WO2021201105A1

WO2021201105A1 - Matte article and method for producing matte article

Info

Publication number: WO2021201105A1
Application number: PCT/JP2021/013846
Authority: WO
Inventors: 祥太西根; 玲子桜井; 亮介西垣; 小笠原　健; 美幸飯原; 朝達洞ヶ瀬
Original assignee: 大日本印刷株式会社
Priority date: 2020-03-31
Filing date: 2021-03-31
Publication date: 2021-10-07
Also published as: JP2022132678A

Abstract

Provided are: a matte article which has excellent visibility and matte effect texture and adopts a matte layer having a 60° gloss value of at most 5.0 and having an uneven shape resulting from irregular wrinkles by containing a predetermined amount of a wrinkle formation stabilizer having various surface characteristics as desired; a matte article used for shaping that can meet a diversity of demands; and a method for producing a matte article or the like having a layer obtained by curing a resin composition under a specific irradiation condition.

Description

Matte article and manufacturing method of matte article

The present invention relates to a matte article and a method for manufacturing a matte article.

Conventionally, for example, interior members of buildings such as walls, ceilings, floors, exterior members such as outer walls, eaves ceilings, roofs, walls, fences, window frames, doors, door frames, handrails, skirts, surrounding edges, etc. In addition to fittings or building members such as malls, general furniture such as stools, shelves, desks, kitchen furniture such as dining tables and sinks, various furniture and members used around water such as kitchens, toilets, bathrooms, and washbasins, or So-called decorative materials and decorative sheets are used as articles for decorating and protecting the surfaces of home appliances, cabinets of OA equipment, etc., and interior or exterior members of vehicles. As such decorative materials and decorative sheets, for example, those having a surface layer having a desired function are used, and mainly surface characteristics such as scratch resistance, stain resistance and weather resistance, various processing characteristics and the like are used. Performance is required.

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

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

As an article such as a decorative material or a decorative sheet used for the above-mentioned applications, for example, in order to impart surface characteristics such as weather resistance, a method of using a curable resin for forming the surface layer and using the cured product as a layer is used. (See, for example, Patent Documents 3 to 5). The decorative sheet described in Patent Document 3 describes that a surface layer (top coat layer) is formed by irradiating an electron beam-curable resin composition with an electron beam and curing it. Describes that a surface layer (gloss adjusting resin layer) is formed by a crosslinked cured product of an ionizing radiation curable resin composition containing matte silica. Further, Patent Document 5 describes that an ultraviolet curable resin layer is used as the surface protective layer.

Among the above applications, exterior members such as outer walls, eaves ceilings, roofs, walls, and fences are used outdoors and have problems such as color change and resin deterioration due to the effects of ultraviolet rays caused by wind and rain and solar radiation. It will occur. As a method for improving the light resistance of a decorative sheet used in such an application, it is common to add an ultraviolet absorber as a weathering agent into the surface protective layer of the decorative material. In addition, even for interior materials that are basically expected to be used indoors, light resistance may be required for those that are exposed to sunlight near windows, etc., as with exterior materials. ..

However, there is a problem that the ultraviolet absorber tends to bleed out from the surface protective layer over time. When the UV absorber bleeds out, the appearance of the surface of the decorative sheet is spoiled, such as stickiness, and the bleed-out UV absorber is gradually lost due to outflow due to rain, etc., and UV absorption in the surface protective layer over time. As the agent concentration decreases, there arises a problem that the weather resistance decreases. Under such circumstances, in order to eliminate the bleed-out of the ultraviolet absorber, for example, an electron beam curable resin containing an electron beam reaction type ultraviolet absorber selected from a specific benzotriazole compound or the like is used as a main component. A decorative sheet having a cured layer of resin has been proposed (for example, Patent Document 1). According to the decorative sheet described in Patent Document 1, the problem of bleed-out of the ultraviolet absorber can be solved.

With the recent increase in customers' preference for high-end products, cosmetic materials and decorative sheets used for the above purposes are also required to have a high-class feel.
As a method of giving a sense of quality, a method of giving an uneven shape to the surface to enhance the texture is generally adopted. Specifically, embossing using a shaping sheet, an embossed plate, or the like, or using a transfer sheet provided with a layer having an uneven shape, the layer having an uneven shape is transferred to the surface to give the uneven shape. Then, a method of expressing a matte effect (matte effect) and the like can be mentioned. For example, Patent Document 6 has a layer having an uneven shape made of an ionizing radiation curable resin on the surface of a base sheet, and imparts a crosslink density so that the uneven shape does not crack when peeled off. A shaped sheet that reproduces a desired pattern shape and a polyester veneer using the shaped sheet have been proposed. Further, Patent Document 2 proposes a decorative sheet in which a printing layer and a transparent resin layer are sequentially provided on a base material, and an embossed pattern is applied to the outermost surface of the transparent resin layer.

In addition, as a decorative material having a matte effect (matte effect) and a decorative sheet, a sheet having a matte coating film formed on the surface constitutes the surface of various writing boards such as a blackboard and a white board. ) May be used for sheets, reflective screens, etc. When the matte coating film forming sheet used for these purposes is installed in a room such as a lecture room or a conference room, the reflection of the interior light or the like is reduced and the gloss is suppressed, so that the writing board, etc. It is required to have excellent visibility of characters and the like displayed on the projection screen.

For example,

Patent Documents

7 and 8 propose a whiteboard sheet having a whiteboard writing layer. In the conventional products such as the whiteboard sheets of

Patent Documents

7 and 8, the reflection of interior lights and the like is suppressed by the scattering of light, and the gloss is suppressed and displayed on the writing board, the projection screen and the like. In order to improve the visibility of characters and the like, matting agents such as silica and calcium carbonate, and other pigments are added to the surface coating film. That is, the conventional product suppresses the reflection and gloss of the interior light by the matting effect of the matting agent, and improves the visibility.

In particular, since writing sheets such as whiteboards support writing and erasing with markers, the writing and erasability of markers are also required by balancing the appropriate wettability and easy cleaning of the surface. For the writability and erasability of the marker, its surface needs to be smoother.

Japanese Unexamined Patent Publication No. 2000-062081 Japanese Unexamined Patent Publication No. 2011-073207 Japanese Unexamined Patent Publication No. 2000-117905 Japanese Unexamined Patent Publication No. 2004-148632 Japanese Unexamined Patent Publication No. 2000-103019 Japanese Unexamined Patent Publication No. 2-235744 Special Fair 7-64155 Gazette Japanese Unexamined Patent Publication No. 11-28892

As a method for improving the texture by the matting effect (matting effect), a matting agent (also referred to as "matting agent") is used as in Patent Document 1, and the light diffusing effect itself has. A method of obtaining a matte effect by the above method, a method of forming an uneven shape on the outermost surface by embossing as in Patent Document 2 above, and the like are mainly mentioned.
However, when a matting agent is used as in Patent Document 1, it is necessary to increase the amount of the matting agent used in order to make the matting effect more excellent. However, as the amount of the matting agent used increases, the matting agent becomes more effective. The surface characteristics tend to be deteriorated due to reasons such as the scratch resistance being lowered by falling off from the coating film and damaging the coating film. On the other hand, if the amount used is reduced in order to suppress the deterioration of the surface characteristics, the matting effect tends to decrease, and the surface characteristics and the matting effect have a bilateral reciprocal relationship. Therefore, there is a limit to the matte effect using a matting agent.
Further, when embossing is used as in Patent Document 2, it is not easy to prepare an embossed plate because it takes a lot of time and effort, and it is necessary to prepare a plate for each desired pattern. Therefore, it cannot be said that the method is sufficiently easy to respond to the diversity of customer demand.

The decrease in scratch resistance due to the matting agent falling off from the coating film and damaging the coating film is caused by, for example, the use of flooring materials among interior members of buildings, and window frames, doors, and door frames that are frequently used. This is remarkable in applications of fitting members such as handrails, blackboard erasers (or whiteboard erasers), and whiteboard sheets to which friction by markers is repeatedly applied.

Further, in recent years, decorative sheets for outdoor use have come to be used under more severe solar radiation conditions due to the rise in average temperature due to the influence of global warming, and conventional cosmetic materials cannot cope with the deterioration. Progress tends to accelerate year by year. Therefore, it can be said that the conventional design concept itself for suppressing the occurrence of bleed-out of the ultraviolet absorber is appropriate, but it is necessary to review the means for realizing this.

Further, a decorative sheet having excellent surface characteristics, especially easy decontamination property (also referred to as "erasability") that easily decontaminates stains adhering to the surface, and excellent matting effect and texture, for example, adheres to stains. While there are demands in fields such as flooring materials for easy buildings and whiteboards where writing and erasing with markers are repeated, there is no decorative sheet that can sufficiently meet these demands.

As described above, in addition to the matting effect, surface characteristics that are more desired are required, but there is no article such as a decorative material or a decorative sheet that can sufficiently cope with this.

As the curable resin forming the surface layer, ionizing radiation curable resins, particularly electron beam curable resins, ultraviolet curable resins and the like are adopted as described in Patent Documents 3 to 5. When an ultraviolet curable resin that can be cured using ultraviolet rays is adopted, as disclosed in Patent Document 5, it is common to usually use a photopolymerization initiator. Since ultraviolet rays have extremely low energy compared to other ionizing radiation such as electron beams, curing by functional groups such as ethylenically unsaturated groups that develop curability by ionizing radiation is not promoted unless a photopolymerization initiator is added. Therefore, the desired surface characteristics cannot be obtained. As described above, while it is necessary to adjust the composition of the resin composition by the curing method of the resin composition forming the surface layer, any resin composition can be used to form a layer having excellent surface properties. Is required. In addition, a matte effect may be required to improve the design.
Under such circumstances, a surface layer made of an ionizing radiation curable resin can obtain excellent surface properties and visibility of a matte effect without adding a photopolymerization initiator when curing the surface layer. The formation method of was sought.

In addition, there is a growing demand for higher quality textures as customers become more enthusiastic about luxury products. However, the uneven shape of the shaped film described in Patent Document 3 is formed by forming a predetermined pattern with a liquid-repellent resin and then applying a two-component curable resin composition containing an inorganic filler to repel the uneven shape. It is formed by repelling only the two-component curable resin composition on the pattern due to the liquid-repellent effect of the liquid resin. Therefore, since there is a limit to the formation of a delicate uneven shape, it is not possible to impart an excellent matting effect, and there are cases where a desired requirement cannot be met.
Further, in the case of the method of forming an uneven shape on the outermost surface by embossing as in Patent Document 2, the production of the embossed plate is not easy because it takes a lot of time and effort, and the plate is made for each desired pattern. Will need to be made. Therefore, it cannot be said that the method is sufficiently easy to respond to the diversity of customer demand.

When the above-mentioned matting agents, pigments, etc. are used for the articles used for the whiteboard sheet having the above-mentioned whiteboard writing layer in order to obtain excellent visibility due to the matting effect, these particles and a coating film are used. The marker easily soaks into the resin, and once it soaks in, the problem that the marker cannot be erased even if it is wiped off (marker erasability deteriorates) tends to occur. In addition, since a large amount of particles are required to suppress the reflection and gloss of light from interior lights and improve visibility by the matting effect using particles such as matting agents and pigments, ink is used. The problem of not being able to erase becomes more pronounced. Further, when a large amount of particles are used, the shape corresponding to the shape of the particles such as the matting agent and the pigment is more exposed, and the smoothness is lost, so that the marker erasability is lowered. In this way, the matting effect using a matting agent, pigment, etc. suppresses the reflection and gloss of the interior light to improve visibility, and in particular, the marker erasing property has a bilateral relationship. There is. Therefore, the whiteboard sheets described in

Patent Documents

1 and 2 are not sufficient in both visibility and marker erasability due to the matting effect, and further improvement is required.

An object of the present invention is to provide a matte article having excellent visibility and texture of a matte effect and having various surface characteristics as desired, and a method for producing the matte article.

In order to solve the above problems, the present invention visually recognizes the matte effect by incorporating a wrinkle formation stabilizer in a predetermined amount and adopting a matte layer having an uneven shape composed of irregular wrinkles. It has been found that a matte article having excellent properties and texture and having various surface properties as desired, and a matte article used for shaping that can meet diversifying demands can be obtained.
Further, regarding the method for producing an article, (i) a matte layer is formed by subjecting a resin composition containing a wrinkle formation stabilizer in a predetermined amount to a specific irradiation treatment, so that the matte layer is irregular. It has a concavo-convex shape composed of wrinkles, is excellent in visibility and texture of the matte effect, and can easily obtain a matte article having various surface characteristics as desired. Further, (ii) photopolymerization. Even if the resin composition does not contain an initiator, by forming a surface wrinkle layer by performing a specific irradiation treatment, the surface wrinkle layer becomes wrinkled, has desired surface characteristics, and also has a desired surface property. It has been found that a matte article that can also have the visibility of a matte effect can be easily obtained.

According to the present invention, a matte article having excellent visibility and texture of a matte effect and having various surface characteristics as desired, a matte article used for shaping that can meet diversifying demands, and a gloss. A method of manufacturing an erasable article can be provided.

It is a schematic diagram in the plan view which shows one Embodiment of the matte article of this invention. It is sectional drawing which shows one Embodiment of the matte layer of the matte article of this invention. It is sectional drawing which shows one Embodiment of the matte article of this invention. It is sectional drawing which shows one Embodiment of the matte article of this invention. 8 is an optical microscope image of the surface of the matte article obtained in Example 1A. 8 is an optical microscope image of the surface of the matte article obtained in Example 2A. 8 is an optical microscope image of the surface of the matte article obtained in Example 3A. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1A. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2A. 6 is an optical microscope image of the surface of the matte article obtained in Example 1B. 8 is an optical microscope image of the surface of the matte article obtained in Example 2B. 8 is an optical microscope image of the surface of the matte article obtained in Example 3B. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1B. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2B. 8 is an optical microscope image of the surface of the matte article obtained in Example 1C. 8 is an optical microscope image of the surface of the matte article obtained in Example 2C. 8 is an optical microscope image of the surface of the matte article obtained in Example 3C. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1C. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2C. 8 is an optical microscope image of the surface of the matte article obtained in Example 1D. 8 is an optical microscope image of the surface of the matte article obtained in Example 2D. 8 is an optical microscope image of the surface of the matte article obtained in Example 3D. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1D. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2D. 8 is an optical microscope image of the surface of the matte article obtained in Example 1E. 8 is an optical microscope image of the surface of the matte article obtained in Example 2E. 8 is an optical microscope image of the surface of the matte article obtained in Example 3E. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1E. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2E. It is an optical microscope image of the surface of the matte article obtained in Example 1F. It is an optical microscope image of the surface of the matte article obtained in Example 2F. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1F. It is an optical microscope image of the surface of the article obtained in Comparative Example 2F. It is sectional drawing which shows one Embodiment of the matte article G of this invention. It is sectional drawing which shows one Embodiment of the matte article G of this invention. 8 is an optical microscope image of the surface of the matte article obtained in Example 1G. 8 is an optical microscope image of the surface of the matte article obtained in Example 2G. 8 is an optical microscope image of the surface of the matte article obtained in Example 3G. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1G. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2G. It is sectional drawing which shows one Embodiment of the matte article H of this invention. It is sectional drawing which shows one Embodiment of the matte article H of this invention. 8 is an optical microscope image of the surface of the matte article obtained in Example 1H. 8 is an optical microscope image of the surface of the matte article obtained in Example 2H. 8 is an optical microscope image of the surface of the matte article obtained in Example 3H. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1H. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2H. 8 is an optical microscope image of the surface of the matte article obtained in Example 1I. 2 is an optical microscope image of the surface of the matte article obtained in Example 2I. 3 is an optical microscope image of the surface of the matte article obtained in Example 3I. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 1I. 2 is an optical microscope image of the surface of the article obtained in Comparative Example 2I. 6 is an optical microscope image of the surface of the matte article obtained in Example 1J. 6 is an optical microscope image of the surface of the matte article obtained in Example 2J. 6 is an optical microscope image of the surface of the matte article obtained in Example 3J. 6 is an optical microscope image of the surface of the article obtained in Comparative Example 2J.

Hereinafter, an embodiment of the present invention (hereinafter, may be referred to as “the present embodiment”) will be described. In addition, in this specification, the numerical values relating to "greater than or equal to", "less than or equal to" and "..." relating to the description of the numerical range are numerical values that can be arbitrarily combined, and the numerical values of Examples are numerical values that can be used for the upper and lower limits of the numerical range. Is.

[Matte article A]
The matte article of the present embodiment is a matte article having a matte layer, and the matte layer is 0.5 parts by mass or more and 6.0 parts by mass of a wrinkle formation stabilizer with respect to 100 parts by mass of the resin. It is composed of a cured product of the resin composition contained below, has an uneven shape in which at least one surface of the matte layer is composed of irregular wrinkles, and the 60 ° gloss value of the matte layer is 5.0. The following is a matte article (hereinafter, also simply referred to as "matte article A"). By having such a structure, the matte article A is excellent in surface characteristics, particularly scratch resistance, and also excellent in visibility and texture of the matte effect.

[Matte layer]
The matte layer in the matte article A is a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of a wrinkle formation stabilizer with respect to 100 parts by mass of the resin (hereinafter, "resin for forming a matte layer". It is a layer composed of a cured product of (sometimes referred to as "composition"). That is, in the present embodiment, the matte layer is a layer containing a wrinkle formation stabilizer at a content of 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 forming the matte layer. be.

(Wrinkle formation stabilizer)
The wrinkle formation stabilizer stabilizes the formation of wrinkles on at least one surface of the matte layer, so that the visibility of the matte effect is uniformly exhibited over the entire surface of the matte article A, and partial gloss unevenness is generated. Along with the reduced visibility of the stable matting effect (hereinafter, the expression "stable matting effect visibility" or a similar expression may be used), the entire surface of the matte article A. It has a function of imparting uniformity of surface condition (also referred to as "texture") by stably forming wrinkles over a period of time. That is, the so-called "matting agent" in the prior art and the "wrinkle forming stabilizer" in the present embodiment have the same matting mechanism (action) even when their constituent substances and average particle diameters are the same. ), The structure for developing matte, and the relationship between the amount used and the degree of gloss (gloss value) on the surface are different.
More specifically, the above-mentioned "stabilizing the formation of wrinkles" possessed by the wrinkle formation stabilizer means the shape of the "wrinkles" and its geometric characteristic value (individual protrusions in the uneven shape of the wrinkles (). Convex length, width and ratio of these), and also, for example, Rz (maximum height), Rsm (average length of curved elements), Ra (arithmetic mean roughness), Sk (skunes), Sk (Kurtosis). Statistical indicators such as, these characteristic values or indicators, and various numerical values and indicators such as the in-plane distribution (dispersion σ) of the 60 ° gloss value of the surface of the matte surface layer due to these. By using the "wrinkle formation stabilizer", it means that it converges as compared with the case where it is not used.

Further, in general, when the surface of the resin layer containing particles such as a matting agent comes into contact with another object and is rubbed, the particles in the vicinity of the surface tend to fall off. Therefore, in the case of a specification in which the gloss of the layer surface is lowered exclusively by adding a matting agent, the loss of such particles causes a gloss change at the time of contact with another object or friction. The gloss change due to such a mechanism becomes more remarkable as the content of the matting agent is higher in the low gloss specification. In particular, if the 60 ° gloss value G ₆₀ is realized by the addition of 10 following surface matting agent with respect to 100 parts by weight of resin, depending on the dispersed form Ikan the (kind of resin and matting agent ,) It is necessary to add about 50 parts by mass or more, and the change in gloss due to contact with other objects and removal of the matting agent during friction becomes large.
In matting layers in matte article A, as demonstrated in Examples and Comparative Examples described later, the 60 ° gloss value G ₆₀ is 5.0 or less of the surface even if realized by matting agent added, the resin The content of the wrinkle formation stabilizer with respect to 100 parts by mass is about 10 parts by mass or less, and more specifically, 6.0 parts by mass or less. For example, in the embodiment of the present invention, 60 ° gloss value G ₆₀ is 5.0 or less in a total content of up to 6 parts by weight of the wrinkle formation stabilizers, further realizes a low gloss of 2.0 or less .. As will be described later, in the present specification, those having a 60 ° gloss value of 5.0 or less are treated as “matte”.
Therefore, in flatting the article A, as demonstrated in Examples and Comparative Examples described below, to achieve the same low gloss surface, in particular 60 ° gloss value G ₆₀ is 10 or less, more 5.0 or less In the case of realization, since the particle content is significantly reduced as compared with the conventional matte article, the change in gloss due to the contact with other objects and the removal of the matting agent at the time of friction is small. ..

In the prior art such as Patent Document 1, the matting agent used for matting expression itself exhibits a matting effect due to the light diffusing effect caused by the physical shape and the inherent refractive index. Is what you do. Specifically, what is generally called a matting agent generally has a difference in refractive index between the matting agent particles and the surrounding resin and air, and the reflection and refractive index of light rays corresponding to the contour shape of the particles. The visibility of the matte effect is exhibited by the light diffusion effect of the interface. On the other hand, in the matte article of the present embodiment, the wrinkle formation stabilizer is caused by the wrinkle formation stabilizer, in which the light diffusion due to the reflection and refraction of light rays by the particles themselves does not exhibit the visibility of the matte effect. By stabilizing the formation of wrinkles on the surface of the matte layer, the matte article is stably given a texture as well as the visibility of the matte effect by the light diffusion effect at the interface between the surface and the air with a refractive index difference. That is. Therefore, the wrinkle-forming stabilizer used in the present embodiment is different from the matting agent that itself exhibits the visibility of the matting effect (even if both constituent substances and the average particle size are the same). ,) The matting mechanism (action) of both, the structure for expressing matting, etc. are different.
Further, the "wrinkle formation stabilizer" and the "matte agent" are also different in the relationship between the content and the gloss (gloss value) of the surface. When the same substance A is used as a wrinkle formation initiator AW (W: wrinkle, an abbreviation for wrinkle) and is contained in a specific amount C to form wrinkles on the surface, the surface 60 ° gloss value G _{60 °} ^AW ( In C), the same substance A is used as a mere matting agent AM (M: abbreviation for matte, matte), and the 60 ° gloss value G of the surface when wrinkles are not formed on the surface even if this is contained in the specific amount C. It is clearly lower than _{60 °} ^{AM (C).} That is, the following relational expression holds.
G _{60 °} ^AW (C) <G _{60 °} ^AM (C)

The matte layer may contain an agent that has been conventionally used as a matting agent, but the visibility and texture of an extremely excellent matting effect that cannot be obtained even if a matting agent is used can be stably obtained. Considering the characteristic of the effect of the invention, it is preferable not to contain a matting agent. As described above, the matte article A has extremely excellent visibility and texture of the matte effect even if it does not substantially contain the matting agent conventionally used for obtaining the visibility of the matte effect. You can say that. Therefore, when a matting agent is included (added), the matting effect due to wrinkles on the surface of the matte layer is only reinforced. Here, "does not contain a matting agent" means that, in addition to not containing a matting agent at all, even if it is contained, it does not have the visibility of a matting effect based on the action effect of the matting agent itself. Specifically, it means that the content of the matting agent is less than 15.0 parts by mass, preferably 10.0 parts by mass or less, and more preferably 3.0 parts by mass or less with respect to 100 parts by mass of the resin. ..
In the specification of the present application, the term "matting agent" is specifically used from the viewpoint of exhibiting the visibility of the matting effect by the light diffusing effect due to the reflection of light rays corresponding to the contour shape of the particles and 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 diameter whose lower limit is the smaller of more than 100% and more than 30 μm of the thickness of the matte layer.

