromagnetic waves or charged particle beams, those having energy quanta capable of polymerizing and/or cross-linking molecules, and usually ultraviolet rays (UV) or electron beams (EB) are used, In addition, electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams are also included.

Examples of ionizing radiation curable resins include electron beam curable resins and ultraviolet curable resins, from the viewpoint of ease of adjustment of the Martens hardness of the matte layer, stabilizing the formation of wrinkles, and improving the matting effect. From the viewpoint of improving visibility and texture, an ultraviolet curable resin is preferred.
Specifically, the ionizing radiation-curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation-curable resins. It is preferable to use

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferred. Here, "(meth)acrylate" means "acrylate or methacrylate".
The (meth)acrylate-based monomer is a monomer having at least a (meth)acryloyl group as an ionizing radiation-curable functional group, and is a monofunctional (meth)acrylate monomer having one ionizing radiation-curable resin, or a polyfunctional monomer having two or more ionizing radiation-curable resins. (Meth)acrylate monomers can be mentioned, and any can be used.

The polymerizable monomer can be used alone or in combination of multiple types, from the viewpoint of ease of adjustment of the Martens hardness of the matte layer, and promotes the formation of wrinkles, resulting in excellent visibility of the matte effect. It is preferable to use two or more kinds of polymerizable monomers in combination from the viewpoint of easily obtaining texture and surface properties such as scratch resistance and weather resistance, and from the viewpoint of improving processability.

When two or more polymerizable monomers are used in combination, a combination of a monofunctional monomer and a polyfunctional monomer, a combination of two or more polyfunctional monomers is preferable, and a combination of a polyfunctional monomer and a polyfunctional monomer is more preferable.
When using a polyfunctional monomer, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less.

When a monofunctional monomer and a polyfunctional monomer are used in combination, the upper limit of the number of functional groups of the polyfunctional monomer is most preferably 2 or less. Moreover, in this case, the monofunctional monomer and the polyfunctional monomer are preferably (meth)acrylate monomers.
Moreover, when using two or more kinds of polyfunctional monomers, it is most preferable to combine a monomer having two functional groups and a monomer having four functional groups. Moreover, in this case, the monofunctional monomer and the polyfunctional monomer are preferably (meth)acrylate monomers.

Polymerizable oligomers include, for example, (meth)acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and at least (meth)acryloyl groups 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, and acrylic (meth)acrylate oligomers.

Furthermore, as polymerizable oligomers, there are also highly hydrophobic polybutadiene (meth)acrylate oligomers having (meth)acrylate groups in the side chains of polybutadiene oligomers, and silicone (meth)acrylate oligomers having polysiloxane bonds in the main chain. , aminoplast resins modified with aminoplast resins having many reactive groups in small molecules (meth)acrylate oligomers, novolac type epoxy resins, bisphenol type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers having cationic polymerizable functional groups.

From the viewpoint of ease of adjustment of the Martens hardness of the matte layer, from the viewpoint of promoting the formation of wrinkles to make it easier to obtain excellent visibility and texture of the matte effect, and the surface such as scratch resistance and weather resistance From the viewpoint of improving properties and processing properties, urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, ) acrylate oligomers are preferred, urethane (meth)acrylate oligomers and polycarbonate (meth)acrylate oligomers are more preferred, and urethane (meth)acrylate oligomers are even more preferred.

These polymerizable oligomers may be used alone or in combination of multiple types, from the viewpoint of ease of adjustment of the Martens hardness of the matte layer, promotes the formation of wrinkles, and has an excellent matte effect. It is preferable to use one type of polymerizable oligomer alone from the viewpoint of making it easier to obtain visibility and texture, and from the viewpoint of improving surface properties such as scratch resistance and weather resistance, and processing properties. It goes without saying that a combination of the organic oligomers may also be used.

The number of functional groups of the polymerizable oligomer is selected from the viewpoints of facilitating adjustment of the Martens hardness of the matte layer, promoting the formation of wrinkles, making it easier to obtain excellent visibility and texture of the matting effect, and further improving the durability. From the viewpoint of improving surface properties such as scratch resistance and weather resistance and processing properties, it is preferably 2 or more, more preferably 3 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, and still more preferably 4 or less. is.

From the same point of view, the weight average molecular weight of these polymerizable oligomers is preferably 1,000 or more and 7,500 or less, more preferably 1,500 or more and 6,500 or less, and 1,750 or more and 5,000. The following are more preferable, and 1,900 or more and 4,000 or less are even more preferable. Here, the weight average molecular weight is the average molecular weight measured by GPC analysis and converted with standard polystyrene.

In the matte article, the resin forming the matte layer preferably contains at least one selected from the above polymerizable monomers and polymerizable oligomers. In this case, the content of the polymerizable monomer or polymerizable oligomer in the resin forming the matte layer is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly It is preferably 100% by mass, that is, the resin is at least one selected from polymerizable monomers and polymerizable oligomers.

The resin that forms the matte layer preferably contains at least one selected from the above polymerizable monomers and polymerizable oligomers, more preferably contains a polymerizable monomer and a polymerizable oligomer, as described above. and polymerizable oligomers, more preferably at least one selected from polymerizable monomers and polymerizable oligomers. It facilitates adjustment of the Martens hardness of the matte layer, promotes the formation of wrinkles, and makes it easier to obtain excellent visibility and texture of the matte effect.
When a polymerizable monomer and a polymerizable oligomer are employed, the content of the polymerizable oligomer with respect to a total of 100 parts by mass of the polymerizable monomer and the polymerizable oligomer is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further It is preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and the upper limit is preferably 45 parts by mass or less, more preferably 40 parts by mass or less, and even more preferably 35 parts by mass or less. When the content of the polymerizable oligomer is within the above range, it is easy to adjust the Martens hardness of the matte layer, promote the formation of wrinkles, and make it easy to obtain excellent visibility and texture of the matte effect. It can also improve surface properties such as scratch resistance and weather resistance, and processing properties.

Considering that the resin that forms the matte layer facilitates the adjustment of the Martens hardness of the matte layer, promotes the formation of wrinkles, and makes it easier to obtain excellent visibility and texture of the matte effect. It preferably contains at least one selected from a polyfunctional monomer and a polyfunctional oligomer, and more preferably contains a polyfunctional monomer and a polyfunctional oligomer.
Also, from the same point of view, the resin that forms the matte layer preferably contains a monofunctional monomer, a polyfunctional monomer and a polyfunctional oligomer, and is a monofunctional monomer, a polyfunctional monomer and a polyfunctional oligomer, i.e. It is preferable to use a monofunctional monomer, a polyfunctional monomer and a polyfunctional oligomer together.

Considering the ease of adjusting the Martens hardness of the matte layer and promoting the formation of wrinkles to make it easier to obtain excellent visibility and texture of the matte effect, it is preferable to use a bifunctional monomer. In this case, the content of the bifunctional monomer is preferably 15 parts by mass or more with respect to 100 parts by mass of the resin, and the upper limit is preferably 50 parts by mass or less, more preferably 35 parts by mass or less.
From the same point of view, it is also preferable to use a monofunctional monomer. In this case, the content of the monofunctional monomer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and still more preferably 35 parts by mass or more with respect to 100 parts by mass of the resin, and the upper limit is preferably 60 parts by mass. Below, more preferably 50 parts by mass or less, still more preferably 45 parts by mass or less.

(resin composition)
The matte layer is composed of a cured resin composition containing the above resin. The resin composition used in the present embodiment may contain other components in addition to the resins described above and optionally a wrinkle-forming stabilizer, depending on desired performance and the like.

The resin composition for forming the matte layer may contain a monofunctional (meth)acrylate that can also be used as the above resin for the purpose of reducing its viscosity, for example. Monofunctional (meth)acrylates may be used alone or in combination. If the resin contains a monofunctional monomer such as a monofunctional (meth)acrylate, the monofunctional monomer functions as a resin and contributes to viscosity reduction. No need.

When the resin is an ultraviolet-curable resin that is cured by ultraviolet rays, it preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. The inclusion of these additives promotes the formation of wrinkles, making it easier to obtain excellent visibility and texture of the matte effect.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler's ketone, benzoin, benzyldimethylketal, benzoylbenzoate, α-acyloxime ester, thioxanthones, and the like.
In addition, the photopolymerization accelerator can reduce polymerization inhibition by air during curing and increase the curing speed. One or more selected types can be mentioned.

Since the matte layer is a layer that can be provided on the outermost surface of the matte article, it is preferably a layer having weather resistance, and preferably contains various weather resistance agents such as ultraviolet absorbers and light stabilizers.
As the UV absorber, any UV absorber that is commonly used for decorative sheets can be used without particular limitation, such as benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, and hydroxyphenyltriazine UV absorbers. agents and the like. As the light stabilizer, any light stabilizer commonly used for decorative sheets can be used without particular limitation, and examples thereof include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers. Moreover, these ultraviolet absorbers and light stabilizers may have a reactive functional group having an ethylenic double bond such as a (meth)acryloyl group, vinyl group or allyl group in the molecule.
Weather resistance agents such as these ultraviolet absorbers and light stabilizers can be used alone or in combination.

[60° gross value]
A matte article is an article having excellent matte effect visibility and texture, and has a 60° gloss value of 5.0 or less. In the present specification, "matte" means that the gloss is difficult to see, and it cannot be said unconditionally because it varies depending on the color tone, pattern, etc. of the article. shall be treated as matte.
Until now, for example, black or other dark colors ("dark colors" means low brightness, for example, CIE (Commission Internationale de l'Eclairage) L ^* a ^* b ^* L in the color system measured in accordance with JIS Z8781-4:2013 ^* value (hereinafter sometimes simply referred to as “L ^* value”) means that it is usually about 40 or less, preferably 30 or less. Although it is possible to obtain an excellent visibility of the matting effect with a 60° gloss value of 20.0 or less, preferably 10.0 or less, since a large amount of matting agent is used, streaks during layer formation may occur. However, since unevenness occurs, it is not easy to manufacture, and the surface characteristics are degraded. In addition, for example, matte articles exhibiting a color tone other than black or other dark colors have a lower limit to the 60° gloss value even if a matting agent is used, and are the same as black matte articles. It has not been possible to easily obtain an article having excellent properties and excellent visibility of the matte effect. Such a tendency becomes more remarkable as the 60° gloss value becomes smaller.

In the matte article, by setting the Martens hardness of the matte layer within the above-mentioned predetermined range, and optionally using a wrinkle-forming stabilizer and reducing the content thereof to a small amount as described above, Wrinkles are formed, and the wrinkles provide excellent visibility and texture of the matte effect. When a wrinkle-forming stabilizer is used, it is possible to suppress a significant increase in the viscosity of the resin composition by suppressing the amount of the wrinkle-forming stabilizer to an extremely small amount, thereby facilitating the formation of the matte layer. It naturally has surface properties such as excellent scratch resistance, stain resistance, weather resistance, etc., depending on the properties.

Although the matte article changes depending on the color tone as described above, the 60° gloss value on the matte layer side is 5.0 or less, further 4.0 or less, 3.6 or less, 3.2 or less, 2.5 or less, which is capable of exhibiting extremely excellent visibility of the matte effect.
Also, a matte article exhibiting a color tone other than black or other dark colors can have the above 60° gloss value. The 60° gloss value of the matte layer side of the matte article is substantially the same as the 60° gloss value of the surface of the layer forming the outermost surface of the article. Further, when there is another layer and the other layer is provided on the surface side from the matte layer, the 60 ° gloss value means the 60 ° gloss value of the other layer. The particular 60° gloss value of the erasable article is due substantially to the composition of the matte layer.
In this specification, the 60° gloss value on the matte layer side is the 60° specular gloss measured in accordance with JIS K 5600-4-7: 1999, and a gloss meter or the like is measured at any 10 points. is the average value of the values that can be measured from the matte layer side using

[Regarding layer structure]
The matte article does not need to have a substrate as long as it has a matte layer with a specific Martens hardness as described above. That is, the matte article has a substrate as desired, and may have a layered structure without a substrate. Therefore, the simplest layer structure of the matte article is a single layer structure of only the matte layer without a substrate, specifically, the surface has an uneven shape due to irregular wrinkles with Martens hardness. , which is composed of a cured product of a resin composition and has a layer structure of a single layer consisting of only a matte layer having a Martens hardness of 200 N/mm ² or less.

(More realistic layer structure)
However, when the matte article has a layer structure of the above single layer, the options for obtaining various performances required for the matte article, such as mechanical strength, post-processing suitability, and design properties, are often limited. . Therefore, the layer structure of the matte article preferably has a base material, that is, a layer structure having a base material and a matte layer. In this case, as shown in FIGS. 3 and 4, the substrate and the matte layer are provided, and the surface having an uneven shape formed by irregular wrinkles of the matte layer is on the opposite side of the substrate. A surface is preferred. This is because the visibility and texture of the matte effect can be improved.