The wrinkle formation stabilizer is not a matting agent as described above, and has an average particle diameter of 100% or less or 30 μm or less of the thickness of the matte layer, whichever is smaller, whichever is the upper limit, for example, organic particles. , Various particles such as inorganic particles can be adopted. In the present embodiment, when the wrinkle formation stabilizer is not used, the formation of wrinkles becomes unstable, and the visibility and texture of the excellent matting effect due to the formation of wrinkles cannot be stably obtained as a whole.

The wrinkle-forming stabilizer used in the matte article A can be used without particular limitation as long as it is not a matting agent and has an average particle size of 100% or less of the thickness of the matte layer. Wrinkle formation stabilizer 1 having an average particle size of 1 μm or more and 100% or less or 30 μm or less of the thickness of the matte layer, whichever is smaller, and wrinkle formation stabilizer 2 having an average particle size of less than 1 μm. Is preferably used. In the present embodiment, one or more kinds of wrinkle formation stabilizer 1 may be used, one or more kinds of wrinkle formation stabilizer 2 may be used, or one or more kinds of wrinkle formation stabilizer 2 may be used as the wrinkle formation stabilizer. Wrinkle formation stabilizer 1 and one or more kinds of wrinkle formation stabilizer 2 may be used in combination. In the present embodiment, from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matting effect, two types of wrinkle formation stabilizers, wrinkle formation stabilizer 1 and wrinkle formation stabilizer 2, are used. Is preferably used.

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

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

The average particle size of the wrinkle formation stabilizer is preferably glossy with respect to the thickness of the matte layer as an upper limit from the viewpoint of stabilizing the formation of wrinkles and improving the visibility and texture of the matte effect. 90% or less of the thickness of the matte layer, more preferably 80% or less of the thickness of the matte layer, further preferably 70% or less of the thickness of the matte layer, and the absolute value is preferably 20 μm or less. It is more preferably 10 μm or less, further preferably 8 μm or less, still more preferably 7 μm or less, and it may be the smaller of the case where the upper limit of the thickness of the matte layer and the upper limit of the absolute value are arbitrarily combined. .. For example, the upper limit may be 90% or less of the thickness of the matte layer or 20 μm or less, whichever is smaller, or 90% or less of the thickness of the matte layer or 10 μm or less, whichever is smaller. You 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 further preferably 5 nm or more.

When used separately for the

wrinkle formation stabilizers

1 and 2 as described above, the average particle size of the wrinkle formation stabilizer 1 stabilizes the formation of wrinkles and stably improves the visibility and texture of the matting effect. From the viewpoint of making the mixture, it is preferably 1.3 μm or more, more preferably 1.5 μm or more, still more preferably 1.8 μm or more, and the upper limit is as described above.
From the same viewpoint as this, the average particle size of the wrinkle formation stabilizer 2 is preferably 1 nm or more, more preferably 3 nm or more, further preferably 5 nm or more, and the upper limit is preferably 900 nm or less, more preferably 700 nm. Below, it is more preferably 500 nm or less.
In the present specification, the average particle size of the wrinkle formation stabilizer is measured as the mass average value d50 in the particle size distribution measurement by the laser light diffraction method.

The content of the wrinkle formation stabilizer, and when the

wrinkle formation stabilizers

1 and 2 are used in combination as the wrinkle formation stabilizer, the total content of these is 0.5 with respect to 100 parts by mass of the resin forming the matte layer. It is not less than a part by mass and not more than 6.0 parts by mass. If it is less than 0.5 parts by mass, the effect of using the wrinkle formation stabilizer cannot be obtained and the formation of wrinkles is not stable, so that the visibility and texture of the matte effect cannot be stably obtained. On the other hand, if it exceeds 6.0 parts by mass, the effect of stabilizing wrinkle formation becomes saturated, and as described in the background technology and its problems, scratch resistance, stain resistance, and easy decontamination (erasability). ), Etc. tend to increase the effect of deterioration of surface characteristics. Furthermore, if it exceeds 6.0 parts by mass, the formation of wrinkles becomes difficult to stabilize depending on the type of wrinkle formation stabilizer and resin, and the formation conditions of the matte layer (or surface wrinkle layer), and the gloss becomes stable. This is because it becomes difficult to obtain the visibility and texture of the erasing effect, and the surface characteristics may be deteriorated.

From the viewpoint of stabilizing the formation of wrinkles by the wrinkle formation stabilizer and stably improving the visibility and texture of the matting effect, the total content of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 is matte. With respect to 100 parts by mass of the resin forming the layer, it is preferably 0.75 parts by mass or more, more preferably 1.0 part by mass or more, still more preferably 1.2 parts by mass or more, and the upper limit is a stable luster. From the viewpoint of improving the visibility of the erasing effect, there is no particular limitation as long as it is 6.0 parts by mass or less.

The content of each of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 is not particularly limited as long as the total content is within the above range, but the content of the wrinkle formation stabilizer 2 is 100 mass by mass of the resin. It is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1.0 part by mass or more, and the upper limit is 6.0 parts by mass or less, preferably 5 parts. It is 0.0 parts by mass or less, more preferably 3.5 parts by mass or less, still more preferably 3.0 parts by mass or less. The blending ratio of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 (wrinkle formation stabilizer 1 / wrinkle formation stabilizer 2) is preferably 0.05 to 0.95, more preferably 0.10 to. It is 0.90, more preferably 0.20 to 0.80, and even more preferably 0.30 to 0.70.

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

(Surface shape of matte layer)
The matte layer is a layer composed of a cured product of a resin composition for forming a matte layer containing the above-mentioned specific wrinkle formation stabilizer in a specific content, and is a layer formed by a cured product of the resin composition for forming the matte layer. In this layer, the formation of wrinkles is stable, and the visibility and texture of the matte effect are stably exhibited by the light diffusion effect caused by the shape of the wrinkles. FIG. 1 is a schematic view in a plan view showing an embodiment of the matte article A of the present embodiment, and is a schematic image of the surface of the matte article A obtained in the embodiment. FIG. 1 shows that the matte article A of the present embodiment has wrinkles formed on its surface, that is, on the surface of the matte layer.

The matte article A has an uneven shape in which at least one surface of the matte layer is composed of irregular wrinkles. The uneven shape formed by such wrinkles is stably formed by the wrinkle forming stabilizer, and the visibility and texture of the matte effect are stably exhibited. Further, the irregular wrinkle is preferably composed of a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions, and the protrusions are linear. It is preferable to have a protrusion. In the present specification, the “streak protrusion” (hereinafter, also referred to as “streak protrusion”) means that the ratio (length / width) of the length to the width of the protrusion is 3 or more, preferably. It means that it is 5 or more, more preferably 10 or more, and the method for determining the length and width is as described later.
In the present embodiment, a more preferable irregular wrinkle is one composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions. ..

Examples of the mode relating to these wrinkles include the mode shown in FIG. In FIG. 1, the surface of the matte article A, 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 streaks. It is configured by including a plurality of convex portions 3 to be formed and a concave portion 2 formed by being surrounded by a plurality of protrusions (plurality of convex portions 3), and at least one of the plurality of curved convex portions 3. In a plan view (observation from the z direction in FIGS. 1 to 3), each portion is formed by meandering linear protrusions, and the meandering recess 2 is surrounded by the meandering linear protrusions. It is also shown to be forming. The matte article A of the present embodiment stably exhibits the visibility and texture of the matte effect due to the stable formation of wrinkles shown in FIG.

Here, "curvature" means having one or more portions in which the extending direction of the convex portion 3 of the continuous line is reversed from one side to the other side in a plan view. As an example of the part where the extending direction is reversed from one side to the other side, for example, when the width of the plan view shape of the convex portion 3 of the line is ignored (when the width is regarded as 0), a continuous curve is used. When approximated, a form having an inflection point and the like can be mentioned. Further, when the width of the convex portion 3 of the line is approximated by a straight line when the width of the plan view shape is ignored, a form having a V-shaped polygonal line or a portion approximated by two sides sandwiching one apex of a triangle. And so on.
Further, "meandering" refers to a portion in which the extending direction of the convex portion 3 of the continuous streak is reversed from one side to the other side (hereinafter, also referred to as "reversed portion") in a plan view of at least 2. When the convex portion 3 of the streak is advanced in the extending direction, the portion where the extending direction of the convex portion 3 of the streak is alternately reversed at the two adjacent portions is provided. Meanders to have. For example, when the width of the convex portion 3 of the line is approximated by a continuous curve when the width of the plan view shape is ignored, a form having a portion approximated by the Roman character "S" can be mentioned. Further, when the width of the convex portion 3 of the line is approximated by a straight line when the width of the plan view shape is ignored, a form having a portion approximated by the Roman character "W" can be mentioned.

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

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

The surface of the matte article A preferably has irregular wrinkles formed at least in a part thereof, and more preferably irregular wrinkles are formed over the entire surface. The portion where the wrinkle is formed is not particularly limited as long as it is the surface of the matte article A. The visibility and texture of the matte effect due to the formation of the wrinkles are exhibited. For example, when a pattern layer described later is provided and irregular wrinkles are formed in a part of the wrinkles, if the wrinkles are formed at a location corresponding to the pattern of the pattern layer (for example, on the pattern), the pattern becomes more visible than the surroundings. Since it is visually recognized as a matte part, it is possible to improve the design.
Further, as shown in FIG. 1, it has a plurality of convex portions formed by a plurality of protrusions having a certain degree of homogeneity although irregular, and a concave portion surrounded by the convex portions. Is preferable. Therefore, it cannot be said that the shape in which the width of the convex portion (protrusion portion) of 1 is extremely changed and the shape in which the height thereof is extremely changed is not a preferable mode for obtaining the visibility and texture of the matte effect. The shapes of the convex portions (protrusions) and the concave portions that form irregular wrinkles will be described below with reference to specific aspects that can be advantageous in stably improving the visibility and texture of the matte effect.

Regarding the shape of the wrinkles formed on at least one surface of the matte layer, the height of the convex portion (height of the protrusion) is preferably 0.5 μm or more, more preferably 1 μm or more, still more preferably 2 μm or more. Yes, the upper limit is about 10 μm or less. The width of the convex portion is preferably 0.1 μm or more, more preferably 0.3 μm or more, still more preferably 0.5 μm or more, and the upper limit is preferably 10 μm or less, more preferably 4 μm or less, still more preferably 3 μm. It is as follows. When the height and width of the convex portion are within the above ranges, the visibility and texture of the matte effect are stably improved in relation to the concave portion.
Here, the above-mentioned dimensions of the convex portion are the arbitrary 10 convex portions (projections) in any 10 locations (100 μm square area × 10 locations) of the matte article of the present embodiment, that is, a total of 100 convex portions. It is an average value. Further, as shown in FIG. 1, since the width of the convex portion (projection portion) of 1 is not the same and is wide and narrow, the width of the convex portion (projection portion) of 1 is the convex portion (projection portion) of 1. ) Is the average value of the widths of any five places. The same applies to the height of the convex portion (protruding portion).

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

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

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

The convex portion and the concave portion may have portions having substantially the same direction and substantially the same width, but the length thereof is preferably short from the viewpoint of stably improving the visibility of the matting effect and improving the texture. Specifically, the continuous length of the convex portions and concave portions in substantially the same direction and substantially the same width is preferably 95 μm or less, more preferably 80 μm or less, further preferably 70 μm or less, and the lower limit is preferably 5 μm or more. It is more preferably 10 μm or more, still more preferably 15 μm or more. When the length is within the above range, wrinkles become more irregular, so that the visibility and texture of the matte effect are stably improved.
Here, 80% or more of any 10 convex portions and concave portions (that is, a total of 100 convex portions and concave portions) in any 10 locations (100 μm square area × 10 locations) of the matte article A are under the above conditions. It is preferable that it satisfies the above conditions, more preferably 85% or more, further preferably 90% or more, still more preferably 95% or more. In addition, "abbreviation" of "substantially the same" in the present specification means that they are almost the same, meaning a difference within ± 3 ° in the case of direction without branching, and ± 5 in the case of width. Means a difference within%.

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

FIG. 2 is a cross-sectional view showing an embodiment of the matte article A, which is a cross-sectional view of the matte article cut along a plane parallel to the thickness direction (Z direction in the figure).
The shape of the concave portion may be, for example, an acute-angled shape as shown in 2a of FIG. 2, a semicircular or semi-elliptical shape as shown in 2b, or a combination thereof. Further, it may have a shape as shown in 2c of FIG. 2 in which one convex portion has a concave portion in a part.
On the other hand, as the shape of the convex portion, although the width is wide and narrow as shown in 3a and 3b of FIG. 2, it exhibits a semicircular or semi-elliptical 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 stably exhibited, but it is easy to produce. In consideration of the above, it is usually 1 μm or more, preferably 2 μm or more, more preferably 3 μm or more, further preferably 4 μm or more, still more preferably 5 μm or more, and the upper limit is preferably 300 μm or less, more preferably 200 μm or less. It is more preferably 150 μm or less, and even more preferably 100 μm or less.
In the present specification, the thickness of the matte layer is the average value of the values of 20 points obtained by measuring the thickness of 20 points from the image taken with a scanning electron microscope (SEM) for the cross section of the matte article. do. The acceleration voltage of the SEM is set to 3 kV, and the magnification is set according to the thickness. The same applies to the thickness of other layers.

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

(resin)
The resin that forms the matte layer is a resin that forms a resin composition for forming a matte layer containing the above wrinkle formation stabilizer in a predetermined amount and is cured to become a cured product and constitutes the matte layer. good. Examples of such a resin include an ionizing radiation curable resin. Since the matte layer is a layer that can be provided on the outermost surface of the matte article A, it is a resin that easily forms wrinkles with a wrinkle formation stabilizer, and is resistant to use as a matte article from the viewpoint of improving usability. It is preferable that the resin easily exhibits surface characteristics such as scratch resistance, stain resistance, and weather resistance, and processing characteristics, and the ionizing radiation curable resin is a preferable resin from these viewpoints. Since the content of the wrinkle-forming stabilizer contained in the matte layer is extremely small in the matte article A, the performance of the resin forming the matte layer is more directly exhibited as its surface property.

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

Examples of the ionizing radiation curable resin include an electron beam curable resin and an ultraviolet curable resin. From the viewpoint of stabilizing the formation of wrinkles by the wrinkle formation stabilizer and improving the visibility and texture of the matte effect, ultraviolet rays are used. A curable resin is preferable.
Specifically, the ionizing radiation curable resin can be appropriately selected and used from the polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. Here, "(meth) acrylate" means "acrylate or methacrylate".
Examples of the polyfunctional (meth) acrylate monomer include a (meth) acrylate monomer having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. The (meth) acrylate monomer is not particularly limited as long as it has a (meth) acryloyl group, but is, for example, a di (meth) acrylate such as diethylene glycol di (meth) acrylate or propylene glycol di (meth) acrylate (number of functional groups:: 2); Tri (meth) acrylate such as trimethyl propanetri (meth) acrylate (number of functional groups: 3); Tetra (meth) acrylate such as trimethylol propanetetra (meth) acrylate and dipentaerythritol tetra (meth) acrylate ( Number of functional groups: 4); Examples thereof include (meth) acrylate having 5 or more (meth) acryloyl groups such as dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate (number of functional groups: 5 or more). ..

Polyfunctionality (meth) from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect, and further improving the surface characteristics such as scratch resistance and weather resistance, and the processing characteristics. ) The number of functional groups of the acrylate monomer is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, further preferably 2 or more and 4 or less, and further preferably 2 or more and 3 or less. These polyfunctional (meth) acrylates may be used alone or in combination of two or more.

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

These polymerizable oligomers may be used alone or in combination of two or more.
Urethane (meth) acrylate from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect, and further improving the surface characteristics such as scratch resistance and weather resistance, and the processing characteristics. Acrylate, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, acrylic (meth) acrylate oligomer are preferable, urethane (meth) acrylate oligomer, polycarbonate (meth) ) Acrylate oligomers are more preferred, and urethane (meth) acrylate oligomers are even more preferred.

The number of functional groups of these polymerizable oligomers determines the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matting effect, as well as the surface characteristics such as scratch resistance and weather resistance, and the processing characteristics. From the viewpoint of improvement, those having 2 or more and 8 or less are preferable, and as the upper limit, 6 or less is more preferable, 4 or less is further preferable, and 3 or less is further preferable.
From the same viewpoint as this, the weight average molecular weight of these polymerizable oligomers is preferably 2,500 or more and 7,500 or less, more preferably 3,000 or more and 7,000 or less, and 3,500 or more and 6,000. The following is more preferable. Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted with standard polystyrene.

In the matte article A, as the resin forming the matte layer, it is preferable to use the above-mentioned polymerizable oligomer and the polymerizable monomer in combination. In this case, the content of the polymerizable oligomer with respect to a total of 100 parts by mass of the polymerizable oligomer and the polymerizable monomer is preferably 40 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 55 parts by mass or more, still more. It is preferably 60 parts by mass or more, and the upper limit is preferably 90 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 70 parts by mass or less. When the content of the polymerizable oligomer is within the above range, the formation of wrinkles can be stabilized, the visibility and texture of the matte effect can be stably improved, and the surface such as scratch resistance and weather resistance can be improved. It is also possible to improve the characteristics and processing characteristics.

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

When the resin is an ultraviolet curable resin that is cured by ultraviolet rays, it preferably contains additives such as a photopolymerization initiator and a photopolymerization accelerator. By including these additives, the formation of wrinkles is promoted, and the visibility and texture of the matte effect are improved.
Examples of the photopolymerization initiator include one or more selected from acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, benzyl dimethyl ketal, benzoyl benzoate, α-acyl oxime ester, thioxanthones and the like.
Further, the photopolymerization accelerator can reduce the polymerization inhibition by air at the time of curing and accelerate the curing rate. For example, from p-dimethylaminobenzoic acid isoamyl ester, p-dimethylaminobenzoic acid ethyl ester and the like. One or more selected species can be mentioned.

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

[60 ° gloss value]
The matte article A is an article having excellent visibility and texture of a matte effect, and has a 60 ° gloss value of 5.0 or less. In the present specification, "matte" means that it is difficult to visually recognize the gloss, and it cannot be said unconditionally because it changes depending on the color tone, pattern, etc. of the article. It shall be treated as "matte".
So far, for example, black and other dark colors (“dark color” means low brightness, for example, CIE (International Commission on Illumination) L ^* a ^* b ^* L in the color system, which is measured in accordance with JIS Z8781-4: 2013. ^For matte articles exhibiting a * value (hereinafter, may be simply referred to as "L ^* value"), which usually means about 40 or less, preferably 30 or less), a matting agent is used. Although it is possible to obtain 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 are obtained. Since unevenness occurs, it is not easy to manufacture, and the surface characteristics are deteriorated. Further, for example, for a matte article exhibiting a color tone other than black or other dark colors, there is a lower limit to the value of the 60 ° gloss value even if a matting agent is used, which is the same as that of a matte article exhibiting black color, and in any case, the surface surface. It was not easy to obtain an article having excellent characteristics and excellent visibility of the matte effect. Such a tendency becomes more remarkable as the 60 ° gloss value is reduced.

In the matte article A, by using a wrinkle formation stabilizer and reducing the content thereof as described above, the formation of wrinkles is stabilized, and the visibility and texture of the matte effect are stable and excellent. Has come to be obtained. Further, by suppressing the amount of the wrinkle formation stabilizer used to an extremely small amount, it is possible to form a layer by suppressing a significant increase in the viscosity of the resin composition, and the surface caused by the particles used in the wrinkle formation stabilizer. Since the effect on the deterioration of the characteristics is also minimized, it naturally has surface characteristics such as excellent scratch resistance, stain resistance, and weather resistance according to the characteristics of the resin used for the matte layer. Become.

Although the matte article A changes according to the color tone as described above, the 60 ° gloss value on the matte layer side is 5.0 or less, and further 4.0 or less, 3.6 or less, 2.0 or less. It is possible to exhibit extremely excellent visibility of the matting effect.
Further, a matte article exhibiting a color tone other than black or other dark colors can also have the above 60 ° gloss value. The 60 ° gloss value on the matte layer side of the matte article A is substantially the same as the 60 ° gloss value on the surface of the layer forming the outermost surface of the article. Further, when the other layer is further provided and the other layer is provided on the surface side of the matte layer, the 60 ° gloss value means the 60 ° gloss value of the other layer, but is glossy. The reason why the erased article A has a specific 60 ° gloss value is substantially due to the composition of the matte layer.
In the present specification, the 60 ° gloss value on the matte layer side is the 60 ° mirror surface gloss measured in accordance with JIS K 5600-4-7: 1999, and a gloss meter or the like at any 10 points is used. It is an average value of values that can be measured from the matte layer side.

Further, it is preferable that the standard deviation (σ) of the matte article A is less than 0.30 with respect to the 60 ° gloss value. The standard deviation (σ) of the 60 ° gloss value is a numerical value indicating the degree of variation of the 60 ° gloss value at any 10 points, and the smaller the deviation, the smaller the variation, that is, the more stable the formation of wrinkles. It is a meaningful index. As shown in Examples described later, the standard deviation (σ) of the 60 ° gloss value of the matte article A is less than 0.30, the formation of wrinkles is stable, and the standard deviation (σ). ) Is small, which leads to excellent surface characteristics, particularly excellent scratch resistance, and excellent visibility and texture of matting effect.

From the viewpoint of improving the surface characteristics, the visibility of the matte effect, and the texture, the standard deviation (σ) of the 60 ° gloss value is preferably 2.8 or less, more preferably 2.5 or less, still more preferably. It is 2.3 or less. The lower limit is not particularly limited because the smaller it is, the more preferable it is. However, it is difficult to completely converge the standard deviation (σ) of the 60 ° gloss value on the surface of the matte layer to 0, and to that extent. Since the need for is not high, the lower limit of the standard deviation (σ) of the 60 ° gloss value is usually set to 0.05 or more.

[Layer structure]
The matte article A may be an article having a specific matte layer as described above, and does not need to have a base material. That is, the matte article A has a base material as desired, and may have a layer structure without a base material. Therefore, the simplest layer structure of the matte article A is a layer structure consisting of a single layer having no base material and only a matte layer, specifically, a wrinkle formation stabilizer is applied to 100 parts by mass of the resin. The matte layer is composed of a cured product of a resin composition containing 5 parts by mass or more and 6.0 parts by mass or less, and has an uneven shape in which at least one surface of the matte layer is formed of irregular wrinkles. The layer structure is composed of a single layer having only a matte layer having a 60 ° gloss value of 5.0 or less.

(More realistic layer structure)
However, when the matte article A has a layer structure consisting of the single layer, options for obtaining various performances required for the matte article, such as mechanical strength, post-processing suitability, and designability, may be restricted. many. Therefore, the layer structure of the matte article A is preferably a layer structure having a base material, that is, a base material and a matte layer. In this case, as shown in FIG. 3, a surface having a base material and a matte layer and having an uneven shape formed by irregular wrinkles of the matte layer is a surface opposite to the base material. It is preferable to have. This is because the visibility and texture of the matte effect can be improved.