〔Base material〕
The matte article may optionally have a substrate in addition to the matte layer, and as described above, preferably has a substrate from the viewpoint of avoiding various restrictions. The substrate functions as a support on which the matte layer is provided.
The form (or shape) of the base material is not particularly limited and may be various shapes such as film, sheet, plate, polyhedron, polygonal prism, cylinder, cone, spherical surface, and spheroidal surface. Films, sheets, and plates are referred to in order of relatively thin thickness. The three kinds of differences do not cause any difference in the interpretation of the rights of the present invention.

As the base material used in the present embodiment, those commonly used as base materials for articles such as decorative materials and decorative sheets can be employed without limitation. Substrates composed of resins, woody materials, metals, non-metallic inorganic materials, and the like are typical examples.
The substrate may be a single layer, or may be a laminate of two or more layers made of the above materials. When the substrate is a laminate of two or more layers, it is preferable to laminate two or more layers of different materials so that the properties of the materials of each layer complement each other. Examples of the substrate formed by laminating two or more layers include the following A to J. In addition, "/" indicates the interface of each layer.
(A) Resin/Wood material (B) Resin/Metal (C) Resin/Fibrous material (D) Resin/Nonmetallic inorganic material (E) Resin 1/Resin 2
(F) Metals/Wood based materials (G) Metals/Non-metallic inorganic materials (H) Metals/Fibrous materials (I) Metal 1/Metal 2
(J) Nonmetallic Inorganic Material/Fibrous Material In E above, Resin 1 and Resin 2 indicate different types of resin (for example, Resin 1 is an olefin resin and Resin 2 is an acrylic resin). In H above, metal 1 and metal 2 indicate different metals (for example, metal 1 is copper and metal 2 is chromium).

In addition, when the base material is a laminate, an adhesive layer, a pressure-sensitive adhesive layer, a primer layer (anchor layer, a primer layer, etc.) may be added between the constituent layers of the laminate as layers for strengthening the adhesive strength between adjacent layers. Also called an adhesive layer) may be further provided.

Examples of base materials for fibrous materials include kraft paper, titanium paper, linter paper, sulfuric acid paper, paraffin paper, glassine paper, parchment paper, wallpaper lining paper, thin paper, fine paper, Japanese paper, cardboard, base paper for gypsum board, and the like. paper base material. For the paper substrate, acrylic resin, styrene-butadiene rubber, melamine resin, and urethane resin are used in order to improve the interlaminar strength between the fibers or the multi-layered paper substrate and to prevent fluffing. (impregnated with resin after papermaking, or filled in during papermaking). Examples of such a paper substrate include inter-paper reinforced paper and resin-impregnated paper. In addition, as a base material in which a resin layer is laminated on a fibrous material layer, various resin layers such as a vinyl chloride resin layer, an olefin resin layer, and an acrylic resin layer are laminated on the surface of wallpaper backing paper that is widely used in the field of building materials. The wallpaper original fabric etc. which carried out are also mentioned.

Non-woven fabric or woven fabric substrates include inorganic fibers made of inorganic materials such as glass, alumina, silica, and carbon; organic fibers made of various synthetic resins such as polyester resins, acrylic resins, polyethylene, and polypropylene; Base materials such as non-woven fabrics or woven fabrics composed of various fibers such as protein-based or cellulose-based natural fibers such as silk, cotton and hemp, glass fibers and carbon fibers, and composites thereof.

Examples of resin substrates include substrates composed of various resins such as synthetic resins and natural resins. A thermoplastic resin and a curable resin can be used as the synthetic resin.
Examples of thermoplastic resins include polyolefin resins such as polypropylene, polyethylene, polymethylpentene, polyolefin thermoplastic elastomers, and ionomers; vinyl chloride resins such as polyvinyl chloride, polyvinylidene chloride, and vinyl chloride-vinyl acetate copolymers; Polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), ethylene glycol-terephthalic acid-isophthalic acid copolymer, polyester thermoplastic elastomer; polymethyl (meth) acrylate, polybutyl ( acrylic resins such as meth)acrylate and methyl (meth)acrylate-butyl (meth)acrylate copolymer; polyamide resins such as nylon 6 and nylon 66; cellulose-based resins such as cellulose triacetate, cellophane and celluloid; polystyrene , acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene resin (ABS resin); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, polyarylate resin, A resin substrate made of a thermoplastic resin such as a polyimide resin can be used.
Examples of the curable resin include ionizing radiation curable resins capable of constituting the above matte layer and other thermosetting resins.
Natural resins include natural rubber, pine resin, amber, and the like.

Examples of the base material of the wood-based material include wood base materials made of wood of various tree species such as cedar, cypress, pine, zelkova, oak, oak, walnut, lauan, teak, and rubber tree. The wood substrate may be in the form of a film or sheet called veneer, or in the form of a plate such as veneer, plywood, laminated wood, particle board, or fiberboard.

Metals include alloys containing aluminum such as aluminum and duralumin; alloys containing iron such as iron, carbon steel and stainless steel; alloys containing copper such as copper, brass and bronze; gold, silver, chromium, nickel, cobalt; Tin, titanium and the like can be mentioned. In addition, as the metal substrate composed of metal, those metals subjected to a treatment such as plating can also be used.
In addition, non-metallic inorganic materials include non-ceramic ceramic materials such as cement, ALC (light cellular concrete), gypsum, calcium silicate, and wood chip cement; ceramic ceramic materials such as ceramics, earthenware, glass, and enamel; (including marble), natural stones such as granite and andesite.

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

When the substrate is colored, examples of coloring agents include white pigments such as titanium white, inorganic pigments such as iron black, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. , isoindolinone yellow, phthalocyanine blue, nickel-azo complexes, azomethine azo black pigments, perylene black pigments, and other organic pigments or dyes; metal pigments made of scale-like foil pieces such as aluminum and brass; titanium dioxide-coated mica, bases coloring agents such as pearl luster (pearl) pigments composed of scaly foil pieces such as organic lead carbonate. For example, when the surface hue of the adherend to which the article is adhered varies, it is desired to conceal the surface hue and improve the stability of the color tone of the pattern layer and the large-area decorative layer provided as desired. , an inorganic pigment such as a white pigment may be used.