〔Base material〕
In addition to the matte layer, the matte article A may further have a base material, if desired, and as described above, it is preferable to have a base material from the viewpoint of avoiding various restrictions. The base material functions as a support for providing a matte layer.
The form (or shape) of the base material can be various shapes such as a film, a sheet, a plate, a polyhedron, a polygonal prism, a cylinder, a cone, a spherical surface, and a rotating elliptical surface, and is not particularly limited. The films, sheets, and plates are referred to as films, sheets, and plates in order from the one having a relatively thin thickness, but in the present specification, it is not meaningful to strictly distinguish these three types, and these three types are used. There is no difference in the interpretation of rights of the present invention due to the three types of differences.

As the base material used in the present embodiment, those usually used as a base material for articles such as decorative materials and decorative sheets can be used without limitation, and for example, fibrous materials such as paper, non-woven fabric and woven cloth, etc. A typical example is a base material made of a resin, a wood-based material, a metal, a non-metallic inorganic material, or the like.
The base material may be a single layer, or may be a stack of two or more layers made of the above materials. When the base material is a laminate of two or more layers, it is preferable that two or more layers of different materials are laminated to complement each other's various performances of the materials of each layer. Examples of the base material formed by laminating two or more layers include the following A to J. In addition, "/" indicates the interface of each layer.
(A) Resin / wood-based material (B) Resin / metal (C) Resin / fibrous material (D) Resin / non-metal inorganic material (E) Resin 1 / Resin 2
(F) Metal / wood-based material (G) Metal / non-metal inorganic material (H) Metal / fibrous material (I) Metal 1 / Metal 2
(J) Non-Metallic Inorganic Material / Fibrous Material In E above, the resin 1 and the resin 2 represent different types of resins (for example, the resin 1 is an olefin resin and the resin 2 is an acrylic resin). Further, in the above H, the metal 1 and the metal 2 represent different types of metals (for example, the metal 1 is copper and the metal 2 is chromium).

When the base material is a laminated body, an adhesive layer, an adhesive layer, and a primer layer (anchor layer, easy) are used as layers for strengthening the adhesive force between the adjacent layers between the layers of each constituent layer of the laminated body. It may be configured to further provide an adhesive layer).

Examples of the base material of the fibrous material include kraft paper, titanium paper, linter paper, sulfated paper, paraffin paper, glassin paper, parchment paper, backing paper for wallpaper, thin leaf paper, high-quality paper, Japanese paper, board paper, base paper for gypsum board, etc. Paper substrate can be mentioned. Further, as the paper base material, in order to improve the interlayer strength between the fibers or between the multi-layered paper base material and to prevent fluffing, further acrylic resin, styrene-butadiene rubber, melamine resin, urethane resin Various resins such as the above may be added (impregnated with the resin after the fabrication or internally filled at the time of the fabrication). Examples of such a paper base material include inter-paper reinforced paper and resin-impregnated paper. Further, 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 a backing paper for wallpaper, which is widely used in the field of building materials. There is also the original wallpaper.

Examples of the base material of the non-woven fabric or woven fabric include inorganic fibers made of inorganic materials such as glass, alumina, silica, and carbon, and organic fibers made of various synthetic resins such as polyester resin, acrylic resin, polyethylene, and polypropylene. Examples thereof include non-woven fabrics or woven fabrics composed of various fibers such as protein-based or cellulose-based natural fibers such as silk, cotton and linen, glass fibers and carbon fibers, and base materials such as composites thereof.

Examples of the base material of the resin include a base material composed of various resins such as synthetic resin and natural resin. As the synthetic resin, a thermoplastic resin and a curable resin can be used.
Examples of the thermoplastic resin include polyolefin resins such as polypropylene, polyethylene, polymethylpentene, polyolefin-based 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-based thermoplastic elastomer; polymethyl (meth) acrylate, polybutyl ( Acrylic resins such as meta) acrylate and methyl (meth) acrylate-butyl (meth) acrylate copolymers; polyamide resins typified by nylon 6, nylon 66 and the like; cellulose-based resins such as cellulose triacetate, cellophane and cellroid; polystyrene , Acrylonitrile-styrene copolymer, styrene resin such as acrylonitrile-butadiene-styrene resin (ABS resin); polyvinyl alcohol, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polycarbonate resin, thermoplastic resin, Examples thereof include a resin base material made of a thermoplastic resin such as a polyimide resin.
Examples of the curable resin include an ionizing radiation curable resin that can form the matte layer described above, and other thermosetting resins.
Moreover, as a natural resin, natural rubber, pine fat, amber and the like can be mentioned.

Examples of the base material for wood-based materials 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 base material may be in the form of a film called veneer or a sheet, or in the form of a single plate, plywood, laminated lumber, particle board, fiber plate or the like.

Metals include aluminum-containing alloys such as aluminum or duralmin, iron-containing alloys such as iron or carbon steel and stainless steel, copper-containing alloys such as copper or brass and bronze, gold, silver, chromium, nickel and cobalt, Examples include tin and titanium. Further, as the metal base material composed of metal, those obtained by subjecting these metals to a treatment such as plating can also be used.
Non-metallic inorganic materials include non-ceramic ceramic materials such as cement, ALC (lightweight cellular concrete), plaster, calcium silicate, and wood piece cement, ceramic ceramic materials such as ceramics, earthenware, glass, and limestone, and limestone. (Including marble), natural stones such as granite and limestone.

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

When the base material is colored, the colorant includes, for example, white pigments such as titanium white, and inorganic pigments such as iron black, yellow lead, titanium yellow, petals, cadmium red, ultramarine blue, and cobalt blue; quinacridone red. Organic pigments or dyes such as isoindolinone yellow, phthalocyanine blue, nickel-azo complex, azomethine azo black pigment, perylene black pigment; metal pigment consisting of scaly foil pieces such as aluminum and brass; titanium dioxide coated mica, base Examples thereof include colorants such as pearl pigments made of scaly foil pieces such as lead carbonate. For example, when the surface hue of the adherend to which the article is attached varies, it is desired to conceal the surface hue and improve the color tone stability of the pattern layer and the wide area decorative layer provided as desired. , Inorganic pigments such as white pigments may be used.

In the case of coloring a synthetic resin, any means can be adopted, such as addition of a colorant to the resin (kneading, kneading), formation by applying a coating film of a paint containing the resin and the colorant, and the like. .. In the case of coloring paper, non-woven fabric, or woven fabric, it can be carried out by any means such as mixed extraction with pulp or fiber material, formation of a coating film, or a combination thereof.
In the case of coloring wood, it can be carried out by either dyeing with a dye, forming a coating film, or a combination thereof. In the case of coloring a metal, in addition to forming a coating film, an electrolytic coloring method for forming a metal oxide film on the surface by using an anodic oxidation method or the like can be adopted. Further, in the case of a non-metallic inorganic material, it can be carried out by either means of forming a coating film or adding it to a base material, or a combination thereof.

Additives may be added to the base material, if necessary. As additives, mainly in the case of resins, 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. And so on. The blending amount of the additive is not particularly limited as long as it does not impair the surface characteristics, processing characteristics, etc., and can be appropriately set according to the required characteristics, etc.

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

The shape and dimensions of the base material are not particularly limited and may be appropriately selected according to the intended use, desired various performances, and processing suitability.
When the base material is a base material in the form of a film, sheet, or plate, thickness is a typical design dimension of the article. The thickness is not particularly limited, but generally, it may be about 10 μm or more and 10 cm or less from the viewpoint of manufacturing processability, mechanical strength, usability, economy, and the like. In the form of a film or sheet, the thickness thereof 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, further preferably 100 μm or less.
When the base material is in the form of a plate, the thickness thereof is preferably 1 mm or more and 2 cm or less.
Further, if the substrate is a paper substrate, basis weight, usually preferably 20 ~ 150g / ^{m 2,} more preferably 30 ~ 100g / ^{m 2.}

In order to improve the adhesion of the base material to the other layers constituting the article and the adherend on which the article is laminated, one or both sides of the base material may be physically surface-treated by an oxidation method, an unevenness method, etc., or chemically. Surface treatment such as surface treatment may be performed, or a primer layer may be formed.
Examples of the oxidation method include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, an ozone-ultraviolet treatment method and the like, and examples of the unevenness method include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of the base material, but in general, the corona discharge treatment is preferable from the viewpoint of the effect and operability of the surface treatment.

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

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

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

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

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

For the purpose of improving the adhesiveness to the adherend, the matte article A is on the side opposite to the wrinkled surface of at least one of the matte layers, and when it has a base material, the matte base material is glossy. A primer layer (also referred to as a "backside primer layer") may be provided on the side opposite to the side on which the vanishing layer is provided.

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

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

The transparent resin layer may be transparent to the extent that the base material side can be visually recognized from the transparent resin layer, and if it has a decorative layer, it may be transparent to the extent that the decorative layer can be visually recognized, and is colorless and transparent. In addition, it may be colored transparent or translucent. That is, in the present specification, "transparency" means that in addition to colorless and transparent, colored transparent and translucent are also included.

The transparent resin layer may contain a weathering agent such as an ultraviolet absorber and a light stabilizer, and an additive such as a colorant. As the additives such as these weather resistant agents and colorants, 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 further preferably 60 μm or more and 100 μm or less, from the viewpoint of protecting the decorative layer and considering processing suitability.

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

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

As the pattern (pattern) of the pattern layer, a pattern as desired may be adopted without particular limitation. For example, a wood grain pattern such as an annual ring or a conduit groove on the surface of a wood board, a stone grain pattern on a stone board surface such as marble or granite, etc. Examples include a texture pattern on the surface of a cloth, a textured pattern on a leather surface, a geometric pattern, characters, figures, and a combination thereof.

The ink used for the decorative layer is a binder resin mixed with colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, ultraviolet absorbers, light stabilizers, etc. as appropriate. used.
The binder resin of the decorative layer is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic copolymer, vinyl chloride-vinyl acetate common weight. Examples thereof include a coalesced resin, a vinyl chloride-vinyl acetate-acrylic copolymer resin, a chlorinated propylene resin, a nitrocellulose resin, and a cellulose acetate resin. Further, various types of resins such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound can be used.

As the colorant, a pigment having excellent hiding power and weather resistance is preferable. As the pigment, the same pigment as those exemplified as the pigment that can be used for the base material can be used.
The content of the colorant is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and 30 parts by mass or more and 70 parts by mass with respect to 100 parts by mass of the resin constituting the decorative layer. The following is more preferable.

The decorative layer may contain an ultraviolet absorber, a weathering agent such as a light stabilizer, and an additive such as a colorant.
The thickness of the decorative layer may be appropriately selected according to the desired pattern, but from the viewpoint of hiding the ground color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, and 1 μm or more. 10 μm or less is more preferable, and 2 μm or more and 5 μm or less is further preferable.

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

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

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

(Performance of matte article A)
Matte articles A, excellent surface property, have inter alia good scratch resistance, for example, a 60 ° gloss value of the matting layer side before performing the following rubbing test and G _0, the rubbing test When the 60 ° gloss value on the matte layer side is G ₁ , the rate of change of the gloss value (| (G _{1 −} G ₀ ) | / G ₀ × 100) is 20% or less. It has excellent scratch resistance (particularly steel wool resistance).
(Rubbing test)
Place the matte article on the base of the abrasion tester type II (JIS L0849: 2013), set steel wool # 0000 so as to contact the matte layer of the matte article, load 1500 g / cm ² , move. It was reciprocated 30 times at a speed of 100 mm / sec and a reciprocating movement distance of 100 mm.

The rate of change in the gloss value is used as an index of steel wool resistance, which is one of the scratch resistance of the matte article, by observing the range of change in the gloss value before and after the rubbing test. The larger the rate of change in the gloss value, the higher the gloss value after the rubbing test, that is, the surface of the matte article becomes glossy due to small scratches, which indicates that the steel wool resistance is inferior.
Since the matte article A has excellent scratch resistance, the rate of change of the gloss value is 20% or less as described above, and further, 15% or less, 10% or less, 8% or less, It can be less than 5%.

[Manufacturing method of matte article A]
As described above, the matte article A may have a layer structure consisting of a single layer of the matte layer, or may have a layer structure including at least a base material. Hereinafter, the method for producing the matte article A will be described separately when it has a single layer and when it has a base material and other layers.

First, in the case of a single layer, the matte article A can be produced by the following method.
The resin composition for forming a matte layer, that is, having an average particle diameter of 1 μm or more and 100% or less or 30 μm or less of the thickness of the matte layer on the surface of the releasable support having a releasable layer. The wrinkle formation stabilizer 1 having the smaller one as the upper limit and the wrinkle formation stabilizer 2 having an average particle diameter of less than 1 μm are 100 parts by mass of the resin as the total amount of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2. A step of applying a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less to form a coating layer, and irradiating with light having a wavelength of at least 100 nm or more and less than 200 nm to cure the matte layer. It is preferably produced through a matte layer forming step of forming. When the resin composition contains a solvent, a solvent drying step may be performed after the step of forming the coating layer.
The releasable support having the releasable layer may be peeled off when the matte article A is used.

Next, when the base material and other layers are provided, the matte article A can be produced by the following method.
The matte article A contains, for example, a wrinkle formation stabilizer on one main surface side of a base material (preferably a base material sheet) in an amount of 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. , A step of applying a resin composition for forming a matte layer to form a coating layer, irradiating with light having a wavelength of at least 100 nm or more and less than 200 nm to cure the coating layer to form a matte layer. It is preferably manufactured through a forming step. 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 the matte article A can be particularly suitable for producing the matte article A having a 60 ° gloss value of 5.0 or less on the matte layer side. Above all, in the method for producing the matte article A, in particular, the amount of particles added on the order of μm is suppressed to a low content of 6.0 parts by mass or less with respect to 100 parts by mass of the resin, and the 60 ° gloss value is 5. In that a matte surface (low gloss, low gloss) of 0 or less can be realized, it is different from the conventionally known methods for manufacturing matte articles such as matte cosmetic materials and matte cosmetic sheets. ..
By such a manufacturing method, the matte article A can be easily obtained. Specifically, when forming the matte layer, a low wavelength (short wavelength) ultraviolet ray of at least 100 nm or more and less than 200 nm is irradiated to a resin composition for matte formation containing a wrinkle formation stabilizer for forming the matte layer. By doing so, wrinkles can be formed on at least one surface of the matte layer, and it becomes easy to stably impart the visibility and texture of the matte effect to the matte article (matte layer).

Regarding the mechanism by which wrinkles are formed on at least one surface of the matte layer by irradiating the resin composition for forming the matte layer with such low-wavelength ultraviolet rays, and the visibility and texture of the matte effect are exhibited. The details of this are unknown, but it is presumed that it is due to the following mechanism.

When a coating material coated with a resin composition for forming a matte layer to a predetermined thickness is irradiated with low-wavelength ultraviolet rays, the energy of the ultraviolet rays permeates only the surface portion, and the energy does not reach the lower layer. Therefore, it is considered that wrinkles are formed by causing curing shrinkage only on the surface because only the surface portion of the resin composition starts to cure. As described above, it is considered that the formation of wrinkles occurs in a state where only a certain thickness direction from the surface of the resin composition for forming a matte layer is cured by irradiation with ultraviolet rays having a low wavelength.
Further, as a comparison between Examples and Comparative Examples described later, when the wrinkle formation stabilizer is not contained, the formation of wrinkles becomes unstable and the visibility of the matte effect is stable over the entire surface of the matte layer, which is sufficient. Therefore, the stable expression of the visibility of the matting effect cannot be explained only by the curing of only the surface portion by low-wavelength ultraviolet rays. That is, in order for the matte article A to stably have wrinkles to exhibit the visibility of the matte effect, it is indispensable to include a wrinkle formation stabilizer. Considering that the stable matting effect due to the stabilization of wrinkle formation is not obtained when the wrinkle formation stabilizer is not contained, the wrinkle formation stabilizer functions like a nucleus that triggers wrinkle formation. The resin on the surface portion of the resin composition gathers around the core, and wrinkles are formed along with the formation of the convex portion (projection portion) and the convex portion (projection portion) of the wrinkle, resulting in wrinkles. It is considered that the formation of is stable. Then, it is considered that the wrinkles formed in this way stably impart the visibility of the matte effect to the matte article A by the light diffusion effect due to its shape, and also stably impart the texture. Be done.

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

In this production method, it is preferable to irradiate the resin composition for forming a matte layer with light having a wavelength of at least 100 nm or more and less than 200 nm. By 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 to cure, so that only the surface undergoes curing shrinkage. As a result, the formation of wrinkles is stable, and the surface layer of the resin composition becomes a cured product having wrinkles, which constitutes a matte layer. After that, the curing progresses from the portion near the surface where the curing progresses slowly to the deep portion separated in the depth direction, and the layer of the resin composition becomes a cured product, thus covering the entire thickness of the resin composition. It constitutes a matte layer having wrinkles that are cured and exhibit a light diffusing effect on the surface. 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, as will be described later.

The wavelength light of at least 100 nm or more and less than 200 nm includes, for example, a rare gas such as Ar, Kr, Xe, Ne, a halide of a rare gas due to a halogen such as F, Cl, I, Br, or a mixed gas thereof. An excited state dimer formed by electric discharge, that is, "excimer light" containing light in the ultraviolet wavelength range from an excimer is preferable. The wavelength of the excimer light and the excimer used as the light source include, for example, light having a wavelength of 126 nm radiated from the excimer of _{Ar 2} _{(hereinafter, abbreviated as “126 nm (Ar 2} )”), 146 _{nm (Kr 2} ), and 157 nm. Light having a wavelength of (F ₂ ), 172 nm (Xe ₂ ), 193 nm (ArF) or the like can be preferably adopted. As the excimer light, either spontaneous emission light or laser light having high coherence (coherence) due to stimulated emission can be used, but it is usually sufficient to use spontaneous emission light. The discharge lamp that emits the light (ultraviolet rays) is also referred to as an "excimer lamp".
Excimer light has a single wavelength peak, and is characterized by having a narrower half-width of wavelength than ordinary ultraviolet rays (for example, ultraviolet rays emitted from a metal halide lamp, a mercury lamp, or the like). By using such excimer light, the formation of wrinkles is stabilized, and the visibility and texture of the matte effect are stably improved.

From the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect, the wavelength is preferably 120 nm or more, more preferably 140 nm or more, still more preferably 150 nm or more, still more preferably 155 nm. As described above, the upper limit is less than 200 nm, and particularly preferably 172 nm (Xe ₂ ). As described above, in the present manufacturing method, from the viewpoint of stably improving the visibility and texture of the matting effect, it is preferable to use light having a lower wavelength, and among the low-wavelength ultraviolet rays (wavelength: 280 nm or less), It can be said that low-wavelength ultraviolet rays in the region of less than 200 nm are preferable.

In the present production method, the integrated light amount of the wavelength light is preferably 1 mJ / cm ² or more, more preferably 10 mJ, from the viewpoint of stabilizing the formation of wrinkles and stably improving the visibility and texture of the matte effect. / cm ² or more, more preferably 30 mJ / cm ² or more, even more preferably 50 mJ / cm ² or more. ^{The upper limit is not particularly limited, and the upper limit is preferably 1,000 mJ / cm 2} or less, more preferably 1,000 mJ / cm 2 or less, from the viewpoint of reducing the number of lights required for irradiating wavelength light and improving productivity such as improvement of production efficiency. It is 500 mJ / cm ² or less, more preferably 300 mJ / cm ² or less.
From the same viewpoint as this, the ultraviolet output 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. It is / cm or less, more preferably 5 W / cm or less, still more preferably 3 W / cm or less.
The oxygen concentration when irradiating the wavelength light is preferably lower, preferably 1,000 ppm or less, more preferably 750 ppm or less, still more preferably 500 ppm or less, still more preferably 300 ppm or less.

In the matte layer forming step in the present production method, in addition to the above-mentioned irradiation with wavelength light of at least 100 nm or more and less than 200 nm, other treatments that contribute to the curing of the resin composition for forming the matte layer may be performed.
For example, from the viewpoint of stabilizing the formation of wrinkles due to the difference in the degree of hardening progress between the surface portion and the deep portion separated from the surface in the depth direction and promoting the progress of hardening to the deep portion, for example, 200 nm or more. Wavelength light of 100 nm or more and less than 200 nm after pre-irradiating with wavelength light of 380 nm or more, preferably 385 nm or more and 400 nm or less to pre-cure the resin composition for forming a matte layer. Or, after irradiation with light having a wavelength of 100 nm or more and less than 200 nm, post-curing may be performed to further cure the resin composition. Regarding pre-curing and post-curing, the necessity of adoption may be appropriately determined according to the desired properties required for the matte layer (for example, surface characteristics such as scratch resistance and stain resistance, and processing characteristics). Further, although the above-mentioned wavelength light belongs to ultraviolet rays, it is also possible to use not only ultraviolet rays but also other ionizing radiations such as electron beams. For example, in post-curing, an electron beam can be preferably used from the viewpoint of improving the surface characteristics of the matte layer.

In the present 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, or a comma coating method. The layer (uncured resin layer) can be formed by irradiating with light having a wavelength of at least 100 nm or more and less than 200 nm.

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

[Cosmetic member A]
As a typical use of the matte article A, the matte article A can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, vehicles, home appliances, etc., or is adhered. It is also possible to use it as a decorative member by laminating it with a material, combining it, or combining it (hereinafter, the decorative member using these matte articles A may be referred to as "decorative member A"). .. Which one to use may be determined as desired.
When the decorative member A has an adherend, the decorative member A has the adherend and the above-mentioned matte article A. Specifically, the surface of the adherend that requires decoration and the matte article A. The matte layer is laminated so that the wrinkles of the matte layer are formed and the surface on the opposite side to the one surface that exhibits the visibility and texture of the matte effect is opposed to each other. Further, when the matte article A has a sheet form, it also has a feature that it can be easily laminated on the adherend.

(Adhesion material)
Examples of the adherend include a member made of a material appropriately selected from the materials exemplified as those that can be adopted as the base material.
The adherend may be appropriately selected from the above depending on the intended use, and may be used as an interior member of a building such as a wall, a ceiling, or a floor, or an exterior member such as an outer wall, a roof, an eaves ceiling, a fence, or a gate, or a window. When fittings or building members such as frames, doors, handrails, skirting boards, surrounding edges, moldings, etc. are used, wood members made of wood-based materials, metal members made of metal, and resins made of resin. It is preferably composed of at least one member selected from the members, and when the use is for exterior members such as entrance doors, window frames, doors and other fittings, those composed of at least one member selected from metal members and resin members. Is preferable.

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, and further preferably 0.5 mm or more and 3 mm or less.

(Adhesive layer)
The adherend and the matte article A 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 a known adhesive can be used and may be appropriately selected depending on the intended use. For example, adhesives such as moisture-curable adhesives, anaerobic curable adhesives, dry-curable adhesives, UV-curable adhesives, heat-sensitive adhesives (for example, hot melt adhesives), and pressure-sensitive adhesives are preferable. Be done.

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

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

(Manufacturing method of decorative member A)
The decorative member A can be manufactured through a step of laminating the matte article A and the adherend.
This step is a step of laminating the adherend and the matte article A, and wrinkles are formed on the surface of the adherend that requires decoration and the matte layer of the matte article A, and the visibility of the matte effect is visible. And the surface opposite to one surface that develops the texture, and if the matte article A has a substrate, the surface on the substrate side is opposed to each other and laminated. Examples of the method of laminating the adherend and the matte article A include a laminating method of laminating the matte article A on a plate-shaped adherend by pressing it with a pressure roller via an adhesive layer. Be done.

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, and 100 for the reactive hot melt adhesive, although it depends on the type of resin constituting the adhesive. It is preferably ° C. or higher and 130 ° C. or lower. Further, in the case of vacuum forming, it is generally performed while heating, and it is preferably 80 ° C. or higher and 130 ° C. or lower, and more preferably 90 ° C. or higher and 120 ° C. or lower.

(Use of decorative member A)
The decorative member A obtained as described above can be arbitrarily cut, and the surface and the end of the wood can be arbitrarily decorated by using a cutting machine such as a router or a cutter to perform grooving, chamfering, or the like. And various uses, for example, interior members of buildings such as walls, ceilings, floors, exterior members such as outer walls, eaves ceilings, roofs, walls, fences, window frames, doors, door frames, handrails, skirts, etc. In addition to fittings or building members such as surrounding edges and malls, general furniture such as stools, shelves and desks, kitchen furniture such as dining tables and sinks, and various furniture used around water such as kitchens, toilets, bathrooms and washbasins. It is suitably used as various members such as members, surface decorative boards for cabinets of home appliances, OA equipment, etc., interior and exterior members of vehicles, and the like. When the matte article A is in the form of a sheet, it is suitably used as a decorative sheet for the above-mentioned various members. Further, considering the surface characteristics of the matte article A, particularly excellent scratch resistance, and excellent visibility and texture of the matte effect, applications in which scratch resistance is particularly required, such as the interior of a building, are considered. Among the members, it is suitably used for flooring, and for fitting members such as window frames, doors, door frames, and handrails that are frequently used.
Further, in addition to the above-mentioned various members, the matte article A may be a packaging material, an antiglare film for a display, a white board or a blackboard, a credit card, etc. It can be used for cash cards, telephone cards, various cards such as various certificates, keys for various keyboards, transparent plates (window glass, etc.) for windows, doors, partitions, artificial leather, and the like.

[Matte article B]
Among the matte articles A of the present embodiment, particularly those using two kinds of wrinkle formation stabilizers, that is, matte articles having a matte layer, the matte layer has an average particle diameter of 1 μm or more. The wrinkle-forming stabilizer 1 having an upper limit of 100% or less and 30 μm or less of the thickness of the matte layer, whichever is smaller, and the wrinkle-forming stabilizer 2 having an average particle diameter of less than 1 μm are used. The total amount of the formation stabilizer 1 and the wrinkle formation stabilizer 2 is composed of a cured product of a resin composition containing 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. A matte article (hereinafter, simply "matte article B") in which at least one surface has an uneven shape composed of irregular wrinkles and the 60 ° gloss value of the matte layer is 5.0 or less. Also referred to as) is preferable. By having such a configuration, the matte article B is also excellent in the visibility and texture of the matte effect.

[Matte layer]
The matte layer in the matte article B includes a wrinkle formation stabilizer 1 having an average particle diameter of 1 μm or more and an upper limit of 100% or less or 30 μm or less of the thickness of the matte layer, whichever is smaller, and average particles. The wrinkle formation stabilizer 2 having a diameter of less than 1 μm is used as the total amount of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 in an amount of 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. It is a layer composed of a cured product of the resin composition containing the mixture. That is, in the present embodiment, the matte layer contains 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 forming the matte layer, and wrinkle formation stabilizer 1 and wrinkle formation. It is a layer containing the stabilizer 2.

(Wrinkle formation stabilizer)
As the wrinkle formation stabilizer, the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 described as those used in the matte article A are adopted.
Regarding the wrinkle formation stabilizer, the average particle size, type, content, etc. of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2, the effects exhibited by using the wrinkle formation stabilizer, the wrinkle formation stabilizer and the matting agent. The difference is the same as the content described for the matte article A.

(Surface shape of matte layer)
The surface shape of the matte layer of the matte article B needs to have irregularities formed by irregular wrinkles on at least one surface, and is the same as the content described for the matte article A. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the surface shape of the matte layer of the matte article B.

(resin)
The resin used for forming the matte layer of the matte article B is the same as that of the resin described for the matte article A.

(Resin composition)
The resin composition used for forming the matte layer of the matte article B is the same as that of the resin composition described for the matte article A.

[60 ° gloss value]
The 60 ° gloss value of the matte article B is 5.0 or less, which is the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value.

[Layer structure]
The layer structure such as the simplest layer structure and the more realistic layer structure of the matte article B is the same as the content regarding the layer structure described for the matte article A.

〔Base material〕
The base material of the matte article B is the same as that of the base material described for the matte article A.

[Other layers]
In addition to the matte layer, the matte article B may have the above-mentioned base material and other layers such as a primer layer, a transparent resin layer, a decorative layer, and an adhesive layer, if necessary. These other layers are the same as those relating to the other layers described for Matte Article A above. Therefore, the layer structure shown in FIGS. 3 and 4 can also be applied to the matte article B.

[Manufacturing method of matte article B]
The manufacturing method of the matte article B is also the same as that of the manufacturing method described for the matte article A.

[Cosmetic member B]
As a typical use of the matte article B, the matte article B can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, vehicles, home appliances, etc., or is adhered. It is also possible to use it as a decorative member by laminating it with a material, combining it, or combining it (hereinafter, the decorative member using these matte articles B may be referred to as "decorative member B"). .. Which one to use may be determined as desired.
The form of the matte article B in the decorative member B, the adherend, the adhesive layer, the use of the decorative member B, and the like are the same as those described in the decorative member A.

[Matte article C]
Among the matte articles A of the present embodiment, those adopting a specific kind of wrinkle formation stabilizer, that is, a matte article having a matte layer, the matte layer has an average particle diameter of 1 μm or more. And, the wrinkle formation stabilizer 1 having the upper limit of 100% or less and 30 μm or less of the thickness of the matte layer, whichever is smaller, is 0.5 parts by mass or more and 6.0 parts by mass with respect to 100 parts by mass of the resin. It is composed of a cured product of the resin composition contained below, has an uneven shape in which at least one surface of the matte layer is composed of irregular wrinkles, and the 60 ° gloss value of the matte layer is 5.0. A matte article (hereinafter, also simply referred to as "matte article C"), which is as follows, is preferable. By having such a configuration, the matte article C is also excellent in the visibility and texture of the matte effect.

[Matte layer]
The matte layer in the matte article C contains a wrinkle-forming stabilizer 1 having an average particle size of 1 μm or more and an upper limit of 100% or less or 30 μm or less of the thickness of the matte layer, whichever is smaller. It is a layer composed of a cured product of a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less with respect to parts by mass. That is, in the present embodiment, the matte layer is a layer containing the wrinkle formation stabilizer 1 in a content of 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 forming the matte layer. Is.

(Wrinkle formation stabilizer)
As the wrinkle formation stabilizer, the wrinkle formation stabilizer 1 described as being adopted in the matte article A is adopted.
Regarding the wrinkle formation stabilizer, the average particle size, type, content, etc. of the wrinkle formation stabilizer 1, the effect developed by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are described above. It is the same as the content described for the matte article A.

(Surface shape of matte layer)
The surface shape of the matte layer of the matte article C needs to have irregularities formed by irregular wrinkles on at least one surface, and is the same as the content described for the matte article A. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the surface shape of the matte layer of the matte article C.

(resin)
The resin used for forming the matte layer of the matte article C is the same as that of the resin described for the matte article A.

(Resin composition)
The resin composition used for forming the matte layer of the matte article C is the same as the content relating to the resin composition described for the matte article A.

[60 ° gloss value]
The 60 ° gloss value of the matte article C is 5.0 or less, which is the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value.

[Layer structure]
The layer structure such as the simplest layer structure and the more realistic layer structure of the matte article C is the same as the content regarding the layer structure described for the matte article A.

〔Base material〕
The base material of the matte article C is the same as that of the base material described for the matte article A.

[Other layers]
In addition to the matte layer, the matte article C may have the above-mentioned base material and other layers such as a primer layer, a transparent resin layer, a decorative layer, and an adhesive layer, if necessary. These other layers are the same as those relating to the other layers described for Matte Article A above. Therefore, the layer structure shown in FIGS. 3 and 4 can also be applied to the matte article C.

[Manufacturing method of matte article C]
The manufacturing method of the matte article C is also the same as that of the manufacturing method described for the matte article A.

[Cosmetic member C]
As a typical use of the matte article C, the matte article C can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, vehicles, home appliances, etc., or is adhered. It is also possible to use it as a decorative member by laminating it with a material, combining it, or combining it (hereinafter, the decorative member using these matte articles C may be referred to as "decorative member C"). .. Which one to use may be determined as desired.
The form of the matte article C in the decorative member C, the adherend, the adhesive layer, the method for producing the decorative member C, the use of the decorative member C, and the like are the same as those described in the decorative member A.

[Matte article D]
Among the matte articles A of the present embodiment, those adopting a specific kind of wrinkle formation stabilizer, that is, a matte article having a matte layer, the matte layer has an average particle size of less than 1 μm. The wrinkle formation stabilizer is composed of a cured product of a resin composition containing 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, and at least one surface of the matte layer is non-existent. A matte article (hereinafter, also simply referred to as "matte article D") having an uneven shape composed of regular wrinkles and having a 60 ° gloss value of 5.0 or less of the matte layer is preferable. .. By having such a configuration, the matte article D is also excellent in the visibility and texture of the matte effect.

[Matte layer]
The matte layer in the matte article D contains a wrinkle-forming stabilizer having an average particle size of less than 1 μm in an amount of 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. It is a layer composed of things. That is, in the present embodiment, the matte layer has a content of 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 forming the matte layer, and the average particle size is less than 1 μm. It is a layer containing a wrinkle formation stabilizer.

(Wrinkle formation stabilizer)
As the wrinkle formation stabilizer, the wrinkle formation stabilizer 2 having an average particle size of less than 1 μm, which has been described as being used in the matte article A, is adopted.
Regarding the wrinkle formation stabilizer, the average particle size, type, content, etc. of the wrinkle formation stabilizer 2, the effect exhibited by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matting agent are described above. It is the same as the content described for the matte article A.

(Surface shape of matte layer)
The surface shape of the matte layer of the matte article D needs to have irregularities formed by irregular wrinkles on at least one surface, and is the same as the content described for the matte article A. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the surface shape of the matte layer of the matte article D.

(resin)
The resin used for forming the matte layer of the matte article D is the same as that of the resin described for the matte article A.

(Resin composition)
The resin composition used for forming the matte layer of the matte article D is the same as the content relating to the resin composition described for the matte article A.

[Layer structure]
The layer structure such as the simplest layer structure and the more realistic layer structure of the matte article D is the same as the content relating to the layer structure described for the matte article A.

〔Base material〕
The base material of the matte article D is the same as that of the base material described for the matte article A.

[Other layers]
In addition to the matte layer, the matte article D may have the above-mentioned base material and other layers such as a primer layer, a transparent resin layer, a decorative layer, and an adhesive layer, if necessary. These other layers are the same as those relating to the other layers described for Matte Article A above. Therefore, the layer structure shown in FIGS. 3 and 4 can also be applied to the matte article D.

[Manufacturing method of matte article D]
The manufacturing method of the matte article D is also the same as that of the manufacturing method described for the matte article A.

[Cosmetic member D]
As a typical use of the matte article D, the matte article D can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, vehicles, home appliances, etc., or is adhered. It is also possible to use it as a decorative member by laminating it with a material, combining it, or combining it (hereinafter, the decorative member using these matte articles D may be referred to as "decorative member D"). .. Which one to use may be determined as desired.
The form of the matte article D in the decorative member D, the adherend, the adhesive layer, the method for producing the decorative member D, the use of the decorative member D, and the like are the same as those described in the decorative member A.

[Matte article E]
The matte article of the present embodiment is a matte article (hereinafter, also simply referred to as "matte article E") in which the matte layer is a matte easy decontamination layer in the matte article A. Specifically, it is a matte article having a matte layer, and the matte layer contains a wrinkle formation stabilizer in an amount of 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. The matte layer is composed of a cured product, has an uneven shape in which at least one surface of the matte layer is composed of irregular wrinkles, and has a 60 ° gloss value of 5.0 or less. A matte article in which the matte layer is an easy matte decontamination layer. By having such a structure, the matte article E is excellent in surface characteristics, particularly easy decontamination, and also excellent in visibility and texture of the matte effect.

[Matte layer (matte easy decontamination layer)]
The matte layer in the matte article E is a matte decontamination layer that exhibits particularly easy decontamination property, and the wrinkle formation stabilizer is added in an amount of 0.5 parts by mass or more and 6.0 parts by mass with respect to 100 parts by mass of the resin. It is a layer composed of the cured product of the resin composition contained below. That is, in the present embodiment, the matte layer is a matte easy decontamination layer that mainly exhibits easy decontamination property, and is 0.5 parts by mass with respect to 100 parts by mass of the resin forming the matte easy decontamination layer. It is a layer containing a wrinkle formation stabilizer with a content of 6.0 parts by mass or less.

(Wrinkle formation stabilizer)
As the wrinkle formation stabilizer, the wrinkle formation stabilizer described as being adopted in the matte article A is adopted. By using a wrinkle formation stabilizer, the formation of wrinkles on the surface of the matte decontamination layer is stabilized, and the visibility due to the matte effect due to the light diffusion effect at the interface between the surface and the air is also visible. , The texture can be obtained stably. Further, as will be described later, by having wrinkles, excellent easy decontamination property can be obtained.
At least one of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, etc. Further, the effect developed by using the wrinkle formation stabilizer and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those described for the matte article A.

(Surface shape of matte decontamination layer)
The surface shape of the matte decontamination layer of the matte article E needs to have irregularities formed by irregular wrinkles on at least one surface, and the content described for the matte layer of the matte article A. Is the same as. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the matte easy decontamination layer of the matte article E. When the surface shape of the matte decontamination layer has the surface shape described for the matte layer of the matte article A, the surface characteristics, especially the easy decontamination property, and the visibility and texture of the matte effect are improved. do.

Here, the effect obtained by the surface shape of the matte easy decontamination layer also includes the effect of stably expressing the visibility and texture of the excellent matte effect obtained by the matte layer of the matte article A. However, an important effect in the matte article F is easy decontamination.
As described above, the matte easy decontamination layer has an uneven shape composed of irregular wrinkles. The irregular wrinkle is preferably composed of a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions, and the protrusions are formed of streaks. It is preferable to have a protrusion. In the case of streaks, when the contaminants are wiped off, the contaminants move smoothly along the wrinkles of the striae, which facilitates decontamination, and thus the decontamination property is particularly improved.
Further, since the wrinkles have a smooth shape with lines as shown in FIG. 1, for example, when the contaminants are wiped off, the contaminants move smoothly along the wrinkles of the stripes. Since it is easy to decontaminate, the easy decontamination property is also stably exhibited.

(resin)
The resin used for forming the matte decontamination layer of the matte article E is the same as that of the resin described for the matte article A.

(Easy decontamination agent)
The matte easy decontamination layer of the matte article E preferably contains an easy decontamination agent. Even if it does not contain an easy decontamination agent, as described above, it has excellent easy decontamination properties due to the wrinkles of the matte easy decontamination layer, but it can be easily removed by using an easy decontamination agent. Dyeability is further improved.
As the easy decontamination agent, those used as antifouling agents, liquid repellents, etc. in articles such as decorative materials and decorative sheets, such as fluororesin, silicone resin, fluorosilicone copolymer resin, etc., and fluorine and silicone-free. Surfactants can also be used.

Among them, a fluororesin is preferable, and a fluorine-containing silicon compound having a hydrolyzable silyl group and the like can be specifically mentioned. Examples of the fluorine-containing silicon compound having a hydrolyzable silyl group include a perfluoropolyether group, a perfluoroalkylene group, and a perfluoroalkyl group, which are attached to the silicon atom of the hydrolyzable silyl group via a linking group. Examples thereof include compounds existing as a fluorine-containing organic group to be directly bonded. The perfluoropolyether group is a divalent group having a structure in which a perfluoroalkylene group and an ethereal oxygen atom are alternately bonded.
Examples of such a fluorine-containing silicon compound include "KP-801", "KY-130", "KY-178", "X-71-195" manufactured by Shin-Etsu Chemical Co., Ltd., and Daikin Industries, Ltd. "Optool DSX", "Optool DSX-E", "Optool UF503", etc. are commercially available, and from the viewpoint of productivity and antifouling property, "X-71-195", "Optool DSX-E", etc. , "Optur UF503" is preferable.

The content of the easy decontamination agent with respect to 100 parts by mass of the resin is preferably 0.5 parts by mass or more, more preferably 1.0 part by mass or more, still more preferably, from the viewpoint of improving the easy decontamination property more efficiently. It is 1.5 parts by mass or more, and the upper limit is preferably 25.0 parts by mass or less, more preferably 15.0 parts by mass or less, and further preferably 10.0 parts by mass or less.

(Resin composition)
The resin composition (resin composition for forming the matte easy decontamination layer) used for forming the matte easy decontamination layer of the matte article E except that it may contain an easy decontamination agent as described above. , The same as the content relating to the resin composition described for the matte article A.

[60 ° gloss value]
The 60 ° gloss value of the matte article E is 5.0 or less, which is the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value.

[Layer structure]
As with the matte article A, the matte article E does not necessarily have a base material. Therefore, as the simplest layer structure of the matte article E, a layer structure consisting of a single layer having no base material and only a matte easy decontamination layer can be adopted.
Further, similarly to the above-mentioned matte article A, when the matte article E has a layer structure consisting of a single layer, various performances usually required for the matte article such as mechanical strength, post-processing suitability, designability, etc. Often the choices to get are limited. Therefore, the layer structure of the matte article E is preferably a layer structure having a base material, that is, a base material and a matte layer.

〔Base material〕
In addition to the matte layer, the matte article E may further have a base material, if desired, and as described above, it is preferable to have a base material from the viewpoint of avoiding various restrictions. The base material functions as a support for providing a matte layer. Further, considering that the matte article E is usually used by being attached to an adherend, the form (or shape) of the base material is preferably a film, a sheet, or a plate, and the film or the sheet is preferable. More preferred.
Other than that, the base material of the matte article E is the same as that of the base material described for the matte article A.

[Other layers]
In addition to the above-mentioned matte layer (matte easy decontamination layer) and base material, the matte article E includes, for example, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, and the like as necessary. Can have. 3 and 4 are cross-sectional views showing an embodiment of the matte article E having these layers. 3 and 4 are also cross-sectional views showing an embodiment of the matte article E. It is sectional drawing which cut | cut the matte article 1 (matte article E) in the plane parallel to the thickness direction (Z direction in the figure).
The matte article 1 (matte article E) shown in FIG. 3 has a substrate 5 and a matte layer (matte easy decontamination layer) 4 in this order, and the matte article 1 (matte article 1) shown in FIG. The matte article E) has a base material 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a matte layer (matte easy decontamination layer) 4 in this order.

(Primer layer)
The primer layer that the matte article E can have is the same as that of the primer layer described for the matte article A.

(Transparent resin layer)
The transparent resin layer that the matte article E can have is the same as that of the transparent resin layer described for the matte article A.

(Decorative layer)
The decorative layer that the matte article E can have is the same as the content relating to the decorative layer described for the matte article A.

(Adhesive layer)
The adhesive layer that the matte article E can have is the same as that of the adhesive layer described for the matte article A.

(Performance of matte article E)
The matte article E has excellent surface properties, especially excellent decontamination property, and is described in, for example, "15.3 C method" of JIS K6902: 2007 (heat-curable resin high-pressure decorative board test method). Compliantly, use acetone (Material No. 3), household ammonia (Material No. 4), 10% pericate (Material No. 5), black oil-based marker (Material No. 12) and crayon (Material No. 14) as pollutants. When the contamination test is performed and the detergency is evaluated according to the criteria of 0 to 5 grades based on "15.35.2 Cleaning Procedure", it is said that the detergency is at least 3 grades or more (3 grades to 0 grades). Stain resistance of at least grade 3 or higher (grade 3 or 5) when the stain resistance is evaluated according to the criteria of

grades

5, 3 and 1 based on "15.3.6.2 Contamination resistance" as well as detergency. It has.

[Manufacturing method of matte article E]
The method for producing the matte article E is different from the above-mentioned matte article A in that the resin composition for forming the matte easy decontamination layer may contain an easy decontamination agent, but other points, that is, Average particle size and type of wrinkle formation stabilizer, type of resin contained in the resin composition for forming a matte decontamination layer, content of wrinkle formation stabilizer, resin composition for forming a matte decontamination layer The coating method, the thickness, the irradiation conditions in the matte easy decontamination layer forming step, and the like are the same as those described for the method for producing the matte article A.
Further, the process of the manufacturing method in the case of using only a single layer of the matte easy decontamination layer (matte layer) and the case of having a base material and other layers also describes the manufacturing method of the matte article A. Is the same as.

[Cosmetic member E]
As a typical use of the matte article E, the matte article E can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, vehicles, home appliances, etc., or is adhered. It is also possible to use it as a decorative member by laminating it with a material, combining it, or combining it (hereinafter, the decorative member using these matte articles E may be referred to as "decorative member E"). .. Which one to use may be determined as desired.
The form of the matte article E in the decorative member E, the adherend, the adhesive layer, the method for producing the decorative member E, the use of the decorative member E, and the like are the same as those described in the decorative member A.

[Matte article F]
In the matte article of the present embodiment, in the matte article A, the matte layer is a matte light-resistant layer, and the resin composition constituting the matte light-resistant layer further contains a hydroxyphenyltriazine-based ultraviolet absorber. (Hereinafter, also simply referred to as "matte article F"), specifically, a matte article having a matte layer, wherein the matte layer is a wrinkle forming stabilizer resin 100. It is composed of a cured product of a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less with respect to parts by mass and containing a hydroxyphenyltriazine-based ultraviolet absorber, and at least one surface of the matte layer is formed. A matte article having an uneven shape composed of irregular wrinkles, the matte layer having a 60 ° gloss value of 5.0 or less, and the matte layer being a matte light resistant layer. By having such a structure, the matte article F is excellent in light resistance and also excellent in visibility and texture of the matte effect.

[Matte layer (matte light resistant layer)]
The matte layer in the matte article F is a matte light-resistant layer that particularly exhibits light resistance, and contains a wrinkle formation stabilizer in an amount of 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. Moreover, it is a layer composed of a cured product of a resin composition containing a hydroxyphenyltriazine-based ultraviolet absorber. That is, in the present embodiment, the matte layer is a matte light-resistant layer that particularly exhibits light resistance, and is 0.5 parts by mass or more and 6.0 parts by mass with respect to 100 parts by mass of the resin forming the matte easy decontamination layer. It is a layer containing a wrinkle formation stabilizer and a hydroxyphenyltriazine-based ultraviolet absorber at a content of less than a part.