In the case of coloring a synthetic resin, any means such as adding (kneading or kneading) a coloring agent into the resin, forming a coating film of a paint containing a resin and a coloring agent, or the like can be adopted. . In the case of coloring paper, non-woven fabric or woven fabric, it can be carried out by any means such as mixing with pulp or fiber material, coating film formation, or a combination thereof.
In the case of coloring of wood, it can be carried out by dyeing with a dye, by forming a coating film, or by a combination thereof. In the case of metal coloring, in addition to coating film formation, an electrolytic coloring method or the like can be employed in which a metal oxide film is formed on the surface using an anodic oxidation method. In the case of a non-metallic inorganic material, it can be carried out by forming a coating film, by adding it to the substrate, or by combining these methods.

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

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

The shape and dimensions of the base material are not particularly limited, and may be appropriately selected according to the application, desired properties, and processability.
When the substrate is in the form of a film, sheet, or plate, thickness is a representative design dimension of the article. Although there is no particular limitation on the thickness, it is generally about 10 μm or more and 10 cm or less from the viewpoint of manufacturing processability, mechanical strength, ease of use and economy. In the case of a film or sheet, the thickness is preferably 20 µm or more, more preferably 40 µm or more, and the upper limit is preferably 300 µm or less, more preferably 200 µm or less, and even more preferably 100 µm or less.
When the substrate is in the form of a plate, its thickness is preferably 1 mm or more and 2 cm or less.
When the substrate is a paper substrate, the basis weight is usually preferably 20-150 g/m ² , more preferably 30-100 g/m ² .

In order to improve the adhesion with other layers that make up the article and the adherend on which the article is laminated, the substrate is subjected to a physical surface treatment such as an oxidation method, a roughening method, or a chemical treatment on one or both sides. Surface treatment such as surface treatment may be applied, or a primer layer may be formed.
Examples of oxidation methods include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment, and the like. Examples of roughening methods include sandblasting and solvent treatment. These surface treatments are appropriately selected according to the type of substrate, but generally corona discharge treatment is preferred from the viewpoint of surface treatment effects, operability, and the like.

[Other layers]
In addition to the matte layer, the matte article may have the base material described above and other layers such as a primer layer, a transparent resin layer, a decorative layer, and an adhesive layer, if necessary. Cross-sectional views showing one embodiment of a matte article having these layers are shown in FIGS. 3 and 4 are cross-sectional views showing one embodiment of the matte article, and the cross section of the matte article 1 (matte article) cut along a plane parallel to its thickness direction (the Z direction in the figure). It is a diagram.
The matte article 1 (matte article) shown in FIG. 3 has a substrate 5 and a matte layer 4 in that order. , a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9 and a matte layer 4 in this order.

(primer layer)
When the matte article is composed of a plurality of layers, for example, it may have a primer layer in order to improve the interlayer adhesion of the plurality of layers as described above.
When the matte article has a layer other than the matte layer, for example, when it has a matte layer and a substrate, a primer layer is provided between the matte layer and the substrate to improve interlayer adhesion. can be done.

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

Binder resins include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, and polycarbonate-based urethane-acrylic copolymers (carbonate bonds in the polymer main chain). urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having two or more hydroxyl groups at the end and side chain), vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl acetate-acrylic copolymer Resins such as coalescent resins, chlorinated propylene resins, nitrocellulose resins (nitrocellulose), and cellulose acetate resins are preferred, and these can be used alone or in combination.
The binder resin may be obtained by adding a curing agent such as an isocyanate-based curing agent or an epoxy-based curing agent to these resins, followed by cross-linking and curing. Among these, a polyol resin such as an acrylic polyol resin is preferably crosslinked and cured with an isocyanate curing agent, and more preferably an acrylic polyol resin is crosslinked and cured with an isocyanate curing agent.

The thickness of the primer layer is preferably 0.5 μm or more and 10 μm or less, more preferably 1 μm or more and 8 μm or less, and even more preferably 2 μm or more and 6 μm or less.

The matte article has at least one wrinkled surface of the matte layer for the purpose of improving adhesion to the adherend, and if it has a substrate, the matte of the substrate A primer layer (also referred to as a "back primer layer") may be provided on the side opposite to the side on which the layer is provided.

(Transparent resin layer)
The matte article may have a transparent resin layer in order to increase its strength, and from the viewpoint of protecting the decorative layer when it has a decorative layer, which will be described later. In particular, it is effective when the matte article is used as a floor material, or as a fitting member such as a window frame, a door, a door frame, and a handrail, which are frequently used.
The transparent resin layer may be provided between the base material and the matte layer, and when a decorative layer is provided, it is provided between the decorative layer and the matte layer in order to protect the decorative layer. Just do it.

Examples of resins constituting the transparent resin layer include polyolefin resins, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as "ABS resins"), acrylic resins, vinyl chloride resins, and the like. Among these, polyolefin-based resins and vinyl chloride resins are preferred from the viewpoint of workability and the like. Also, two or more of these various resins may be laminated or mixed for use.

The transparent resin layer may be transparent to the extent that the base material side of the transparent resin layer is visible, and if it has a decorative layer, it may be transparent to the extent that the decorative layer can be visually recognized. In addition, it may be colored, transparent, or translucent. That is, in the present specification, "transparency" means colorless transparency, as well as colored transparency and semi-transparency.

The transparent resin layer may contain additives such as UV absorbers, light stabilizers and other weather resistance agents, and colorants and the like. As the additives such as the weather resistance agent and the colorant, those described above may be used.
The thickness of the transparent resin layer is preferably 20 μm or more and 150 μm or less, more preferably 40 μm or more and 120 μm or less, and even more preferably 60 μm or more and 100 μm or less, from the standpoint of protecting the decorative layer and considering workability.

(decorative layer)
The matte article may have a decorative layer from the viewpoint of improving the design. The decorative layer may be provided on the surface opposite to at least one wrinkled surface of the matte layer. If they are provided, the decoration layer, the transparent resin layer and the matte layer may be provided in this order.

The decorative layer may be, for example, a colored layer covering the entire surface (so-called solid colored layer, "6a" in FIG. 4), or may be formed by printing various patterns using ink and a printing machine. It may be a pattern layer (“6b” in FIG. 4) that is to be printed. Further, as shown in FIG. 4, a solid colored layer and a pattern layer may be combined.

The pattern (pattern) of the pattern layer is not particularly limited, and any desired pattern may be adopted. Examples include texture patterns on the surface of fabric, grain patterns on the surface of leather, geometric patterns, characters, figures, and combinations thereof.

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

As the colorant, a pigment having excellent hiding properties and weather resistance is preferred. Pigments similar to those exemplified as pigments that can be used in the substrate can be used.
The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the resin constituting the decorative layer. More preferred are:

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

(adhesion layer)
When the matte article has a transparent resin layer, an adhesive layer may be provided between the substrate and the transparent resin layer to improve 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 a transparent resin layer in this order, or an adhesive layer, a decoration layer, and a transparent resin layer in this order from the side closer to the substrate.