(Wrinkle formation stabilizer)
As the wrinkle formation stabilizer, the wrinkle formation stabilizer described as being adopted in the matte article A is adopted. By stabilizing the formation of wrinkles on the surface of the matte light-resistant layer by using a wrinkle formation stabilizer, the texture as well as the visibility due to the matte effect due to the light diffusion effect at the interface between the surface and the air with a refractive index difference. Can be obtained stably. Further, as will be described later, even when used in an environment exposed to outdoor sunlight, wind and rain, and changes in cold heat such as exterior members, the effect of less change in gloss is obtained as compared with conventional matting agents. Be done.
At least one of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, etc. Further, the effect developed by using the wrinkle formation stabilizer and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those described for the matte article A.

Further, in the matte article F, in relation to its main use, by using the wrinkle formation stabilizer, an excellent effect can be obtained as compared with the conventional matte agent in the following points.
Since the matte article F is an article having excellent light resistance, it is widely used in an environment exposed to sunlight, wind and rain, and cold changes such as exterior members such as outer walls, eaves ceilings, roofs, walls, and fences. Become. In general, when a resin layer containing particles such as a matting agent is exposed to outdoor sunlight, wind and rain, and changes in cold heat, particles near the surface tend to fall off over time. Therefore, if the specifications are such that the gloss of the layer surface is reduced solely by the addition of a matting agent, the shedding of such particles causes a gloss change over time of outdoor exposure. The gloss change during outdoor exposure due to such a mechanism becomes more remarkable as the low gloss specification has a higher content of the matting agent. In particular, if the 60 ° gloss value G ₆₀ is realized by matting agent added 10 following surface, with respect to 100 parts by weight of the resin, (depending on the kind and dispersion form Ikan of resin and matting agent) It is necessary to add about 50 parts by mass or more, and the gloss change at the time of outdoor exposure due to the removal of the matting agent becomes large.

In matte light layer of matte article F, as demonstrated in Examples and Comparative Examples described later, the 60 ° gloss value G ₆₀ is 5.0 or less of the surface even if realized by matting agent added, The content of the wrinkle formation stabilizer with respect to 100 parts by mass of the resin is about 10 parts by mass or less. For example, in the Examples below, 60 ° gloss value G ₆₀ is 5.0 or less in a total content of up to 6 parts by weight of the wrinkle formation stabilizers, further realizes a low gloss of 2.0 or less.
Thus, in the matte article F, as demonstrated in Examples and Comparative Examples described below, to achieve the same low gloss surface, in the case of particularly 60 ° gloss value G ₆₀ realize the 10 or less, the conventional Compared with matte articles such as matte cosmetic materials and decorative sheets, the particle content is significantly reduced, so that the change in gloss is small even with the aging of outdoor exposure.

(Surface shape of matte light resistant layer)
The surface shape of the matte light-resistant layer of the matte article F needs to have irregularities formed by irregular wrinkles on at least one surface, which is the same as the content described for the matte layer of the matte article A. Is. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the matte light resistant layer of the matte article F. When the surface shape of the matte light-resistant layer has the surface shape described for the matte layer of the matte article A, the light resistance, the visibility of the matte effect, and the texture are improved.

(resin)
The resin used for forming the matte light-resistant layer of the matte article F is the same as that of the resin described for the matte article A.

(UV absorber)
The matte light-resistant layer of the matte article F contains a hydroxyphenyltriazine-based ultraviolet absorber as an ultraviolet absorber. If the ultraviolet absorber is not contained, excellent light resistance cannot be obtained. As the hydroxyphenyltriazine-based ultraviolet absorber, those represented by the following general formula (1) are preferably mentioned.

In the general formula (1), R ¹¹ is a single-bonded or divalent organic group, R ¹² is a hydrocarbon group or an ester group represented by -C (= O) OR ¹⁵ , -OC (= O). It is an acyloxy group represented by R ¹⁶ or an alkoxy group represented by ^{−OR 17} ^{, and R 13} , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ are independently monovalent organic groups, respectively, and n ₁₁ and n. ₁₂ is an independently integer of 0 to 5.

As shown by the general formula (1), the hydroxyphenyltriazine-based ultraviolet absorber has a large molecular structure, and therefore has a molecular structure that bleeds out from the matte light-resistant layer and is difficult to remove from the viewpoint of steric hindrance. It has the above characteristics. Therefore, the matte article F can maintain excellent light resistance for a long period of time.

The divalent organic group R ^11, an alkylene group, an aliphatic hydrocarbon group, an alkenylene group is preferably exemplified, from the viewpoint of weather resistance, an alkylene group is more preferable. The number of carbon atoms of these aliphatic hydrocarbon groups is preferably 1 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, still more preferably 8 or less, and particularly preferably 4 or less. The alkylene group and the alkaneylene group may be linear, branched or cyclic, but linear or branched is preferable.

As the ^{monovalent organic group of R 12} , an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like are preferably mentioned, and an alkyl group is more preferable. The number of carbon atoms of the alkyl group is preferably 1 or more, more preferably 3 or more, still more preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, still more preferably 12 or less. The alkyl group or alkenyl group may be linear, branched or cyclic, but linear or branched is preferable, and branched is more preferable.

Examples of the monovalent organic group of R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aromatic hydrocarbon group such as an aryl group and an arylalkyl group can be used. Preferably, an aryl group is preferred.

The ^{number of carbon atoms of the aryl groups of R 13} and R ¹⁴ is preferably 6 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and further preferably 10 or less. The number of carbon atoms of the arylalkyl group is preferably 7 or more, and the upper limit is preferably 20 or less, more preferably 12 or less, and further preferably 10 or less.

Examples of the monovalent organic group of R ¹⁵ , R ¹⁶ and R ¹⁷ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an arylalkyl group and the like, and an aliphatic hydrocarbon such as an alkyl group and an alkenyl group. Groups are preferred, alkyl groups are more preferred. When R ¹⁵ , R ¹⁶ and R ¹⁷ are an alkyl group or an alkenyl group, the number of carbon atoms is preferably 2 or more, more preferably 4 or more, and the upper limit is preferably 20 or less, more preferably 16 or less, still more preferable. Is 12 or less.

The groups of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ described above have substituents such as halogen atoms, hydroxyl groups, amino groups, and alkyl groups having 1 to 4 carbon atoms. May be.

Further, n ₁₁ and n ₁₂ are independently integers of 1 to 5, preferably an integer of 1 to 3, and more preferably an integer of 1 to 2. When n ₁₁ and n ₁₂ are integers of 2 or more, the plurality of R ¹³ and R ¹⁴ may be the same or different, and are preferably the same from the viewpoint of availability.

Among the hydroxyphenyltriazine-based ultraviolet absorbers represented by the general formula (1), the hydroxyphenyltriazine-based ultraviolet absorbers represented by the following chemical formulas (2) to (4) are particularly preferable. UV absorber represented by the chemical formula (2), in the above-mentioned formula ^{(1), R 11} is an ethylene ^{group, R 12} is -O-C (= ^O) acyloxy group ^{(R 16} represented by ^{R 16} is 3- Heptyl group), R ¹³ and R ¹⁴ are hydrogen atoms, and are available as, for example, commercially available products (“ADEKA STAB LA-46 (product number)”, melting point: 106 ° C., manufactured by ADEKA Corporation).

In the above general formula (1), the ultraviolet absorber represented by the chemical formula (3) has R ¹¹ as a single bond, R ¹² as an isooctyl group, R ¹³ and R ¹⁴ as a phenyl group, and n ₁₁ and n ₁₂ as 1. For example, it is available as a commercially available product (“Tinuvin 1600 (product number)”, melting point: 120 ° C., manufactured by BASF).

The ultraviolet absorber represented by the chemical formula (4) has, in the above general formula (1), that R ¹¹ is a single bond, R ¹² is a hexyl group, and R ¹³ and R ¹⁴ are hydrogen atoms. It is available as "Tinuvin 1577 (product number)", melting point: 148 ° C., manufactured by BASF).

In the matte article F, the content of the hydroxyphenyltriazine-based ultraviolet absorber is preferably 0.1 part by mass or more, more preferably 0.1 part by mass or more, based on 100 parts by mass of the resin in the resin composition for forming the matte light-resistant layer. It is 1.0 part by mass or more, more preferably 2.0 part by mass or more, still more preferably 3.0 part by mass or more, and from the viewpoint of suppressing bleed-out, the upper limit is preferably 10.0 parts by mass or less, more preferably 10.0 parts by mass or more. It is 8.0 parts by mass or less, more preferably 7.0 parts by mass or less, and even more preferably 6.0 parts by mass or less. As described above, by adopting a specific ultraviolet absorber, loss due to bleed-out of the ultraviolet absorber can be suppressed, so that excellent light resistance can be obtained even if the amount is smaller than the amount normally blended. Further, by adopting an ionizing radiation curable resin as the resin used in the resin composition for forming the matte light-resistant layer, bleed-out can be further suppressed, so that excellent light resistance can be obtained even with a smaller amount. It will be.

(Resin composition)
The resin composition (resin composition for forming the matte light-resistant layer) used for forming the matte light-resistant layer of the matte article F is described above except that it contains a hydroxyphenyltriazine-based ultraviolet absorber as described above. It is the same as the content regarding the resin composition described for the matte article A.

[60 ° gloss value]
The 60 ° gloss value of the matte article F is 5.0 or less, which is the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value.

[Layer structure]
As with the matte article A, the matte article F does not have to have a base material. Therefore, as the simplest layer structure of the matte article E, a layer structure having only a matte light-resistant layer without a base material can be adopted.
Further, similarly to the above-mentioned matte article A, when the matte article F has a layer structure consisting of a single layer, various performances usually required for the matte article such as mechanical strength, post-processing suitability, designability, etc. Often the choices to get are limited. Therefore, the layer structure of the matte article F is preferably a layer structure having a base material, that is, a base material and a matte layer.

〔Base material〕
In addition to the matte layer, the matte article F may further have a base material, if desired, and as described above, it is preferable to have a base material from the viewpoint of avoiding various restrictions. The base material functions as a support for providing a matte layer. Further, considering that the matte article F is usually used by being attached to an adherend, the form (or shape) of the base material is preferably a film, a sheet, or a plate, and the film or the sheet is preferable. More preferred.
The base material of the matte article F is the same as that of the base material described for the matte article A.

[Other layers]
The matte article F has, for example, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, and the like as other layers in addition to the above-mentioned matte layer (matte light-resistant layer) and base material, if necessary. obtain. 3 and 4 are cross-sectional views showing an embodiment of the matte article F having these layers. 3 and 4 are also cross-sectional views showing an embodiment of the matte article F. It is sectional drawing which cut | cut the matte article 1 (matte article F) in the plane parallel to the thickness direction (Z direction in the figure).
The matte article 1 (matte article F) shown in FIG. 3 has a base material 5 and a matte layer (matte light resistant layer) 4 in this order, and the matte article 1 (matte article F) shown in FIG. Article F) has a base material 5, a decorative layer 6, an adhesive layer 7, a transparent resin layer 8, a primer layer 9, and a matte layer (matte light resistant layer) 4 in this order.

(Primer layer)
The primer layer that the matte article F can have is the same as that of the primer layer described for the matte article A.

(Transparent resin layer)
The transparent resin layer that the matte article F can have is the same as that of the transparent resin layer described for the matte article A.

(Decorative layer)
The decorative layer that the matte article F can have is the same as the content regarding the decorative layer described for the matte article A.

(Adhesive layer)
The adhesive layer that the matte article F can have is the same as that of the adhesive layer described for the matte article A.

(Performance of matte article F)
The matte article F has excellent surface characteristics, especially excellent light resistance. For example, a weather resistance test device "S-UV (with rain)" is used to perform a weather resistance test for 200 hours. When the 60 ° gloss value on the matte light-resistant layer side before the weather resistance test is set to G ₀ and the 60 ° gloss value on the matte light-resistant layer side after the weather resistance test is set to G _1. , The rate of change of the gloss value (| (G _{1 −} G ₀ ) | / G ₀ × 100) is 20% or less, which is an excellent light resistance.

The rate of change in the gloss value is used as an index of the light resistance of the matte article F by observing the range of change in the gloss value before and after the weather resistance test. The larger the rate of change in the gloss value, the higher the gloss value after the weather resistance test, that is, the surface of the matte article F becomes more glossy due to deterioration, which indicates that the light resistance is inferior.
Since the matte article F of the present embodiment has excellent light resistance, the rate of change of the gloss value is 20% or less as described above, and further 15% or less, 10% or less, 8 It can be less than%.

[Manufacturing method of matte article F]
The method for producing the matte article F is different from the above-mentioned matte article A in that the resin composition for forming the matte light-resistant layer contains a hydroxyphenyltriazine-based ultraviolet absorber, but other points, that is, wrinkle formation. Average particle size and type of stabilizer, type of resin contained in the resin composition for forming a matte light-resistant layer, content of wrinkle-forming stabilizer, application method and thickness of the resin composition for forming a matte light-resistant layer. The irradiation conditions and the like in the matte light-resistant layer forming step are the same as those described for the method for producing the matte article A.
Further, when a single layer having only a matte light resistant layer (matte layer) is used, or when a base material and other layers are provided, the steps of the manufacturing method are the same as those described for the manufacturing method of the matte article A. Is.

[Cosmetic member F]
As a typical use of the matte article F, the matte article F can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, vehicles, home appliances, etc., or is adhered. It is also possible to use it as a decorative member by laminating it with a material, combining it, or combining it (hereinafter, the decorative member using these matte articles F may be referred to as "decorative member F"). .. Which one to use may be determined as desired.
The form of the matte article F in the decorative member F, the adherend, the adhesive layer, the method for producing the decorative member F, the use of the decorative member F, and the like are the same as those described in the decorative member A.

[Matte article G]
The matte article of the present embodiment is a matte article (hereinafter, also simply referred to as "matte article G") in which the matte layer is a matte writing layer in the matte article A, and is specific. Is a matte article having a matte layer, and the matte layer contains a wrinkle formation stabilizer in an amount of 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. It is composed of a cured product, has an uneven shape in which at least one surface of the matte layer is composed of irregular wrinkles, the 60 ° gloss value of the matte layer is 5.0 or less, and the matte layer. A matte article in which the layer is a matte writing layer. By having such a configuration, the matte article G is excellent in visibility due to the matte effect and marker erasability.

[Matte layer (matte writing layer)]
The matte layer in the matte article G is a matte writing layer that particularly exhibits marker erasability, and contains a wrinkle formation stabilizer in an amount of 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. It is a layer composed of a cured product of the resin composition. That is, in the present embodiment, the matte layer is a matte writing layer that particularly exhibits marker erasability, and is 0.5 parts by mass or more and 6.0 parts by mass with respect to 100 parts by mass of the resin forming the matte writing layer. It is a layer containing a wrinkle formation stabilizer at the following contents.

(Wrinkle formation stabilizer)
As the wrinkle formation stabilizer, the wrinkle formation stabilizer described as being adopted in the matte article A is adopted. By stabilizing the formation of wrinkles on the surface of the matte writing layer by using a wrinkle formation stabilizer, a marker as well as visibility due to the matte effect due to the light diffusion effect at the interface between the surface and the air with a refractive index difference. Stable erasability can be obtained.
At least one of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, etc. Further, the effect developed by using the wrinkle formation stabilizer and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those described for the matte article A.

(Surface shape of matte writing layer)
The surface shape of the matte writing layer of the matte article G needs to have irregularities formed by irregular wrinkles on at least one surface, which is the same as the content described for the matte layer of the matte article A. Is. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the matte writing layer of the matte article G. When the surface shape of the matte writing layer has the surface shape described for the matte layer of the matte article A, the visibility and marker erasability due to the matte effect are improved.

Here, the effect obtained by the surface shape of the matte writing layer includes the effect of stably expressing the excellent visibility and texture of the matte effect obtained by the matte layer of the matte article A. An important effect in the matte article G is marker erasability.
The matte writing layer has an uneven shape composed of irregular wrinkles as described above. The irregular wrinkle is preferably composed of a plurality of convex portions formed by a plurality of protrusions and a concave portion formed by being surrounded by the plurality of protrusions, and the protrusions are formed of streaks. It is preferable to have a protrusion. In the case of a streak, when the marker is wiped off, the marker moves smoothly along the wrinkles of the streak, which makes it easier to erase the marker, so that the marker erasability is particularly improved.
Further, since the wrinkles have a smooth shape with the streaks as shown in FIG. 1, for example, when the marker is wiped off, the marker is erased by smoothly moving along the wrinkles of the streaks. Since it becomes easy, the marker scavenging property is also stably expressed.

(resin)
The resin used for forming the matte writing layer of the matte article G is the same as that of the resin described for the matte article A.

(Resin composition)
The resin composition (resin composition for forming the matte writing layer) used for forming the matte writing layer of the matte article G is the same as the content relating to the resin composition described for the matte article A.

[60 ° gloss value]
The 60 ° gloss value of the matte article G is 5.0 or less, which is the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value.

[Layer structure]
As with the matte article A, the matte article G does not necessarily have a base material. Therefore, as the simplest layer structure of the matte article G, a layer structure consisting of a single layer having no base material and having only a matte easy decontamination layer can be adopted.
Further, similarly to the above-mentioned matte article A, when the matte article G has a layer structure consisting of a single layer, various performances usually required for the matte article such as mechanical strength, post-processing suitability, designability, etc. Often the choices to get are limited. Therefore, the layer structure of the matte article G is preferably a layer structure having a base material, that is, a base material and a matte layer.

〔Base material〕
In addition to the matte layer, the matte article G may further have a base material, if desired, and as described above, it is preferable to have a base material from the viewpoint of avoiding various restrictions. The base material functions as a support for providing a matte layer. Further, considering that the matte article G is usually used by being attached to an adherend, the form (or shape) of the base material is preferably a film, a sheet, or a plate, and the film or the sheet is preferable. More preferred.
In addition, regarding the base material of the matte article G, the materials and the like constituting the base material are the same as those relating to the base material described for the matte article A.

Further, the base material used in the matte article G preferably has a base material (base material sheet) which is a form sheet thereof and a colored layer. In this case, an ink containing the above-mentioned colorant may be used to provide a colored layer so as to obtain a desired color tone.
As the ink used for the coloring layer, an ink obtained by appropriately mixing the above-mentioned coloring agent, extender pigment, solvent, stabilizer, plasticizer, catalyst, curing agent, ultraviolet absorber, light stabilizer, etc. with the binder resin is used. NS.

The binder resin of the ink used for forming the colored layer of the base sheet is not particularly limited, and for example, urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane-acrylic. Examples thereof include copolymers, vinyl chloride-vinyl acetate copolymer resins, vinyl chloride-vinyl acetate-acrylic copolymer resins, chlorinated propylene resins, nitrocellulose resins, cellulose acetate resins and the like. Further, various types of resins such as a one-component curable resin and a two-component curable resin with a curing agent such as an isocyanate compound can be used.
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 colored layer. The following is more preferable.

The colored layer may contain additives such as an ultraviolet absorber, a weathering agent such as a light stabilizer, and the like.
The thickness of the colored layer may be appropriately selected according to the desired color tone and the like, but from the viewpoint of hiding the ground color of the adherend and improving the design, it is preferably 0.5 μm or more and 20 μm or less, and 1 μm. More than 10 μm is more preferable, and 2 μm or more and 5 μm or less is further preferable.

Further, as a method other than the above-mentioned formation of the coloring layer, in the case of coloring a synthetic resin, the formation by adding a coloring agent (kneading, kneading) into the resin and applying a coating film of a paint containing the resin and the coloring agent. Any means such as, etc. 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 mixed extraction with pulp or fiber material, formation of a coating film, or a combination thereof.
In the case of coloring wood, it can be carried out by either dyeing with a dye, forming a coating film, or a combination thereof. In the case of coloring a metal, in addition to forming a coating film, an electrolytic coloring method for forming a metal oxide film on the surface by using an anodic oxidation method or the like can be adopted. Further, in the case of a non-metallic inorganic material, it can be carried out by either means of forming a coating film or adding it to a base material, or a combination thereof.

The colored layer of the base sheet is basically a layer composed of a so-called solid colored layer that covers the entire surface, but has a pattern layer having various patterns, for example, a dot pattern or the like, if desired. May be good.

[Other layers]
The matte article G has, for example, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, and the like as other layers in addition to the above-mentioned matte layer (matte writing layer) and base material, if necessary. obtain. A cross-sectional view showing an embodiment of the matte article G having these layers is shown in FIGS. 34 and 35. It is sectional drawing which cut | cut the matte article 1 (matte article G) in the plane parallel to the thickness direction (Z direction in the figure).
The matte article 1 (matte article G) shown in FIG. 34 has a base material 5 (a two-layer laminated structure of a base material sheet 51 and a colored layer 52) and a matte layer (matte writing layer) 4 in this order. The matte article 1 (matte article G) shown in FIG. 35 includes a colored base sheet 5 (a two-layer laminated structure of a base sheet 51 and a colored layer 52), an adhesive layer 6, and the like. It has a transparent resin layer 7, a primer layer 8, and a matte layer (matte writing layer) 4 in this order.

(Primer layer)
The primer layer that the matte article G can have is the same as that of the primer layer described for the matte article A.

(Transparent resin layer)
The transparent resin layer that the matte article G can have is the same as that of the transparent resin layer described for the matte article A.

(Decorative layer)
The decorative layer that the matte article G can have is the same as the content relating to the decorative layer described for the matte article A.

(Adhesive layer)
The adhesive layer that the matte article G can have is the same as that of the adhesive layer described for the matte article A.

(Performance of matte article G)
The matte article G has excellent marker erasability. For example, "a black marker ^{having a round core and a middle character 1)} ^{defined by JIS S6052: 2014" (Note 1).} The middle character means that the thickness of the writing line is about 1.5 mm to 2.5 mm), and the marker's ease of dropping test was performed according to the methods a) to c) below, and before the test. The color difference (ΔE ^* ab) after the test is 3.0 or less, which means that the marker has excellent marker erasability.
(Test of marker dropability)
a) Fill the matte writing layer of the sheet with the marker in an area of 2 cm x 4 cm.
b) One minute after painting, erase using an unused melamine foam whiteboard eraser (2 cm x 2 cm, whiteboard sharp drop eraser (Auto Co., Ltd.)).
c) Repeat a) and b) above 50 times.

For the color difference (ΔE ^* ab), the measured values of brightness and chromaticity before the test are L ^* ₁ , a ^* ₁ and b ^* _1, and the measured values of brightness and chromaticity after the above test are L ^* ₂ , a ^*. It is a calculated value obtained by the following formula when ₂ and b ^* _{2 are set.}
ΔE ^* ab = [(L ^* _2- L ^* ₁ ) ² + (a ^* _2- a ^* ₁ ) ² + (b ^* _2- a ^* ₂ ) ² ] ^1/2
Further, L ^* , a ^* , and b ^* are defined in the color display method of JIS Z8781-5: 2013, and are commercially available spectrophotometers (for example, spectrocolorimeter / color difference meter "SE6000" (for example). Model number), manufactured by Nippon Denshoku Kogyo Co., Ltd.), etc. can be used for measurement.

[Manufacturing method of matte article G]
Regarding the method for producing the matte article G, the average particle size and type of the wrinkle formation stabilizer, the type of resin contained in the resin composition for forming the matte writing layer, the content of the wrinkle formation stabilizer, and the formation of the matte writing layer. The method of applying the resin composition for use, the thickness, the irradiation conditions in the process of forming the matte writing layer, and the like are the same as those described for the method for producing the matte article A.
Further, when a single layer having only a matte writing layer (matte layer) is used, or when a base material and other layers are provided, the steps of the manufacturing method are the same as those described for the manufacturing method of the matte article A. Is.