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

The thickness of the adhesive layer is preferably 0.1 μm or more and 30 μm or less, more preferably 1 μm or more and 15 μm or less, and even more preferably 2 μm or more and 10 μm or less, from the viewpoint of efficiently obtaining a desired adhesive strength.

[Method for producing matte article]
As described above, the matte article may have a layer structure with a single matte layer, or may have a layer structure including at least a substrate. In the following, the method of manufacturing the matte article will be described separately for the case of a single layer and the case of having a substrate and other layers.

First, in the case of a single layer, a matte article can be produced by the following method.
The resin composition for forming a matte layer, that is, the resin composition containing the above resin, a wrinkle-forming stabilizer used as necessary, and other additives is applied to the release layer-bearing surface of the release support. A step of coating to form a coating layer, preferably a matte layer forming step of forming a matte layer by irradiating it with ionizing radiation such as ultraviolet light having a low wavelength (short wavelength) of at least 100 nm or more and less than 200 nm to cure it. It is preferable to manufacture through. Moreover, when the resin composition contains a solvent, a solvent drying step may be performed after the step of forming the coating layer.
A release support having a release layer may be peeled off when the matte article is used.

Next, when having a base material and other layers, a matte article can be produced by the following method.
The matte article is, for example, a resin composition containing the matte layer-forming resin composition, that is, the resin, the wrinkle-forming stabilizer used as necessary, and other additives on one main surface side of the base material. A step of applying a substance to form a coating layer, preferably at least 100 nm or more and less than 200 nm. It is preferable to manufacture through a matte layer forming step. Moreover, when the resin composition contains a solvent, a solvent drying step may be performed after the step of forming the coating layer.

The method for producing a matte article can be particularly suitable for producing a matte article having a 60° gloss value of 5.0 or less on the matte layer side. Among them, the method for producing a matte article is particularly characterized by suppressing the addition amount of μm-order particles to a low content of 15 parts by mass or less with respect to 100 parts by mass of the resin, and achieving a 60° gloss value of 5.0 or less. In that a matte (low-gloss, low-gloss) surface can be achieved, the method is distinct from conventional methods for producing matte articles such as matte decorative materials and matte decorative sheets.

Such a manufacturing method makes it possible to easily obtain a matte article. When manufacturing a matte article in which the matte layer has a 60° gloss value of 5.0 or less, in forming the matte layer, as described above, preferably a low wavelength (short wavelength) of at least 100 nm or more and less than 200 nm Ultraviolet rays are applied to a resin composition for forming a matte layer containing a wrinkle-forming stabilizer. This makes it easier to form wrinkles on at least one surface of the matte layer, and makes it easier to provide the matte article (matte layer) with excellent visibility and texture of the matte effect.

When the resin composition for forming the matte layer is irradiated with such low-wavelength (short-wavelength) ultraviolet rays, wrinkles are formed on at least one surface of the matte layer, and the visibility and texture of the matte effect are expressed. Although the details of the mechanism that makes it easier to do so are unknown, it is presumed to be due to the following mechanism.

When a coated article coated with a resin composition for forming a matte layer with a predetermined thickness is irradiated with ultraviolet rays of a low wavelength (short wavelength), the energy of the ultraviolet rays penetrates only the surface portion, and the energy is transferred to the lower layer. It is thought that only the surface portion of the resin composition begins to cure due to the fact that the surface does not reach, and wrinkles are formed by curing shrinkage occurring only on the surface. Thus, the formation of wrinkles is considered to occur in a state in which only a certain thickness direction from the surface of the resin composition for forming the matte layer is cured by irradiation with ultraviolet light having a low wavelength (short wavelength). .

From the comparison of the examples and comparative examples described later, when the Martens hardness is greater than 200 N / mm ² , the visibility and texture of the matte effect due to the formation of wrinkles are not obtained. The visibility and texture of the matte effect cannot be explained only by the curing of only the surface portion by low-wavelength (short-wavelength) ultraviolet rays. That is, in order for the matte article to exhibit the visibility of the matte effect by having wrinkles, it is essential that the Martens hardness is 200 N/mm ² or less. In addition, considering that when the Martens hardness is greater than 200 N/mm ² , excellent visibility of the matting effect is not obtained due to the formation of wrinkles, the wrinkle-forming stabilizer has a Martens hardness of 200 N/mm ² or less. In the case of , it expresses a function like a nucleus that triggers the formation of wrinkles, and around the nucleus, the resin on the surface portion of the resin composition gathers to form wrinkle protrusions (projections) and protrusions ( It is thought that recesses are formed along with the formation of protrusions, and as a result, the formation of wrinkles is promoted. It is believed that the wrinkles formed in this way can easily impart a texture to the excellent matte article as well as the visibility of the matte effect due to the light diffusion effect resulting from the shape of the wrinkles.

The wrinkle-forming stabilizer and the resin composition for forming the matte layer containing the wrinkle-forming stabilizer used in the present production method are the wrinkle-forming stabilizer and the resin composition for forming the matte layer that can be used in the above matte article. It is the same as the content explained as a thing.

In this production method, it is preferable to irradiate the resin composition for forming the matte layer with light having a wavelength of at least 100 nm or more and less than 200 nm. Due to this irradiation, the energy of the 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 starts curing, so only the surface causes curing shrinkage. Thus, the formation of wrinkles is stabilized, and the surface layer of the resin composition becomes a cured product having wrinkles and constitutes a matte layer. Then, after that, curing progresses from the near-surface portion where curing progresses slowly to the deep portion away from the depth direction, and the layer of the resin composition becomes a cured product, thereby covering the entire thickness of the resin composition. It hardens and constitutes a matte layer having wrinkles on the surface that exhibit a light diffusion effect. From the viewpoint of accelerating the progress of curing to the deep portion, it is preferable to perform another irradiation treatment after irradiating with light having a wavelength of 100 nm or more and less than 200 nm.

(About irradiation treatment)
In the matte layer forming step in this manufacturing method, the following irradiation treatments (1) and (2) are performed in order from the viewpoint of promoting the formation of wrinkles and making it easier to obtain excellent visibility and texture of the matte effect. preferably.
(1) Irradiation treatment with light having a wavelength of 100 nm or more and less than 200 nm (2) Irradiation treatment with at least one of an electron beam and light having a wavelength of 200 nm or more and 400 nm or less Following the irradiation treatment of (1) above, the irradiation treatment of (2) above. By performing the treatment, the cured state of the resin composition in which wrinkles are maintained by the irradiation treatment in (1) above can be further advanced, so that not only the surface characteristics but also the visibility and texture of the excellent matting effect can be obtained. more likely to be

The light having a wavelength of 100 nm or more and less than 200 nm, which is employed in the irradiation treatment of (1), includes, for example, rare gases such as Ar, Kr, Xe, and Ne, halogens of rare gases such as halogens such as F, Cl, I, and Br Excimer light, which includes light in the ultraviolet wavelength range from an excited dimer, ie, an excimer, formed by discharge of a gas such as a compound or a mixture of these gases, is preferred. The wavelength of the excimer light and the excimer serving as the light source include, for example, light with a wavelength of 126 nm emitted from the excimer of Ar ₂ (hereinafter abbreviated as “126 nm (Ar ₂ )”), 146 nm (Kr ₂ ), and 157 nm. Wavelength light such as (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF) can be preferably employed. As the excimer light, either spontaneous emission light or laser light with high coherence due to stimulated emission can be used, but the use of spontaneous emission light is usually sufficient. A discharge lamp that emits the light (ultraviolet rays) is also called an “excimer lamp”.
The excimer light has a single wavelength peak and is characterized by a narrow half width of the wavelength compared to ordinary ultraviolet rays (for example, ultraviolet rays emitted from metal halide lamps, mercury lamps, etc.). The use of such excimer light promotes the formation of wrinkles, making it easier to obtain excellent visibility and texture of the matting effect.

From the viewpoint of promoting the formation of wrinkles and making it easier to obtain excellent visibility and texture of the matting effect, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, and even more preferably. It is 155 nm or more, and the upper limit is less than 200 nm, particularly preferably 172 nm (Xe ₂ ). Thus, in the present production method, it is preferable to use light with a lower wavelength (short wavelength) from the viewpoint of making it easier to obtain excellent visibility and texture of the matte effect. It can be said that among ultraviolet rays (wavelength: 280 nm or less), ultraviolet rays having a low wavelength (short wavelength) in the region of less than 200 nm are preferable.

In the present production method, the integrated amount of light of the above wavelength is preferably 1 mJ/cm ² or more, more preferably 1 mJ/cm 2 or more, from the viewpoint of promoting the formation of wrinkles and easily obtaining excellent visibility and texture of the matting effect. 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 from the viewpoint of productivity such as reducing the number of lamps required for irradiation of wavelength light and improving production efficiency, the upper limit is preferably 1,000 mJ/cm ² or less, more preferably 1,000 mJ/cm 2 or less. It is 500 mJ/cm ² or less, more preferably 300 mJ/cm ² or less.
From the same point of view, the ultraviolet power density is preferably 0.01 W/cm or more, more preferably 0.1 W/cm or more, still more preferably 0.5 W/cm or more, and the upper limit is preferably 10 W. /cm or less, more preferably 5 W/cm or less, and still more preferably 3 W/cm or less.
Further, the oxygen concentration at the time of irradiation with light of the above wavelength is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, even more preferably 500 ppm or less, and even more preferably 300 ppm or less.

In the matte layer forming step in the present production method, after the above (1) irradiation treatment with light having a wavelength of 100 nm or more and less than 200 nm, (2) irradiation with at least one of an electron beam and light having a wavelength of 200 nm or more and 400 nm or less. Treatment is preferred.

The electron beam irradiation conditions employed in the irradiation treatment of (2) are not particularly limited as long as the resin composition for forming the matte layer is cured, but the electron beam acceleration voltage is preferably 10 kV or more, more preferably. is 30 kV or more, more preferably 50 kV, and even more preferably 75 kV or more, and the upper limit is preferably 300 kV or less, more preferably 250 kV or less, and still more preferably 200 kV or less. When the acceleration voltage of the electron beam is within the above range, the shape of the wrinkles is easily maintained as it is, so that excellent visibility and texture of the matte effect can be easily obtained. Curing effectively provides excellent surface properties.
From the same viewpoint, the electron beam irradiation dose is preferably 5 kGy or more, more preferably 10 kGy or more, and still more preferably 15 kGy or more, and the upper limit is preferably 150 kGy or less, more preferably 125 kGy or less, and still more preferably. is 100 kGy or less.
The electron beam source is not particularly limited as long as it can exhibit the irradiation conditions described above. , high-frequency type electron beam accelerators, etc. can be used.

(2) Ultraviolet rays of 200 nm or more and 400 nm or less used in irradiation treatment, for example, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, black light fluorescent lamps, metal halide lamps, etc. Use an ultraviolet irradiation device with a light source. can be irradiated. Also, excimer light of 200 nm or more and 400 nm or less, for example, wavelength light of 222 nm (KrCl), 247 nm (KrF), 308 nm (XeCl), or the like may be used.

(2) The wavelength of the ultraviolet rays employed in the irradiation treatment is preferably 330 nm or more, and the upper limit is preferably 390 nm or less. When the wavelength of the ultraviolet rays is within the above range, the shape of wrinkles can be easily maintained as it is, so that the visibility and texture of the excellent matte effect can be easily obtained, and the curing of the resin composition for forming the matte layer Excellent surface properties are obtained efficiently.
From the same point of view, the output of the ultraviolet irradiation device that can be used in the irradiation treatment of (2) is preferably 50 W/cm or more, more preferably 100 W/cm or more, and the upper limit is preferably 300 W/cm or less. More preferably, it is 200 W/cm or less. The irradiation rate is preferably 1 r/min or more, more preferably 3 r/min or more, and the upper limit is preferably 50 r/min or less, more preferably 10 r/min or less.

Further, in this manufacturing method, (3) irradiation treatment for pre-curing may be performed before the irradiation treatments (1) and (2). (3) By performing irradiation treatment for pre-curing, the visibility and texture of the matte effect of the matte layer are improved, and the surface properties are also improved. (3) Wavelength light used in the irradiation treatment for pre-curing includes, for example, wavelength light of more than 320 nm, preferably more than 320 nm and 400 nm or less, more preferably 385 nm or more and 400 nm or less. The resin composition for forming the matte layer can be entirely pre-cured by previously irradiating with light of this wavelength.
Whether precuring is necessary or not may be appropriately determined according to desired properties (for example, surface properties such as processing properties and stain resistance) required for the matte layer. Moreover, although the above wavelength light belongs to ultraviolet rays, it is possible to use not only ultraviolet rays but also other ionizing radiation such as electron beams.