[Cosmetic member G]
A typical use of the matte article G is a writing board such as a white board or a blackboard in a form in which the matte article G is used alone or laminated with an adherend and combined or combined. (Hereinafter, a decorative member using these matte articles G may be referred to as "decorative member G"). Which form may be used may be determined as desired.
When having an adherend, the decorative member G (writing board) has the adherend and the matte article G of the present embodiment described above, and specifically, the writability of the adherend is improved. The required surface and the surface opposite to one surface on which wrinkles of the matte writing layer of the matte article G are formed to exhibit visibility and marker erasability are laminated so as to face each other.

The adherend may be appropriately selected from those described as the adherends that can be used in the decorative member A, but in consideration of the use as a writing board, flat plates, sheets (or films) and the like of various materials are preferable. .. 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, and further preferably 0.5 mm or more and 3 mm or less.
Further, the matte article G of the present embodiment preferably has a sheet form as described above, considering the ease of laminating on the adherend.

In addition, the form of the matte article G in the decorative member G, the adherend, the adhesive layer, the manufacturing method of the decorative member G, and the like are the same as those described in the decorative member A.

The decorative member G (writing board) obtained as described above is arbitrarily cut, and grooving, chamfering, bending, etc. are arbitrarily applied to the surface and the end of the wood using a cutting machine such as a router or a cutter. Can be decorated.

[Matte article H]
The matte article of the present embodiment is a matte article (hereinafter, also simply referred to as "matte article H") in which the matte layer is a matte-type layer in the matte article A, and is specific. Specifically, it is a matte article having a matte layer, and the matte layer contains a wrinkle formation stabilizer in an amount of 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. The matte layer has a concavo-convex shape composed of irregular wrinkles on at least one surface of the matte layer, and the matte layer has a 60 ° gloss value of 5.0 or less. A matte article in which the matte layer is a matte type layer. By having such a configuration, the matte article H can easily respond to the diversifying demands of customers, and is used as a type sheet, that is, an article that imparts excellent visibility and texture of a matte effect.

[Matte layer (matte type layer)]
The matte layer in the matte article H is a matte type layer that can easily respond to the diversifying demands of customers and imparts excellent visibility and texture of the matte effect, and the wrinkle formation stabilizer is resin 100. It is a layer composed of a cured product of a resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less with respect to parts by mass. That is, in the present embodiment, the matte layer is a matte type layer that can easily respond to the diversifying demands of customers and imparts excellent visibility and texture of the matte effect. It is a layer containing a wrinkle formation stabilizer at a content of 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 to be formed.

(Wrinkle formation stabilizer)
As the wrinkle formation stabilizer, the wrinkle formation stabilizer described as being adopted in the matte article A is adopted. By stabilizing the formation of wrinkles on the surface of the matte writing layer by using a wrinkle formation stabilizer, the texture as well as the visibility due to the matte effect due to the light diffusion effect at the interface between the surface and the air with a refractive index difference. Can be granted.
In addition, at least one of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer. The amount and the like, the effect exhibited by using the wrinkle formation stabilizer, and the difference between the wrinkle formation stabilizer and the matte agent are basically the same as those described for the matte article A.

(Surface shape of matte type layer)
The surface shape of the matte-type layer of the matte article H needs to have irregularities formed by irregular wrinkles on at least one surface, and is the same as the content described for the matte layer of the matte article A. It is the same. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the matte type layer of the matte article H. By having the surface shape of the matte-type layer having the surface shape described for the matte layer of the matte article A, it is possible to easily respond to the diversifying demands of customers, and the visibility of the excellent matte effect and the visibility of the matte effect are excellent. Texture can be added.

(resin)
The resin used for forming the matte-type layer of the matte article H is the same as that of the resin described for the matte article A.

(Resin composition)
The resin composition used for forming the matte-type layer of the matte article H (resin composition for forming the matte-type layer) is the same as the content relating to the resin composition described for the matte article A. ..

Further, with respect to the matte article H, it is necessary to peel off the matte article H after molding with the matte article H, so that the matte type layer preferably has peelability. From this point of view, it is preferable that the matte type layer contains a release agent, that is, the resin composition for forming the matte type layer preferably contains a release agent. .. Examples of the release agent include a fluorine-based release agent, a silicone-based release agent, and the like, and a silicone-based release agent is preferable from the viewpoint of obtaining cheaper and higher releasability.

Examples of the silicone-based mold release agent include those having a polysiloxane structure as a basic structure, and among them, modified silicone oil in which an organic group is introduced into at least one of the side chain and the terminal thereof is preferable, and organic groups are present at both ends. The introduced modified silicone oil is more preferred. As the organic group, from the viewpoint of obtaining a design with a higher texture, a reactive functional group such as a (meth) acrylic group, an amino group, an epoxy group, a mercapto group, a carbinol group, a phenol group or a carboxyl group, or a polyether group , Non-reactive group functional groups such as aralkyl group, fluoroalkyl group, alkyl group, fatty acid amide group and phenyl group are preferably mentioned. Among them, a reactive functional group is preferable, and a (meth) acrylic group is particularly preferable, that is, a (meth) acrylic-modified silicone oil is particularly preferable. Further, these organic groups may have substituents such as a nitrogen atom, a sulfur atom, a hydroxyl group and an alkyl group.

The content of the release agent is preferably 0.1 to 5 parts by mass, more preferably 0.5 to 3 parts by mass, and further preferably 1 to 1 to 100 parts by mass with respect to 100 parts by mass of the resin forming the matte type layer. 2 parts by mass. When the content of the release agent is within the above range, the effect of adding the release agent can be efficiently obtained.

[60 ° gloss value]
The 60 ° gloss value of the matte article H is 5.0 or less, which is the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value. Since the matte article H is mainly used as a shaping sheet, the 60 ° gloss value of the matte article H is the 60 ° gloss value that the matte article H can give (60 ° of the shaped object). It also means that it is a gloss value).
If the matte-type sheet of the present embodiment has a stable matte effect and texture due to the stable formation of wrinkles, the decorative material molded using the matte-type sheet also has a stable matte effect. It can be a high-class decorative material having the visibility and texture of the effect. Further, if the 60 ° gloss value of the shaped sheet and the 60 ° gloss value of the decorative material obtained by using the fixed sheet have the same color tone, some differences will occur. Basically it will be about the same.

[Layer structure]
As with the matte article A, the matte article H does not have to have a base material. Therefore, as the simplest layer structure of the matte article H, a layer structure having only a matte-type layer without a base material can be adopted.
Further, similarly to the above-mentioned matte article A, when the matte article H has a layer structure consisting of a single layer, various performances usually required for the matte article such as mechanical strength, post-processing suitability, designability, etc. Often the choices to get are limited. Therefore, the layer structure of the matte article H is preferably a layer structure having a base material, that is, a base material and a matte layer.

〔Base material〕
In addition to the matte layer, the matte article H may further have a base material, if desired, and as described above, it is preferable to have a base material from the viewpoint of avoiding various restrictions. The base material functions as a support for providing a matte layer. Further, considering that the matte article H is usually used by being attached to an adherend, the form (or shape) of the base material is preferably a film, a sheet, or a plate, and the film or the sheet is preferable. More preferred.
In addition, regarding the base material of the matte article H, the materials and the like constituting the base material are the same as those relating to the base material described for the matte article A.

[Other layers]
The matte article H may have, for example, a primer layer, a resin layer, an adhesive layer and the like as other layers in addition to the above-mentioned matte layer (matte type layer) and base material, if necessary. 41 and 42 are cross-sectional views showing an embodiment of the matte article H having these layers. It is sectional drawing which cut | cut the matte article 1 (matte article H) in the plane parallel to the thickness direction (Z direction in the figure).
The matte article 1 (matte article H) shown in FIG. 41 has a base material 5 and a matte-type layer 4 in this order, and the matte article 1 (matte article H) shown in FIG. 42 has a substrate 5 and a matte-type layer 4 in this order. , A base material 5, an adhesive layer 6, a resin layer 7, a primer layer 8 and a matte type layer 4 in this order. As described above, the matte article H is used as a shaping sheet, and unlike other matte articles, it is not used as a decorative member by itself, so that it does not have to have a decorative layer. good.

(Primer layer)
The primer layer that the matte article H can have is the same as that of the primer layer described for the matte article A.

(Resin layer)
Since the matte article H is used as a shaping sheet, it may have a resin layer in order to increase its strength. When the matte article H is repeatedly used as a shaping sheet, durability is required, so it is effective to have a resin layer.
The resin layer may be provided between the base material sheet and the matte type layer.
Other, for example, the type of resin is the same as that of the transparent resin layer described for the matte article A.

(Adhesive layer)
The adhesive layer that the matte article H can have is the same as that of the adhesive layer described for the matte article A.

[Manufacturing method of matte article H]
Regarding the method for producing the matte article H, the average particle size and type of the wrinkle formation stabilizer, the type of resin contained in the resin composition for forming the matte type layer, the content of the wrinkle formation stabilizer, and the matte type. The method of applying the resin composition for layer formation, the thickness, the irradiation conditions in the matte-imparted layer forming step, and the like are the same as those described for the method for producing the matte article A.
Further, when a single layer having only a matte type layer (matte layer) is used, or when a base material and other layers are provided, the steps of the manufacturing method are also the same as those described for the manufacturing method of the matte article A. It is the same.

[Matte decorative material H]
The matte article H is used as a shaping sheet as described above, and unlike other matte articles, it is not used as a decorative member by itself. A product molded using the matte article H is referred to as a matte decorative material H, and a method for producing the matte decorative material H will be described below.

(Manufacturing method of matte decorative material H)
The method for producing the matte decorative material H is characterized in that the above-mentioned matte article H is used as a shaping sheet for shaping. The matte article H is suitably used as a shaping sheet in a method for producing a matte decorative material. Since the matte article H has the visibility and texture of the matte effect stably due to the stable formation of wrinkles, the matte decorative material H obtained by molding using this has the visibility of the matte effect. It will have a sense of quality and texture.

One of the preferred embodiments in the method for producing the matte decorative material H is an embodiment in which the matte article H is molded by using an embossing roller arranged on a roller. As a result, it is possible to mold the wrinkles of the matte article H on the member to be shaped, and to impart the visibility of a stable matting effect due to the wrinkles and a high-class feeling with a texture.
In this case, since the matte article H functions as a substitute for the embossed plate, the embossed plate can be used without particular limitation as long as the embossed plate is used to impart an uneven shape to the surface. ..

Further, as one of the other preferable aspects in the method for producing the matte decorative material H, the base material impregnated with the resin composition and the matte article H are combined with the matte-imparted layer of the matte article H. An embodiment is described in which the resin composition is arranged so as to face the base material, heat-press molded to cure the resin composition, and then the matte article H is peeled off to form a shape. In this embodiment, melamine resin veneer and diallyl phthalate (DAP) resin veneer are mainly used for surface veneer of general furniture such as porcelain, shelves, desks, fittings such as doors, and various counters. , A method preferably adopted for a method for producing a heat-curable resin decorative board such as a polyester decorative board, a guanamine resin decorative board, and a phenol resin decorative board.

As the base material impregnated with the resin composition, for example, a fiber base material or a paper base material impregnated with a thermosetting resin can be adopted.
The thermosetting resin contained in the resin composition can be used without particular limitation as long as it can be cured at room temperature or by heating. For example, melamine resin, urea resin, melamine-urea resin, guanamine resin, etc. Diallyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin and the like are preferable, and melamine resin, urea resin, melamine-urea resin, guanamine resin, sulfonamide resin and the like are heat-cured. Examples thereof include melamine resin, diallyl phthalate resin, polyester resin, guanamine resin, phenol resin and the like, which are widely used resins.

In addition to the base material impregnated with the above resin composition, a fiber base material or a paper base material impregnated with a thermosetting resin may be used as the reinforcing layer, and the thermosetting resin in this case is phenol. A resin is preferable, that is, a phenol resin impregnated paper which is widely used as a core paper such as a melamine resin decorative board is preferable. More specifically, for example, kraft paper having a basis weight of 150 to 250 g / m ² is impregnated with a phenol resin and dried at about 100 to 140 ° C. to obtain the same. Further, the fiber base material or the paper base material impregnated with the thermosetting resin used as the reinforcing layer may be one sheet or a plurality of sheets.

The conditions for heat and pressure molding may be appropriately adjusted according to the type of thermosetting resin used, and are not particularly limited, but are usually 100 ° C. or higher and 200 ° C. or lower, preferably 120 ° C. or higher and 160 ° C. or lower. Under the conditions, the pressure is 0.1 MPa or more, preferably 0.49 MPa or more, and the upper limit is preferably about 1.47 MPa or less, and the time is 10 seconds to 120 minutes.

In addition, each configuration for forming the resin veneer may follow the configuration adopted in the conventional resin veneer, and there is no particular limitation.

The matte decorative material H obtained as described above can be arbitrarily cut, and the surface and the end of the wood can be arbitrarily decorated by grooving, chamfering, etc. using a cutting machine such as a router or a cutter. .. And various uses, for example, interior members of buildings such as walls, ceilings, floors, exterior members such as outer walls, eaves ceilings, roofs, walls, fences, window frames, doors, door frames, handrails, skirting trees, etc. In addition to fittings or building components such as surrounding edges and malls, general furniture such as stools, shelves and desks, kitchen furniture such as dining tables and sinks, surface decorative boards such as cabinets for home appliances and OA equipment, vehicle interiors and exteriors. It can be used for materials, packaging materials, antiglare films for displays, and the like. That is, the matte article H of the present embodiment is suitably used as a shaping sheet for shaping the uneven shape on these various members.
Further, among the matte decorative materials H, the resin decorative board is mainly preferably used for the surface decorative board of general furniture such as chests of drawers, shelves and desks, fittings such as doors, and various counters.

[Manufacturing method of matte article I]
The method for manufacturing the matte article of the present embodiment is
The resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of the wrinkle formation stabilizer with respect to 100 parts by mass of the resin and containing the photopolymerization initiator is irradiated with the following (1) and (2). The treatment is carried out in order, and the step of curing the resin composition to form a matte layer is included.
At least one surface of the matte layer has an uneven shape composed of irregular wrinkles.
A matte article having a 60 ° gloss value of 5.0 or less in the matte layer is manufactured.
(Hereinafter, it may be simply referred to as "manufacturing method I").
(1) Irradiation treatment of wavelength light of 100 nm or more and less than 200 nm (2) Irradiation treatment of at least one of electron beam and wavelength light of 200 nm or more and 400 nm or less It is possible to easily manufacture a matte article having the visibility and texture of the matte effect.

The production method I is different from the production method described as the production method of the matte article A in that the irradiation treatment of the above (2) is required, but the other irradiation treatment of (1), the wrinkle formation stabilizer, and the like. The matte layer and its surface shape, the resin and resin composition forming the matte layer, the 60 ° gloss value of the obtained matte article, each layer constituting the obtained matte article, etc. are basically the above-mentioned matte. It is the same as the content described in Article A.
Hereinafter, the manufacturing method I will be described in more detail.

[Step of forming a matte layer]
In the step of forming the matte layer, the resin composition containing a wrinkle formation stabilizer in an amount of 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 and containing a photopolymerization initiator is described above. The irradiation treatments (1) and (2) are carried out in order, and the resin composition is cured to form a matte layer.
In the production method I, a resin composition containing a predetermined amount of a wrinkle formation stabilizer and a photopolymerization initiator is subjected to the two types of irradiation treatments (1) and (2) in this order, and the resin composition is cured. By having a step of forming a matte layer having wrinkles on at least one surface, a matte article having excellent surface characteristics as well as excellent visibility and texture of a matte effect can be easily produced. It is possible to manufacture the product. That is, the matte layer contained in the matte article obtained by the manufacturing method I (hereinafter, the matte article obtained by the manufacturing method I may be referred to as "matte article I") forms a predetermined amount of wrinkles. A resin composition containing a stabilizer and a photopolymerization initiator is subjected to the above two types of irradiation treatments (1) and (2) in order, and the resin composition is cured to obtain irregularities on at least one surface. It can be said that the layer has an uneven shape composed of wrinkles.

(Wrinkle formation stabilizer)
In the production method I, as the wrinkle formation stabilizer, the wrinkle formation stabilizer described as being adopted in the matte article A is adopted.
At least one of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2, the type and content of the wrinkle formation stabilizer, etc. Further, the effect developed by using the wrinkle formation stabilizer and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those described for the matte article A.

(Surface shape of matte layer)
The surface shape of the matte layer of the matte article I obtained by the manufacturing method I needs to have irregularities formed by irregular wrinkles on at least one surface of the matte article A. It is the same as the explanation. Further, FIGS. 1 and 2 used for explaining the surface shape of the matte layer of the matte article A can also be applied to the matte layer of the matte article I. Since the surface shape of the matte layer has the surface shape described for the matte layer of the matte article A, the matte article I has excellent surface characteristics as well as excellent visibility and texture of the matte effect. It becomes a thing.

(resin)
In the production method I, the resin used for forming the matte layer is the same as the content relating to the resin described for the matte article A.

(Photopolymerization initiator)
In the production method I, the matte layer contains a photopolymerization initiator because it is a layer formed by curing a resin composition containing a wrinkle formation stabilizer in a predetermined amount and containing a photopolymerization initiator. It differs from the above-mentioned matte article A in that it needs to contain a photopolymerization initiator.
A production method in which the wrinkles of the matte layer, which are mainly developed by using a wrinkle formation stabilizer, are retained by appropriately curing the resin in the resin composition for forming the matte layer using a photopolymerization initiator. The visibility and texture of the matte effect of the matte article I obtained by I can be made excellent. Further, since the curing of the resin composition is promoted, excellent surface properties can be obtained. In particular, when irradiation with ultraviolet rays is adopted in the irradiation treatment of (2) described later, it is effective to include a photopolymerization initiator in terms of obtaining excellent surface characteristics.

Examples of the photopolymerization initiator include those exemplified as the photopolymerization initiator that can be contained in the resin composition constituting the matte layer of the matte article A, that is, acetophenone, benzophenone, α-hydroxyalkylphenone, Michler ketone, benzoin, and benzyl. Examples thereof include dimethyl ketal, benzoyl benzoate, α-acyl oxime ester, thioxanthones, and compounds having these as a basic structure.
In the present embodiment, as the photopolymerization initiator, these can be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.1 part by mass or more with respect to 100 parts by mass of the resin forming the matte layer from the viewpoint of maintaining the shape of the wrinkles and stably improving the matting effect. , More preferably 0.3 parts by mass or more, further preferably 0.5 parts by mass or more, and the upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, still more preferably 1.5 parts by mass or less. Even more preferably, it is 1.0 part by mass or less.

(Resin composition)
In the production method I, the resin composition used for forming the matte layer (resin composition for forming the matte layer) needs to contain a photopolymerization initiator as described above, and the matte article A is described above. However, other additives such as various weather resistant agents that may be contained are the same as those relating to the resin composition described for the matte article A.

(Irradiation treatment)
In the production method I of the present embodiment, in order to form the matte layer by curing the resin composition for forming the matte layer described above, the following irradiation treatments (1) and (2) are sequentially performed. It takes.
(1) Irradiation treatment of wavelength light of 100 nm or more and less than 200 nm (2) Irradiation treatment of at least one of electron beam and wavelength light of 200 nm or more and 400 nm or less

The irradiation treatment of (1) is the same as that of the irradiation treatment of (1) described in the method for producing the matte article A, and 100 nm or more is formed by the irradiation treatment of (1) in forming the matte layer. By irradiating a resin composition for matting formation containing a wrinkle formation stabilizer and a photopolymerization initiator forming a matte layer with ultraviolet rays having a wavelength of less than 200 nm, the surface of at least one of the matte layers is exposed to ultraviolet rays. , Wrinkles can be formed.
Regarding the need for the irradiation treatment of (2) above, by performing the irradiation treatment of (2) following the irradiation treatment of (1) above, the electron beam and wavelength light (ultraviolet rays) having a wavelength longer than the lower wavelength are obtained. ), The resin composition in which the wrinkles are retained can be cured as it is by irradiating at least one of them. Article I can be easily manufactured.

In the production method I of the present embodiment, after the irradiation treatment of (1) above, irradiation treatment of at least one of the electron beam of (2) and the ultraviolet rays having a wavelength of 200 nm or more and 400 nm or less is performed. As described above, by the irradiation treatment of (2), the shape of the wrinkles formed by the irradiation treatment of (1) above is cured as it is, and excellent visibility and texture of a matte effect can be stably obtained. By curing the resin forming the matte layer, excellent surface characteristics can be obtained.

The irradiation conditions of the electron beam adopted 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 acceleration voltage of the electron beam is preferably 10 kV or more, more preferably. Is 30 kV or more, more preferably 50 kV, still more preferably 75 kV or more, and the upper limit is preferably 300 kV or less, more preferably 250 kV or less, 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 can be easily maintained as it is, so that the visibility and texture of the matte effect are stably improved, and the resin composition for forming the matte layer is cured. Excellent surface properties can be obtained efficiently.
From the same viewpoint as this, the irradiation dose of the electron beam is preferably 5 kGy or more, more preferably 10 kGy or more, still more preferably 15 kGy or more, and the upper limit is preferably 150 kGy or less, more preferably 125 kGy or less, still more preferably. Is 100 kGy or less.
The electron beam source is not particularly limited as long as it can exhibit the above irradiation conditions. For example, a cockloft Walton type, a van de Graaff type, a resonance transformer type, an insulated core transformer type, a linear type, and a dynamitron type. , High frequency type and other various electron beam accelerators can be used.

(2) For the ultraviolet rays of 200 nm or more and 400 nm or less used in the irradiation treatment, for example, an ultraviolet irradiation device using an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light fluorescent lamp, a metal halide lamp, or the like as a light source is used. Can be irradiated. Further, 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 ultraviolet rays used in the irradiation treatment is preferably 330 nm or more, and the upper limit is preferably 390 nm or less. When the wavelength of ultraviolet rays is within the above range, the shape of the wrinkles can be easily maintained as it is, so that the visibility and texture of the matte effect are stably improved, and the resin composition for forming the matte layer is cured. Surface properties can be obtained efficiently.
From the same viewpoint as this, the output of the ultraviolet irradiation device that can be used for 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.

In the manufacturing method I of the present embodiment, if the irradiation treatment of (2) is performed by irradiation treatment of at least one of electron beam and ultraviolet light, not only excellent surface characteristics but also excellent visibility and texture of matting effect can be obtained. It can be obtained stably.

In the production method I of the present embodiment, (3) irradiation treatment for pre-curing may be performed before the irradiation treatments (1) and (2) above. (3) By performing the irradiation treatment for pre-curing, the visibility and texture of the matte effect of the matte layer are improved, and the surface characteristics are also improved. (3) Examples of the wavelength light used in the irradiation treatment for pre-curing include wavelength light of more than 320 nm, preferably more than 320 nm and 400 nm or less, and more preferably 385 nm or more and 400 nm or less. The resin composition for forming a matte layer can be pre-cured as a whole by irradiating it in advance using this wavelength light.
Regarding the pre-curing, the necessity of adoption may be appropriately determined according to the desired properties required for the matte layer (for example, surface characteristics such as processing characteristics and stain resistance). Further, although the above-mentioned wavelength light belongs to ultraviolet rays, it is also possible to use not only ultraviolet rays but also other ionizing radiations such as electron beams.