In this production method, the matte layer is coated by applying 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, a comma coating method, or the like. A layer (uncured resin layer) can be formed by irradiating light with a wavelength of at least 100 nm or more and less than 200 nm.

In addition, the matte article obtained by this production method may have other layers such as a transparent resin layer in addition to the substrate described as the layer that can be employed in the above matte article.
For example, the decorative layer, the adhesive layer, and the primer layer can be formed by applying a coating liquid containing the composition for forming each layer by the known method described above, and drying and curing as necessary. Moreover, when forming a transparent resin layer, a resin film forming the transparent resin layer can be formed by dry lamination or the like.

[Decorative parts]
Typical applications of the matte article include the use of the matte article as it is as a so-called decorative member that constitutes the surface of buildings, various furniture, vehicles, home appliances, etc., or as an adherend. It is also possible to laminate, combine, or combine to use as a decorative member. Which one to use may be determined as desired.
In the case of having an adherend, the decorative member has the adherend and the above matte article, and specifically, the surface of the adherend requiring decoration and the matte layer of the matte article. The surface opposite to the one surface on which wrinkles are formed to express the visibility and texture of the matte effect is laminated so as to face each other. In addition, when the matte article has a sheet form, it also has the feature of being easily laminated on the adherend.

(Substrate)
Examples of the adherend include a member made of a material appropriately selected from the materials exemplified as those that can be employed as the base material.
The adherend may be appropriately selected from the above according to the application, and may be used as interior members of buildings such as walls, ceilings, and floors, or exterior members such as outer walls, roofs, eaves, fences, gates, and windows. When used as fittings or fixtures such as frames, doors, handrails, baseboards, rims, and moldings, wooden members made of wood-based materials, metal members made of metal, and resin made of resin It is preferably made of at least one kind of member selected from members, and when it is used as an exterior member such as an entrance door, or fittings such as window frames and doors, it is made of at least one kind of member selected from metal members and resin members. is preferred.

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

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

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

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

Although the thickness of the adhesive layer is not particularly limited, it is preferably 1 μm to 100 μm, more preferably 5 μm to 50 μm, even more preferably 10 μm to 30 μm, from the viewpoint of obtaining excellent adhesiveness.

(Manufacturing method of decorative member)
The decorative member can be manufactured through a process of laminating a matte article and an adherend.
This step is a step of laminating the adherend and the matte article, and wrinkles are formed on the surface of the adherend to be decorated and the matte layer of the matte article, so that the visibility and texture of the matte effect are improved. In the case where the matte article has a substrate, the substrate side surface is opposed to the surface opposite to the one surface expressing the . Examples of the method for laminating the adherend and the matte article include a lamination method in which the matte article is laminated on a plate-like adherend by pressing with a pressure roller via an adhesive layer.

When a hot-melt adhesive (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 that constitutes the adhesive. °C or higher and 130 °C or lower. Moreover, in the case of vacuum forming, it is common to carry out while heating, and the temperature is preferably 80° C. or higher and 130° C. or lower, more preferably 90° C. or higher and 120° C. or lower.

(Use of decorative member)
The decorative member obtained as described above can be arbitrarily cut, and the surface and the butt end portion can be arbitrarily decorated such as grooving and chamfering using a cutting machine such as a router and a cutter. And various uses, for example, interior members of buildings such as walls, ceilings and floors, exterior members such as outer walls, eaves, roofs, fences and fences, window frames, doors, door frames, handrails, baseboards, In addition to fittings or fixtures such as rims and malls, general furniture such as chests, shelves, desks, etc., kitchen furniture such as dining tables and sinks, various types of furniture used around water such as kitchens, toilets, bathrooms, washbasins, etc. It is suitably used as various members such as members, surface decorative boards for cabinets of home appliances and OA equipment, interior and exterior members of vehicles, signboards, soundproof walls, and the like. When the matte article is in the form of a sheet, it is suitably used as a decorative sheet for the above various members. In addition, considering the surface characteristics of the matte article, especially the excellent scratch resistance, and the excellent visibility and texture of the matte effect, applications where scratch resistance is particularly required, such as interior decoration of buildings Among the members, it is suitably used for applications such as floor materials, and frequently used fitting members such as window frames, doors, door frames, handrails, and the like.
Furthermore, in addition to the various members described above, matte articles can be used alone, or laminated or combined with other materials, such as packaging materials, antiglare films for displays, whiteboards or blackboards, credit cards, and cash. It can be used for cards, telephone cards, various cards such as various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (window glass, etc.), artificial leather, and the like.

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

(Evaluation method: 60° gloss value)
For the articles obtained in Examples and Comparative Examples, a gloss meter ("Microgloss (model name)", manufactured by BYK Gardner) was used to measure 60° specular glossiness in accordance with K 5600-4-7: 1999. was measured.

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

(Measurement of Martens hardness)
The Martens hardness of the matte layer of the article obtained in each example and comparative example was measured by the following method.
Using an ultra-micro hardness tester (micro-hardness tester, "Picodenter HM-500", manufactured by Fisher Instruments), the load is continuously applied at an acceleration rate of 0.15 mN / 20 s at room temperature (23 ° C.). The pressure was increased to a maximum load of 3.0 mN, and a pyramid-shaped diamond indenter was pressed into the sample (the surface of the matte layer). Measure the test load F (N) when the indentation depth reaches 2 μm, calculate the surface area A (mm ² ) from the length of the diagonal line of the pyramidal depression formed on the surface, and test load F (N ) by the surface area A, the Martens hardness was calculated. The creep time was 5 seconds.
The Martens hardness of the matte layers of the articles of Examples and Comparative Examples was defined as the average value of the Martens hardness calculated by performing the above measurements on 10 arbitrary points.

[Example 1]
A corona discharge-treated polypropylene sheet (thickness: 60 μm) is used as a base material, and printing ink (binder resin: two-liquid curing acrylic-urethane resin) is applied to one side of the base material by gravure. A colored layer (thickness: 3 μm) is provided, a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied on the colored layer to provide a primer layer (thickness: 2 μm), and the primer layer is coated with , a resin composition for forming a matte layer (trifunctional urethane (meth) acrylate oligomer): 30 parts by mass, a monofunctional acrylate monomer: 40 parts by mass,
Bifunctional acrylate monomer: 30 parts by mass, wrinkle-forming stabilizer 1 (silica particles, average particle size: 3 μm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass), gravure method (coating amount: 5 g/m ² (when dry)), then using a UV irradiation device composed of LEDs to irradiate ultraviolet rays (wavelength: 395 nm, amount of ultraviolet rays: 0.6 W/cm ² ), and then Ultraviolet rays are irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet power density: 1 W/cm, integrated light quantity: 10 to 100 mJ/cm ² , nitrogen atmosphere (oxygen concentration: 200 ppm or less)), and then further. A matte layer was provided on the substrate by irradiation using a high-pressure mercury lamp (wavelength: 365 nm, UV power density: 200 W/cm) to obtain a matte article having a substrate and a matte layer. The 60° gloss value and Martens hardness of the obtained matte article were measured by the methods described above. Table 1 shows the measurement results. Table 1 also shows the texture evaluation.