In the production method I of the present embodiment, the matte layer is 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, in which a resin composition for forming a matte layer is used. The coating layer (uncured resin layer) coated in 1 is subjected to the irradiation treatments (1) and (2) above in order.
When the matte decorative material obtained by the production method of the present embodiment has a base material described later, the resin composition for forming a matte layer can be applied to at least one main surface side of the base material. A matting agent is formed on the surface side.

(60 ° gloss value)
The 60 ° gloss value of the matte article I obtained by the manufacturing method I is 5.0 or less, which is the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value.
According to the production method I of the present embodiment, the amount of the wrinkle formation stabilizer is small as described above, the resin composition containing the photopolymerization initiator is adopted, and the specific conditions of the above (1) and (2) are specified. By performing the irradiation treatment with the above, the visibility and texture of the excellent matting effect can be stably obtained. Further, by suppressing the amount of the wrinkle formation stabilizer used to a small amount, it is possible to easily form a layer by suppressing a significant increase in the viscosity of the resin composition, and it is possible to easily form a layer according to the characteristics of the resin used for the matte layer. It naturally has surface characteristics such as excellent stain resistance, scratch resistance, and weather resistance.

[Formation of other layers]
The matte article I obtained by the production method I may have other layers such as a base material and other transparent resin layers, as will be described later. The manufacturing method in the case of having another layer will be described by taking, for example, the matte articles shown in FIGS. 3 and 4 described later as an example. 3 and 4 are cross-sectional views showing an embodiment of the matte article I obtained by the manufacturing method I of the present embodiment, and the matte article 1 (matte article I) is taken in the thickness direction (in the same figure). Is a cross-sectional view cut along a plane parallel to (Z direction).

In the case of a matte article having the base material 5 and the matte layer 4 shown in FIG. 3, a resin composition for forming the matte layer is applied to one main surface side of the base material, and the above (1) and By performing the irradiation treatment of (2) in order, the resin composition is cured to form a matte layer, whereby the matte article shown in FIG. 3 can be obtained.

In the case of a matte article having the base material 5, the decorative layer 6, the adhesive layer 7, the transparent resin layer 8, the primer layer 9, and the matte layer 4 shown in FIG. 4, on one main surface of the base material, A coating liquid containing a composition for forming a decorative layer and an adhesive layer is applied by the above-mentioned known method, and if necessary, dried and cured to form the decorative layer and the adhesive layer. Next, a resin film for forming a transparent resin layer on the adhesive layer is formed by dry lamination, and a composition for forming a primer layer on the transparent resin layer is applied by the above-mentioned known method, and if necessary. A primer layer is formed by drying and curing. Further, a resin composition for forming a matte layer is applied onto the primer layer, and the irradiation treatments (1) and (2) above are carried out in order to cure the resin composition and form a matte layer. By forming, the matte article shown in FIG. 4 is obtained. If there is an unnecessary layer according to the desired performance, it may be omitted as appropriate.

3 and 4 both show that the matte article I is a matte article having a base material, but as will be described later, it does not have a base material, that is, a layer consisting of a single layer having only a matte layer. It can also be configured. The manufacturing method of the matte article I in this case is the same as the content regarding the manufacturing method in the case of adopting the layer structure with a single layer described in the above-mentioned matte article A, on the surface of the releasable support having the release layer. It suffices to have a step of forming a coating layer for applying a resin composition for forming a matte layer, and a step of forming a matte layer for curing the resin composition to form a matte layer. The irradiation treatments (1) and (2) above may be carried out in order. Further, it is also the same that a solvent drying step may be provided if necessary, and the releasable support having a release layer may be peeled off and used when the matte article I is used.

[Other layers]
The matte article I obtained by the manufacturing method I requires, for example, a base material, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. as other layers in addition to the above-mentioned matte layer as described above. May have depending on. Each of the above layers that the matte article I that can be produced by the production method I can have will be described.

〔Base material〕
The matte article I may have a base material in addition to the matte layer as described in the above-mentioned matte article A, and as described above, various restrictions may be provided. It is preferable to have a base material from the viewpoint of avoiding the above. That is, the simplest layer structure of the matte article I is, like the matte article A, a layer structure consisting of a single layer having no base material and only a matte layer. In the case of having a base material, as described above, from the viewpoint of improving the visibility and texture of the matte effect, the base material should be provided on the surface opposite to at least one surface having wrinkles in the matte layer. Is preferable.
The base material that can be used in the matte article I is the same as that of the base material described for the matte article A.

(Primer layer)
The primer layer that the matte article I can have is the same as that of the primer layer described for the matte article A.

(Transparent resin layer)
The transparent resin layer that the matte article I can have is the same as that of the transparent resin layer described for the matte article A.

(Decorative layer)
The decorative layer that the matte article I can have is the same as the content regarding the decorative layer described for the matte article A.

(Adhesive layer)
The adhesive layer that the matte article I can have is the same as that of the adhesive layer described for the matte article A.

[Cosmetic member I]
As a typical use of the matte article I obtained by the manufacturing method I, the matte article I can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, vehicles, home appliances, etc. It is also possible to use it as a decorative member by laminating it with an adherend, combining it, or combining it (hereinafter, the decorative member using these matte articles I is referred to as "decorative member I". It may be called.). Which one to use may be determined as desired.
The form of the matte article I in the decorative member I, the adherend, the adhesive layer, the method for producing the decorative member I, the use of the decorative member I, and the like are the same as those described in the decorative member A.

[Manufacturing method J of goods]
The method for manufacturing the article of the present embodiment is
The resin composition containing no photopolymerization initiator is subjected to the irradiation treatments (1) and (2) in this order, and the resin composition is cured to form a surface wrinkle layer.
(Hereinafter, it may be simply referred to as "manufacturing method J").
(1) Irradiation treatment of wavelength light of 100 nm or more and less than 200 nm (2) Irradiation treatment of at least one of electron beam and wavelength light of 200 nm or more and 400 nm or less A cosmetic having excellent surface characteristics by a manufacturing method including such a step. The material can be easily manufactured. Further, by adopting the irradiation treatment having the above-mentioned characteristics (1) and (2) when curing the surface layer, excellent surface characteristics can be obtained without adding a photopolymerization initiator, and a matting effect can be obtained. Visibility can also be obtained.

The production method J is different from the production method described as the production method of the matte article A in that the resin composition does not contain a photopolymerization initiator and that the irradiation treatment of the above (2) is required. Formes the other irradiation treatment of (1), the wrinkle formation stabilizer, the matte layer (corresponding to the "surface wrinkle layer" in the manufacturing method J), its surface shape, and the matte layer (surface wrinkle layer). The resin and the resin composition, the 60 ° gloss value of the obtained article, each layer constituting the obtained article, and the like are basically the same as those described in the above-mentioned matte article A.
Hereinafter, the manufacturing method J will be described in more detail.

[Step of forming a surface wrinkle layer]
In the step of forming the surface wrinkle layer, the resin composition containing no photopolymerization initiator is subjected to the irradiation treatments (1) and (2) in this order, and the resin composition is cured to form the surface wrinkle layer. Is what you do.
In the production method J, the resin composition containing no photopolymerization initiator is subjected to the above two types of irradiation treatments (1) and (2) in order, the resin composition is cured, and wrinkles are formed on at least one surface. By having a step of forming a surface wrinkle layer having a surface wrinkle layer, it is possible to easily manufacture an article having excellent surface characteristics. That is, the surface wrinkle layer of the article obtained by the production method J is subjected to the two types of irradiation treatments (1) and (2) above in order for the resin composition containing no photopolymerization initiator, and the resin composition is obtained. It can be said that it is a layer having wrinkles on at least one surface obtained by curing.
Further, the surface wrinkle layer preferably contains a wrinkle formation stabilizer as described later. Even if the wrinkle formation stabilizer is not contained, the surface wrinkle layer will have wrinkles by performing the above two types of irradiation treatment in order, but the wrinkle formation stabilizer is included to stabilize the formation of wrinkles. It will be easier to do. Then, by stabilizing the formation of wrinkles, at least one surface of the surface wrinkle layer has an uneven shape composed of irregular wrinkles, and the 60 ° gloss value of the surface wrinkle layer becomes 5.0 or less. It becomes easy to obtain stable and excellent visibility of the matte effect.

The wrinkles on the surface wrinkle layer can exhibit the visibility of the matting effect, and according to the production method J, the resin composition containing no photopolymerization initiator is subjected to two specific types of irradiation treatment. Therefore, not only the excellent surface characteristics can be obtained by curing the resin composition, but also the visibility of the matte effect can be obtained due to the wrinkles contained in the surface wrinkle layer.
In order to promote the formation of wrinkles in the surface wrinkle layer and stably obtain the visibility of the matting effect, it is preferable that the resin composition for forming the surface wrinkle layer contains a wrinkle formation stabilizer. First, the wrinkle formation stabilizer will be described.

(Wrinkle formation stabilizer)
As the wrinkle-forming stabilizer preferably used in the production method J, the wrinkle-forming stabilizer described as being used in the matte article A is adopted.
At least one of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2 can be used as the wrinkle formation stabilizer, the average particle size of the wrinkle formation stabilizer 1 and the wrinkle formation stabilizer 2, the type of the wrinkle formation stabilizer, etc. The effects exhibited by using the formation stabilizer and the difference between the wrinkle formation stabilizer and the matting agent are basically the same as those described for the matte article A.

When a wrinkle formation stabilizer is used, its content is preferably 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 forming the surface wrinkle layer. Other preferable ranges are the same as those described for the matte article A.

(Surface shape of surface wrinkle layer)
The surface wrinkle layer of the article J (hereinafter, also simply referred to as “article J”) obtained by the production method J is a resin composition for forming a surface wrinkle layer containing no photopolymerization initiator, preferably a wrinkle formation stabilizer. It is a layer composed of a cured product of the containing resin composition. By forming wrinkles by two specific types of irradiation treatment as described above, curing of the resin composition proceeds even without a photopolymerization initiator or a wrinkle formation stabilizer. As a result, not only excellent surface characteristics can be obtained, but also a layer that exhibits a matte effect due to a light diffusing effect due to the shape of wrinkles. Further, by further using a wrinkle formation stabilizer, the formation of the wrinkles is stabilized, and the layer becomes a layer capable of stably exhibiting the visibility of the matting effect.

The surface shape of the surface wrinkle layer of the article J is basically the same as the content described for the matte layer of the matte article A. FIGS. 1 and 2 can also be applied to the surface wrinkle layer of the article J obtained by the manufacturing method J.
FIG. 1 is a schematic view in a plan view showing an embodiment of the article J obtained by the manufacturing method J, and is a schematic image of the surface of the article obtained in the examples. FIG. 1 shows that the article J obtained by the production method J has wrinkles formed on its surface, that is, on the surface of the surface wrinkle layer.

Regarding the surface shape of the surface wrinkle layer of Article J, even when the wrinkle formation stabilizer is not contained, at least one surface of the surface wrinkle layer has an uneven shape composed of irregular wrinkles. .. When the wrinkle formation stabilizer is included, the uneven shape composed of irregular wrinkles is more stably expressed, and the visibility of the matting effect can be stably exhibited. As described above, in Article J, the surface wrinkle layer is a layer that literally has wrinkles even if it does not contain a wrinkle formation stabilizer, and is a layer that can exhibit the visibility of the matte effect, but wrinkle formation. By using a stabilizer, the wrinkles are stably formed, so that it can be said that the layer can stably exhibit the visibility of the matting effect.

(resin)
In the production method J, the resin used for forming the matte layer is the same as the content relating to the resin described for the matte article A.

(Resin composition)
In the production method J, the resin composition used for forming the matte layer (resin composition for forming the matte layer) does not contain a photopolymerization initiator and may not contain a photopolymerization initiator. Although different from the matte article A, other additives such as various weather resistant agents that may be contained are the same as those relating to the resin composition described for the matte article A.

(Irradiation treatment)
In the production method J, it is necessary to perform the irradiation treatments (1) and (2) above in order. These irradiation treatments are the same as those relating to the irradiation treatment described in the above-mentioned production method I. In the above-mentioned production method I, (3) irradiation treatment for pre-curing may be performed as desired, but in production method J, (3) pre-curing is unnecessary.

(60 ° gloss value)
The article J obtained by the production method J has the visibility of the matting effect due to the wrinkles of the surface wrinkle layer, and the visibility of the effect is improved by using the wrinkle formation stabilizer. The 60 ° gloss value of the article J is preferably 5.0 or less, and the article J can be said to be a matte article having the visibility of the matting effect. In addition, the 60 ° gloss value of the article J is basically the same as the content regarding the 60 ° gloss value described for the matte article A. Therefore, the same applies to the standard deviation (σ) of the 60 ° gloss value.

According to the production method J of the present embodiment, the surface of the surface wrinkle layer is formed by adopting a resin composition containing no photopolymerization initiator and performing irradiation treatment under the specific conditions of (1) and (2) above. By forming wrinkles on the surface, the visibility of the matte effect has been obtained. Further, the wrinkle formation stabilizer preferably used makes it possible to stably obtain the visibility of the matting effect due to wrinkles, and by suppressing the amount used to a small amount as described above, the resin composition has a remarkable viscosity. By suppressing the rise, layer formation becomes possible, and surface characteristics such as excellent stain resistance, scratch resistance, and weather resistance are naturally provided according to the characteristics of the resin used for the surface wrinkle layer. ..

[Formation of other layers]
The formation of the other layer in the manufacturing method J is the same as the content relating to the formation of the other layer described in the manufacturing method I.
Therefore, the matte article J obtained by the manufacturing method J can have a layer structure having a base material and other layers as shown in FIGS. 3 and 4, and also has a layer structure consisting of a single layer having only a matte layer. obtain. The production method in the case of adopting a layer structure consisting of a single layer having only a matte layer and the case of adopting a layer structure having a base material and other layers is the same as the content described for the above-mentioned production method I.

[Other layers]
The matte article J obtained by the manufacturing method J requires, for example, a base material, a primer layer, a transparent resin layer, a decorative layer, an adhesive layer, etc. as other layers in addition to the above-mentioned matte layer as described above. May have depending on. Each of the above layers that the matte article J that can be manufactured by the manufacturing method J can have will be described.

〔Base material〕
The matte article J may have a base material in addition to the matte layer as described in the above-mentioned matte article A, and as described above, various restrictions may be provided. It is preferable to have a base material from the viewpoint of avoiding. That is, the simplest layer structure of the matte article J is, like the matte article A, a layer structure consisting of a single layer having only a matte layer and having no base material. In the case of having a base material, as described above, from the viewpoint of improving the visibility and texture of the matte effect, the base material should be provided on the surface opposite to at least one surface having wrinkles in the matte layer. Is preferable.
The base material that can be used in the matte article J is the same as that of the base material described for the matte article A.

(Primer layer)
The primer layer that the matte article J can have is the same as that of the primer layer described for the matte article A.

(Transparent resin layer)
The transparent resin layer that the matte article J can have is the same as that of the transparent resin layer described for the matte article A.

(Decorative layer)
The decorative layer that the matte article J can have is the same as the content relating to the decorative layer described for the matte article A.

(Adhesive layer)
The adhesive layer that the matte article J can have is the same as that of the adhesive layer described for the matte article A.

[Cosmetic member J]
As a typical use of the article J obtained by the manufacturing method J, the matte article J can be used as it is as a so-called decorative member that constitutes the surface of a building, various furniture, a vehicle, a home electric appliance, or the like. It is also possible to use it as a decorative member by laminating it with an adherend, combining it, or combining it (hereinafter, the decorative member using these matte articles J is referred to as "decorative member J". There is.). Which one to use may be determined as desired.
The form of the matte article J in the decorative member J, the adherend, the adhesive layer, the manufacturing method of the decorative member J, the use of the decorative member J, and the like are the same as those described in the decorative member A.

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

(Evaluation method: 60 ° gloss value)
For the articles obtained in Examples and Comparative Examples, a gloss meter (“Micro Gloss (model name)”, manufactured by BYK Gardner) was used to achieve a 60 ° mirror glossiness in accordance with K 5600-4-7: 1999. Was measured at any 10 points, and the average value of the 10 points was taken as a 60 ° gloss value.

(Standard deviation of 60 ° gross value (σ))
For the articles obtained in Examples and Comparative Examples, a gloss meter (“Micro Gloss (model name)”, manufactured by BYK Gardner) was used to achieve a 60 ° mirror glossiness in accordance with K 5600-4-7: 1999. Was measured at any 10 points, and the standard deviation (σ) was calculated based on the measured values at the 10 points. The standard deviation (σ) value is an index of the stability of wrinkle formation. When it is 0.3 or less, the stability of wrinkle formation is high, and when it is less than 0.30, the stability of wrinkle formation is sufficient. It can be judged that it is not.

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

(Evaluation of scratch resistance (steel wool resistance))
The following rubbing tests were performed on the articles obtained in Examples 1A to 3A and Comparative Examples 1A and 2A. Gloss value when the 60 ° gloss value on the matte layer side before the following rubbing test is G ₀ and the 60 ° gloss value on the matte layer side after the rubbing test is G _1. The rate of change of (| (G _{1 −} G ₀ ) | / G ₀ × 100) was calculated. If it is 20% or less, it is considered to have excellent steel wool resistance and is accepted.
(Rubbing test)
Place the obtained article on the base of the abrasion tester type II (JIS L0849: 2013), set steel wool # 0000 so as to contact the matte layer of the matte article, and load 1500 g / cm ² The movement speed was 100 mm / sec, and the reciprocating movement distance was 100 mm, and the mixture was reciprocated 30 times.

(Evaluation of scratch resistance (scratch resistance))
The articles obtained in Examples 1A to 3A and Comparative Examples 1A and 2A were subjected to a scratch test using a paint adhesion tester (“Hoffman Scratch Hard Nestester (product name)”, manufactured by BYK Gardener), and continuously. The maximum load at which no scratches were generated was measured. The larger the maximum load, the better the scratch resistance (scratch resistance).

(Evaluation of easy decontamination)
The articles obtained in Examples 1E to 3E and Comparative Examples 1E and 2E were subjected to acetone as a contaminant in accordance with "15.3 C method" of JIS K6902: 2007 (thermosetting resin high-pressure decorative board test method). Contamination test was performed using (Material No. 3), household ammonia (Material No. 4), 10% phosphoric acid (Material No. 5), black oil-based marker (Material No. 12) and crayon (Material No. 14), and " The detergency was evaluated according to the criteria of grades 0 to 5 based on "15.35.2 Cleaning Procedure". The closer it is to 0 grade, the better the cleanliness.
In addition, the stain resistance was evaluated according to the criteria of

grades

5, 3 and 1 based on "15.3.6.2 stain resistance". The closer it is to grade 5, the better the stain resistance.
The above was the evaluation of easy decontamination.

(Evaluation of light resistance)
The articles obtained in Examples 1F to 3F and Comparative Examples 1F to 3F were subjected to a weather resistance test for 200 hours using a weather resistance test device "S-UV (with rain)". When the 60 ° gloss value on the matte light resistant layer side before the weather resistance test is G ₀ and the 60 ° gloss value on the matte light resistant layer side after the weather resistance test is G ₁ The rate of change of the gross value (| (G _{1 −} G ₀ ) | / G ₀ × 100) was calculated. If it is 20% or less, it is considered to have excellent light resistance and is accepted.

(Evaluation of marker erasability)
For the articles obtained in Examples 1G to 3G, Comparative Examples 1G and 2G, the ease of removing the markers according to the methods a) to c) below using the black markers specified in JIS S6052: 2014. The brightness and chromaticity before and after the test were measured using a spectrophotometer (“SE6000” (model number), manufactured by Japanese Industrial Standards Co., Ltd.), and the color difference was measured by the following formula. (ΔE ^* ab) was calculated.
ΔE ^* ab = [(L ^* _2- L ^* ₁ ) ² + (a ^* _2- a ^* ₁ ) ² + (b ^* _2- a ^* ₂ ) ² ] ^1/2
(Test of marker dropability)
a) Fill the matte writing layer of the sheet with the marker in an area of 2 cm x 4 cm.
b) One minute after painting, erase using an unused melamine foam whiteboard eraser (2 cm x 2 cm, whiteboard sharp drop eraser (Auto Co., Ltd.)).
c) Repeat a) and b) above 50 times.

[Example 1A]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. , Resin composition for forming a matte layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle size: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied by the gravure method. (Applying amount: 5 g / m ² (when dried)), then irradiating ultraviolet rays using a UV irradiating device composed of LEDs (wavelength: 395 nm, ultraviolet amount: 6 W / cm ² ), and then using an excima light irradiating device. Irradiate with ultraviolet rays (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), and then using a high-pressure mercury lamp. After irradiation (wavelength: 365 nm, ultraviolet output density: 200 W / cm), a matte layer was provided on the base material to obtain a matte article having the base material and the matte layer. For the obtained matte article, the 60 ° gloss value and the rate of change of the gloss value were measured by the above method. The measurement results are shown in Table 1A.

[Examples 2A and 3A]
In Example 1A, a matte article was obtained in the same manner as in Example 1A, except that the wrinkle formation stabilizer in the resin composition for forming a matte layer was used in the amount shown in Table 1A. Table 1A shows the 60 ° gloss value and the rate of change of the gloss value on the matte layer side of the obtained matte article.

[Comparative Example 1A]
In Example 1A, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, that is, the same as in Example 1A except that the wrinkle formation stabilizer was not used. , Got the goods. Table 1A shows the 60 ° gloss value on the matte layer side of the obtained article and the rate of change of the gloss value.

[Comparative Example 2A]
In Example 1A, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, and 15.0 parts by mass of the matting agent (average particle size: 8.0 μm) was used instead. Then, an article was obtained in the same manner as in Example 1A, except that only an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) was irradiated. Table 1A shows the 60 ° gloss value on the matte layer side of the obtained article and the rate of change of the gloss value.

From the results in Table 1A, the matte article A of the present embodiment has a 60 ° gloss value of 2.0 or less on the matte layer side, and is an article having extremely excellent visibility of the matte effect. Was confirmed. Regarding scratch resistance, the rate of change of the gloss value is 20% or less, the scratch resistance is 400 g, and it may have excellent scratch resistance (steel wool resistance and scratch resistance). confirmed. It has also been confirmed that wrinkle formation is stable because the standard deviation (σ) is less than 0.30, and the stability of wrinkle formation leads to the visibility, texture and scratch resistance of the matte effect. It is thought that it is.

On the other hand, in the article of Comparative Example 1A containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 8, stable visibility of the matting effect could not be obtained. There was a part where the gloss value was the same as that of the example, but there was a part with a high gloss and the surface condition was unstable, so it could not be said that the texture was excellent. The instability can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
Even if the article of Comparative Example 2A containing a matte agent contains 15.0 parts by mass, which is larger than the content of the wrinkle formation stabilizer in the example, wrinkles are formed in the surface layer corresponding to the matte layer. It was confirmed that the 60 ° gloss value was 8.3, which was inferior to the gloss value of the matte article of the example, and was also inferior to the texture. Further, it was confirmed that the rate of change of the gloss value of the article of Comparative Example 2A was 23.7% and the scratch resistance was 300 g, which were inferior in scratch resistance.