[Examples 2 to 5]
A matte article was obtained in the same manner as in Example 1, except that the composition of the resin composition for forming the matte layer was changed to that shown in Table 1. Table 1 shows the 60° gloss value, Martens hardness and texture evaluation of the matte layer side of the obtained matte article.

[Comparative Examples 1 and 2]
An article was obtained in the same manner as in Example 1, except that the composition of the resin composition for forming the matte layer was changed to that shown in Table 1. Table 1 shows the 60° gloss value, Martens hardness and texture evaluation of the matte layer side of the obtained article.

From the results in Table 1, the matte article of the present embodiment has a 60° gloss value of 2.0 or less on the matte layer side, and the visibility of the matte effect is extremely excellent, and the texture is also good. It was confirmed to be an excellent product. In addition, the Martens hardness of the matte layer in the examples is 200 N/mm ² or less, and the Martens hardness of the comparative examples is all greater than 200 N/mm ² , so the visibility and texture of the matte effect and the Martens hardness was also found to be correlated. That is, it was confirmed that when the matte layer had a Martens hardness of 200 N/mm ² or less, excellent visibility and texture of the matte effect were obtained.

On the other hand, the article of Comparative Example 1, in which the matte layer has a Martens hardness of more than 200 N/mm ² , exhibited excellent luster although some wrinkles occurred on the surface as shown in the optical microscope image of FIG. The visibility of the erasing effect was not obtained, and there were parts with the same gloss value as in the example, but there were parts with high gloss and the surface condition was unstable, and the texture was excellent. It was nothing. The article of Comparative Example ² also had some wrinkles on its surface as shown in the optical microscope image of FIG. Since the gloss value was as high as 6.1, the matting effect was low and the texture was also low. From this, it was also found that even if a wrinkle-forming stabilizer is used, the effect of using the wrinkling-forming stabilizer cannot be obtained unless the matte layer has a Martens hardness of 200 N/mm ² or less.

Also, according to the optical microscope images of Examples 1-5 (FIGS. 5-9, respectively), it can be confirmed that the matte articles of these Examples have irregular wrinkles on their surfaces. On the other hand, according to the optical microscope image of Comparative Example 1 (FIG. 10) and the optical microscope image of Comparative Example 2 (FIG. 11), as described above, some wrinkles were generated on the surface, and the operation was partially performed. Although there are areas with wrinkles similar to those in the example, it can be seen that the formation of wrinkles is unstable (not uniform) and mixed with areas without wrinkles. 5 to 11 are 203.3 μm×271.5 μm in length and width, respectively.
From this result, the matte article of the present embodiment formed irregular wrinkles on the surface by setting the Martens hardness of the matte layer to 200 N/mm ² or less, and was extremely excellent due to the wrinkles. It was confirmed that the visibility and texture of the matte effect were expressed.

The matte article of the present embodiment can be used in various applications, for example, interior members of buildings such as walls, ceilings and floors, exterior members such as outer walls, eaves, roofs, fences and fences, window frames, doors, Door frames, handrails, baseboards, rims, moldings and other fittings or fixtures, general furniture such as wardrobes, shelves, desks, kitchen furniture such as dining tables and sinks, kitchens, toilets, bathrooms, washstands, etc. It can be suitably used as various types of furniture and members used around water, decorative surface panels for cabinets such as household appliances and OA equipment, and various members such as interior and exterior members for vehicles.
Furthermore, in addition to the above-mentioned various members, matte articles, etc. can be used alone or in a form laminated or combined with other materials, such as packaging materials, antiglare films for displays, whiteboards or blackboards, credit cards, It can be used for cash cards, telephone cards, various cards such as various certificates, keyboards of various keyboards, windows, doors, transparent plates such as partitions (window glass, etc.), artificial leather, and the like.

Claims (11)

A matte article,
The matte article has an uneven shape due to irregular wrinkles on the surface,
The irregular wrinkles are composed of a plurality of protrusions formed by a plurality of filamentary protrusions and a recess formed by being surrounded by the plurality of filamentary protrusions,
The convex portion and the concave portion are based on the median value of the height distribution in the uneven shape, and the region having a height exceeding the median value is a convex portion, and the region having a height equal to or less than the median value is a concave portion. and
The matte article has a matte layer composed of a cured resin composition,
The matte layer is disposed on the surface of the matte article,
A matte article, wherein the matte layer has a Martens hardness of 200 N/mm ² or less. 2. The matte article according to claim 1, wherein the resin composition contains a wrinkle-forming stabilizer whose upper limit is the average particle size of 100% or less of the thickness of the surface wrinkle layer or 30 μm or less, whichever is smaller. . 3. The matte article according to claim 2, wherein the content of said wrinkle-forming stabilizer is 0.5 parts by mass or more and 6.0 parts by mass or less with respect to 100 parts by mass of the resin contained in said resin composition. Any one of claims 1 to 3 , wherein the matte layer does not contain a matte agent having an average particle size with a lower limit of more than 100% of the thickness of the matte layer and more than 30 μm, whichever is smaller. Matte article according to paragraph. The matte article according to any one of claims 1 to 4 , wherein the matte layer is provided over the entire surface. The matte article according to any one of claims 1 to 5 , wherein the resin is an ionizing radiation curable resin. The matte article according to any one of claims 1 to 6 , further comprising a substrate. 8. The matte article according to claim 7 , wherein the uneven shape is present on the surface of the matte layer opposite to the substrate. 9. The matte article according to claim 7, further comprising a decorative layer between said substrate and said matte layer. The matte article according to any one of claims 1 to 9, wherein the resin contained in the resin composition contains a polymerizable monomer and a polymerizable oligomer. 11. The matte article according to claim 10, wherein the content of the polymerizable oligomer is 5 parts by mass or more and 45 parts by mass or less with respect to a total of 100 parts by mass of the polymerizable monomer and the polymerizable oligomer.

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