Further, according to the optical microscope images of Examples 1A to 3A (FIGS. 5 to 7 respectively), it can be confirmed that the matte articles of these Examples have irregular wrinkles on the surface thereof. On the other hand, according to the optical microscope image of Comparative Example 1A (FIG. 8), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 9) of Comparative Example 2A, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the matte article A of the present embodiment exhibits extremely excellent visibility of the matte effect due to the wrinkles on the surface thereof. Further, the matte article A of the present embodiment has a high surface texture and a high-class feeling due to the formation of wrinkles, but the surface of the article of Comparative Example 1A has some wrinkles. , The matte effect could not be obtained stably, and the texture of the surface was monotonous, so it could not be said that it had a high-class feel.

[Example 1B]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. , Resin composition for forming a matte layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle size: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied by the gravure method. (Applying amount: 5 g / m ² (when dried)), then irradiating ultraviolet rays using a UV irradiating device composed of LEDs (wavelength: 395 nm, ultraviolet amount: 6 W / cm ² ), and then using an excima light irradiating device. Irradiate with ultraviolet rays (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), and then using a high-pressure mercury lamp. After irradiation (wavelength: 365 nm, ultraviolet output density: 200 W / cm), a matte layer was provided on the base material to obtain a matte article having the base material and the matte layer. The gloss value of the obtained matte article was measured at 60 ° from the matte layer side and found to be 1.4.

[Examples 2B and 3B]
In Example 1B, a matte article was obtained in the same manner as in Example 1B, except that the wrinkle formation stabilizer in the resin composition for forming a matte layer was used in the amount shown in Table 1B. Table 1B shows the evaluation of the 60 ° gloss value and texture of the obtained matte decorative material on the matte layer side. The evaluation of the texture is also shown in Table 1B.

[Comparative Example 1B]
In Example 1B, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, that is, the same as in Example 1B except that the wrinkle formation stabilizer was not used. , Got the goods. Table 1B shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

[Comparative Example 2B]
In Example 1B, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, and 15.0 parts by mass of the matting agent (average particle size: 8.0 μm) was used instead. Then, an article was obtained in the same manner as in Example 1B except that only an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) was irradiated. Table 1B shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

From the results in Table 1B, the matte article B of the present embodiment has a 60 ° gloss value of 1.8 or less on the matte layer side, and is an article having extremely excellent visibility of the matte effect. It was confirmed that the texture was also excellent. In addition, since the standard deviation (σ) is less than 0.30, it has been confirmed that the formation of wrinkles is stable, and it is considered that the stability of the formation of wrinkles leads to the visibility and texture of the matte effect. Conceivable.

On the other hand, in the article of Comparative Example 1B containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 13, stable visibility of the matting effect could not be obtained. There was a part where the gloss value was the same as in the example, but there was a part with high gloss and the surface condition was unstable (not uniform), and it could not be said that the texture was excellent. .. The instability can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
Further, even if the article of Comparative Example 2B containing a matte agent contains 15.0 parts by mass, which is larger than the content of the wrinkle formation stabilizer in the examples, the surface layer corresponding to the matte layer has wrinkles. It was confirmed that there was no formation, the 60 ° gloss value was 8.3, which was inferior to the gloss value of the matte article of the example, and the texture was also inferior.

Further, according to the optical microscope images of Examples 1B to 3B (FIGS. 10 to 12 respectively), it can be confirmed that the matte decorative materials of these Examples have irregular wrinkles on the surface thereof. On the other hand, according to the optical microscope image of Comparative Example 1B (FIG. 13), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 14) of Comparative Example 2B, wrinkles like the matte article B of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the matte article B of the present embodiment exhibited extremely excellent visibility and texture of the matte effect due to the wrinkles on the surface thereof.

[Example 1C]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. , Resin composition for forming a matte layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle size: 3 μm): 3 .0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) is applied by the gravure method (application amount: 5 g / m ² (when dried)), and then a UV irradiation device composed of LEDs. Is irradiated with ultraviolet rays (wavelength: 395 nm, amount of ultraviolet rays: 6 W / cm ² ), and then ultraviolet rays are irradiated using an excimer light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, Integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), then further irradiated with a high-pressure mercury lamp (ultraviolet output density: 200 W / cm) to provide a matte layer on the substrate. A matte article having a base material and a matte layer was obtained. The gloss value of the obtained matte article was measured at 60 ° from the matte layer side and found to be 1.5. The evaluation of the texture is also shown in Table 1C.

[Examples 2C and 3C]
In Example 1C, a matte article was obtained in the same manner as in Example 1C, except that the wrinkle formation stabilizer in the resin composition for forming a matte layer was used in the amount shown in Table 1C. Table 1C shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side.

[Comparative Example 1C]
In Example 1C, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, that is, the same as in Example 1C except that the wrinkle formation stabilizer was not used. , Got the goods. Table 1C shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

[Comparative Example 2C]
In Example 1C, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, and 15.0 parts by mass of the matting agent (average particle size: 8.0 μm) was used instead. Then, an article was obtained in the same manner as in Example 1C except that only an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) was irradiated. Table 1C shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

From the results in Table 1C, the matte article C of the present embodiment has a 60 ° gloss value of 1.8 or less on the matte layer side, and is an article having extremely excellent visibility of the matte effect. Was confirmed. In addition, since the standard deviation (σ) is less than 0.30, it has been confirmed that the formation of wrinkles is stable, and it is considered that the stability of the formation of wrinkles leads to the visibility and texture of the matte effect. Conceivable.

On the other hand, in the article of Comparative Example 1C containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 18, stable visibility of the matting effect could not be obtained. There was a part where the gloss value was the same as in the example, but there was a part with high gloss and the surface condition was unstable (not uniform), and it could not be said that the texture was excellent. .. The instability can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
Further, the decorative material of Comparative Example 2C containing a large amount of a matting agent did not form wrinkles in the surface layer corresponding to the matte layer, and its 60 ° gloss value was 8.3, which is the gloss of the matte article of the example. It was confirmed that the value was inferior and the texture was also inferior.

Further, according to the optical microscope images of Examples 1C to 3C (FIGS. 15 to 17 respectively), it can be confirmed that the matte articles of these Examples have irregular wrinkles on the surface thereof. On the other hand, according to the optical microscope image of Comparative Example 1C (FIG. 18), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 19) of Comparative Example 2C, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the matte article C of the present embodiment exhibited extremely excellent visibility and texture of the matte effect due to the wrinkles on the surface thereof.

[Example 1D]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. , Resin composition for forming a matte layer (polyfunctional urethane acrylate oligomer (number of functional groups: 4): 65 parts by mass, polyfunctional acrylate monomer (number of functional groups: 4): 35 parts by mass, wrinkle formation stabilizer (silica particles, Average particle size: 5 nm): 5.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) was applied by the gravure method (application amount: 5 g / m ² (when dried)), and then Ultraviolet rays are irradiated using a UV irradiation device composed of LEDs (wavelength: 395 nm, amount of ultraviolet rays: 6 W / cm ² ), and then ultraviolet rays are irradiated using an excima light irradiation device (wavelength: 172 nm (Xe ₂ )). Ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less), then further irradiated with a high-pressure mercury lamp (ultraviolet output density: 200 W / cm), substrate A matte layer was provided on the top, and a matte article having a base material and a matte layer was obtained. The gloss value of the obtained matte article was measured at 60 ° from the matte layer side and found to be 1.5.

[Examples 2D and 3D]
In Example 1D, a matte article was obtained in the same manner as in Example 1D, except that the wrinkle formation stabilizer in the resin composition for forming a matte layer was used in the amount shown in Table 1D. Table 1D shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side. The evaluation of the texture is also shown in Table 1D.

[Comparative Example 1D]
In Example 1D, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, that is, the same as in Example 1D except that the wrinkle formation stabilizer was not used. , Got the goods. Table 1D shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

[Comparative Example 2D]
In Example 1D, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, and 15.0 parts by mass of the matting agent (average particle size: 8.0 μm) was used instead. Then, an article was obtained in the same manner as in Example 1D, except that only an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) was irradiated. Table 1D shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

From the results in Table 1D, the matte article D of the present embodiment has a 60 ° gloss value of 2.0 or less on the matte layer side, and is an article having extremely excellent visibility of the matte effect. It was confirmed that the texture was also excellent. In addition, since the standard deviation (σ) is less than 0.30, it has been confirmed that the formation of wrinkles is stable, and it is considered that the stability of the formation of wrinkles leads to the visibility and texture of the matte effect. Conceivable.

On the other hand, in the article of Comparative Example 1D containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 23, stable visibility of the matting effect could not be obtained. There was a part where the gloss value was the same as in the example, but there was a part with high gloss and the surface condition was unstable (not uniform), and it could not be said that the texture was excellent. .. The instability can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
Further, even if the decorative material of Comparative Example 2D containing a matte agent contains 15.0 parts by mass, which is larger than the content of the wrinkle formation stabilizer in the examples, wrinkles are formed on the surface layer corresponding to the matte layer. It was confirmed that the 60 ° gloss value was 8.3, which was inferior to the gloss value of the matte article of the example, and was also inferior to the texture.

Further, according to the 1D to 3D optical microscope images of Examples (FIGS. 20 to 22 respectively), it can be confirmed that the matte decorative materials of these Examples have irregular wrinkles uniformly over the entire surface thereof. .. On the other hand, according to the optical microscope image of Comparative Example 1D (FIG. 23), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 24) of Comparative Example 2D, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the matte article D of the present embodiment exhibited extremely excellent visibility and texture of the matte effect due to the wrinkles on the surface thereof.

[Example 1E]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. , Resin composition for forming a matte decontamination layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle size: 3 μm): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle size: 5 nm): 3.0 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) by gravure method (Applying amount: 5 g / m ² (when dried)), then irradiating ultraviolet rays using a UV irradiation device composed of LEDs (wavelength: 395 nm, ultraviolet amount: 6 W / cm ² ), and then excimer light. Ultraviolet rays are irradiated using an irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), and then a high-pressure mercury lamp. Is irradiated with (wavelength: 365 nm, ultraviolet output density: 200 W / cm), a matte decontamination layer is provided on the base material, and the base material (sheet) and the matte decontamination layer are provided. I got the goods. The 60 ° gloss value of the obtained matte article was measured by the above method. The measurement results are shown in Table 1E. In addition, the easy decontamination property was evaluated by the above method. The evaluation results are shown in Table 1E.

[Examples 2E and 3E]
In Example 1E, a matte article was obtained in the same manner as in Example 1E, except that the wrinkle formation stabilizer in the resin composition for forming the matte decontamination layer was used in the amount shown in Table 1E. .. The 60 ° gloss value of the obtained matte article was measured by the above method. The measurement results are shown in Table 1E. In addition, the easy decontamination property was evaluated by the above method. The evaluation results are shown in Table 1E.

[Comparative Example 1E]
In Example 1E, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte decontamination layer was set to 0 parts by mass, that is, the wrinkle formation stabilizer was not used. In the same way, an article was obtained. The 60 ° gloss value of the obtained article was measured by the above method. The measurement results are shown in Table 1E. In addition, the easy decontamination property was evaluated by the above method. The evaluation results are shown in Table 1E.

[Comparative Example 2E]
In Example 1E, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte decontamination layer was set to 0 parts by mass, and the matting agent (average particle size: 8.0 μm) was used instead as 15.0. An article was obtained in the same manner as in Example 1E, except that parts by mass were used and only an electron beam (acceleration voltage: 75 kV, irradiation dose: 3c0 kGy (3Mrad)) was irradiated. The 60 ° gloss value of the obtained article was measured by the above method. The measurement results are shown in Table 1E. In addition, the easy decontamination property was evaluated by the above method. The evaluation results are shown in Table 1E.

From the results in Table 1E, the matte article E of the present embodiment has a 60 ° gloss value of 1.8 or less on the matte easy decontamination layer side, and is extremely excellent in visibility of the matte effect. It was confirmed that. Regarding easy decontamination, detergency was grade 3 for black oil-based markers and crayons, but grade 0 for other pollutants, and it had excellent cleanliness, and stain resistance was all contamination. Since the substance was grade 5 and had excellent stain resistance, it was confirmed that it had excellent easy decontamination properties.
It has also been confirmed that wrinkle formation is stable because the standard deviation (σ) is less than 0.30, and the stability of wrinkle formation leads to the visibility, texture and stain resistance of the matte effect. It is thought that it is.

On the other hand, in the article of Comparative Example 1E containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 28, stable visibility of the matting effect could not be obtained. There was a part where the gloss value was the same as that of the example, but there was a part with a high gloss and the surface condition was unstable, so it could not be said that the texture was excellent. The instability can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
The article of Comparative Example 2E containing a matting agent has wrinkles on the surface layer corresponding to the matte easy decontamination layer even if it contains 15.0 parts by mass, which is larger than the content of the wrinkle formation stabilizer in the examples. It was confirmed that the 60 ° gloss value was 8.3, which was inferior to the gloss value of the matte article of the example, and was also inferior to the texture.
Regarding the easy decontamination property of the article of Comparative Example 2E, the detergency of the black oil-based marker and the crayon was 4th grade and 5th grade, respectively, and the stain resistance was 3rd grade and 1st grade, respectively. It was confirmed to be inferior.

Further, according to the optical microscope images of Examples 1E to 3E (FIGS. 25 to 27, respectively), it can be confirmed that the matte articles of these Examples have irregular wrinkles on the surface thereof. On the other hand, according to the optical microscope image of Comparative Example 1E (FIG. 28), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 29) of Comparative Example 2E, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the matte article E of the present embodiment exhibits extremely excellent visibility of the matte effect due to the wrinkles on the surface thereof. Further, the matte article E of the present embodiment has a high surface texture and a high-class feeling due to the formation of wrinkles, but the surface of the article of Comparative Example 1E has some wrinkles. The visibility of the matte effect could not be obtained stably, and the texture of the surface was monotonous, so it could not be said that it had a high-class feeling.

[Example 1F]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. In addition, a resin composition for forming a matte light-resistant layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle diameter: 3 μm). ): 3.0 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3.0 parts by mass, UV absorber (trade name: Adecaster LA-46, hydroxyphenyltriazine UV absorber, (Manufactured by ADEKA Co., Ltd.) 1.0 part by mass, photopolymerization initiator (benzophenone type): 0.8 part by mass) is applied by the gravure method (application amount: 5 g / m ² (when dried)), and then from the LED. Ultraviolet rays are irradiated using the configured UV irradiation device (wavelength: 395 nm, ultraviolet ray amount: 6 W / cm ² ), and then ultraviolet rays are irradiated using the Exima light irradiation device (wavelength: 172 nm (Xe ₂ ), and ultraviolet rays are output. Density: 1 W / cm, integrated light intensity: 10-100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), then further irradiated with a high-pressure mercury lamp (wavelength: 365 nm, ultraviolet output density: 200 W / cm). A matte light-resistant layer was provided on the base material to obtain a matte article having a base material sheet and a matte light-resistant layer. For the obtained matte article, the 60 ° gloss value and the rate of change of the gloss value were measured by the above method. The measurement results are shown in Table 1F. The evaluation results evaluated by the above method are shown in Table 1F.

[Examples 2F and 3F]
In Example 1F, a matte article was obtained in the same manner as in Example 1F, except that the wrinkle formation stabilizer in the resin composition for forming a matte light resistant layer was used in the amount shown in Table 1F. Table 1F shows the 60 ° gloss value and the rate of change of the gloss value on the matte light resistant layer side of the obtained matte article. The evaluation results evaluated by the above method are shown in Table 1F.

[Comparative Example 1F]
In Example 1F, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte light resistant layer was set to 0 parts by mass, that is, the same as in Example 1F except that the wrinkle formation stabilizer was not used. And got the goods. Table 1F shows the 60 ° gloss value and the rate of change of the gloss value on the matte light resistant layer side of the obtained article. The evaluation results evaluated by the above method are shown in Table 1F.

[Comparative Example 2F]
In Example 1F, the amount of the wrinkle-forming stabilizer used in the resin composition for forming a matte light-resistant layer was set to 0 parts by mass, and instead, a matting agent (average particle size: 8.0 μm) was used in an amount of 15.0 parts by mass. An article was obtained in the same manner as in Example 1F, except that it was used and irradiated only with ultraviolet rays (wavelength: 365 nm, ultraviolet output density: 200 W / cm) using a high-pressure mercury lamp. Table 1F shows the 60 ° gloss value and the rate of change of the gloss value on the matte light resistant layer side of the obtained article. The evaluation results evaluated by the above method are shown in Table 1F.

[Comparative Example 3F]
In Example 1F, the amount of the ultraviolet absorber used in the resin composition for forming the matte light-resistant layer was set to 0 parts by mass, that is, the same as in Example 1F except that the ultraviolet absorber was not used. I got the goods. Table 1F shows the 60 ° gloss value and the rate of change of the gloss value on the matte light resistant layer side of the obtained article. The evaluation results evaluated by the above method are shown in Table 1F.

From the results in Table 1F, the matte article F of the present embodiment has an extremely excellent visibility of the matte effect and has a texture because the 60 ° gloss value on the matte light resistant layer side is 1.8 or less. It was confirmed that it is an excellent product. Regarding the light resistance, since the rate of change of the gloss value was 20% or less, it was confirmed that the product had excellent light resistance.
It has also been confirmed that wrinkle formation is stable because the standard deviation (σ) is less than 0.30, and the stability of wrinkle formation leads to the visibility, texture and light resistance of the matte effect. It is thought that there is.

On the other hand, in the article of Comparative Example 1F containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 33, stable visibility of the matting effect could not be obtained. There was a part where the gloss value was the same as that of the example, but there was a part with a high gloss and the surface condition was unstable, so it could not be said that the texture was excellent. The instability can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
Even if the article of Comparative Example 2F containing a matting agent contains 15.0 parts by mass, which is larger than the content of the wrinkle forming stabilizer in the example, wrinkles are formed on the surface layer corresponding to the matte light resistant layer. The 60 ° gloss value is 8.3, which is inferior to the gloss value of the matte article of the example, and even if a larger amount of the matting agent than the amount of the wrinkle formation stabilizer used in the example is used, It was confirmed that the 60 ° gloss value of the example was not reached. In addition, the article of Comparative Example 3F containing no ultraviolet absorber contained a wrinkle formation stabilizer, so that the 60 ° gloss value before the test was as small as 1.4, and the texture was excellent, but the 60 ° gloss. The value increased by 64.3%, and it could not be said that the light resistance was excellent.

Further, according to the optical microscope images of Examples 1F and 2F (FIGS. 30 and 31, respectively), it can be confirmed that the matte articles of these Examples have irregular wrinkles uniformly on the surface thereof. On the other hand, according to the optical microscope image (FIG. 32) on the 1st floor of Comparative Example, as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 33) of Comparative Example 2F, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the matte article F of the present embodiment exhibits extremely excellent visibility of the matte effect due to the wrinkles on the surface thereof.

[Example 1G]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. In addition, a resin composition for forming a matte writing layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer 1 (silica particles, average particle size: 3 μm). ): 3 parts by mass, wrinkle formation stabilizer 2 (silica particles, average particle diameter: 5 nm): 3 parts by mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) is applied (applied) by the gravure method. Amount: 5 g / m ² (when dry)), then irradiate with ultraviolet light using a UV irradiator composed of LEDs (wavelength: 395 nm, amount of ultraviolet light: 6 W / cm ² ), then using an excima light irradiator. Irradiate with ultraviolet rays (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration of 200 ppm or less)), and then further irradiate with a high-pressure mercury lamp. (Radio: 365 nm, ultraviolet output density: 200 W / cm), a matte writing layer was provided on the base material, and a matte article having the base material and the matte writing layer was obtained. The 60 ° gloss value of the obtained matte article was measured by the above method. The measurement results are shown in Table 1G. In addition, the marker erasability was evaluated by the above method. The evaluation results are shown in Table 1G.

[Examples 2G and 3G]
In Example 1G, a matte article was obtained in the same manner as in Example 1G, except that the amount of the wrinkle formation stabilizer in the resin composition for forming the matte writing layer was the amount shown in Table 1G. The 60 ° gloss value of the obtained matte article was measured by the above method. The measurement results are shown in Table 1G. In addition, the marker erasability was evaluated by the above method. The evaluation results are shown in Table 1G.

[Comparative Example 1G]
In Example 1G, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte writing layer was set to 0 parts by mass, that is, the same as in Example 1G except that the wrinkle formation stabilizer was not used. And got the goods. The 60 ° gloss value of the obtained article was measured by the above method. The measurement results are shown in Table 1G. In addition, the marker erasability was evaluated by the above method. The evaluation results are shown in Table 1G.

[Comparative Example 2G]
In Example 1G, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte writing layer was set to 0 parts by mass, and the amount of the matting agent (average particle size: 8.0 μm) was set to 15.0 parts by mass instead. An article was obtained in the same manner as in Example 1G except that it was used and irradiated only with an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)). The 60 ° gloss value of the obtained article was measured by the above method. The measurement results are shown in Table 1G. In addition, the marker erasability was evaluated by the above method. The evaluation results are shown in Table 1G.

From the results in Table 1G, the matte article G of the present embodiment has a 60 ° gloss value of 2.0 or less on the matte writing layer side, and is an article having excellent visibility due to the matte effect. Was confirmed. It was also confirmed that the marker erasability was excellent with a small color difference and excellent texture.
It has also been confirmed that wrinkle formation is stable because the standard deviation (σ) is less than 0.30, and the stability of wrinkle formation leads to the visibility of the matte effect, texture, and marker erasability. It is thought that it is.

On the other hand, in the article of Comparative Example 1 containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 39, the visibility due to the matting effect could not be stably obtained. There was a part where the gloss value was the same as in the example, but there was a part with high gloss and the surface condition was unstable (not uniform), and it could not be said that the texture was excellent. .. The instability can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
The article of Comparative Example 2G containing a matting agent and not irradiating the surface with excimer light had no wrinkles on the surface layer corresponding to the matte writing layer, and its 60 ° gloss value was 8.3, which is an example. It was confirmed that the gloss value of the writing sheet was inferior, the visibility was inferior due to the matte effect, and the texture was also inferior.
It was also confirmed that the marker erasability of the article of Comparative Example 2G was inferior due to the large color difference.

Further, according to the optical microscope images of Examples 1G to 3G (FIGS. 36 to 38, respectively), it can be confirmed that the matte articles of these Examples have irregular wrinkles uniformly on the surface thereof. On the other hand, according to the optical microscope image of Comparative Example 1G (FIG. 39), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 40) of Comparative Example 2G, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, the matte article G of the present embodiment exhibits the visibility due to the extremely excellent matte effect due to the wrinkles on the surface thereof, and also exhibits the excellent marker erasability and is excellent in texture. It was confirmed that

[Example 1H]
A PET sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and a resin composition containing acrylic resin and urethane resin as a binder resin is applied to one surface of the base material to apply a primer layer (thickness). : 2 μm) is provided, and a resin composition for forming a matte-type layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stable on the primer layer. The agent (silica particles, average particle size: 3 μm): 1.0 part by mass, photopolymerization initiator (benzophenone type): 0.8 part by mass) was applied by the gravure method (application amount: 5 g / m ² (drying). (Time)), then irradiate ultraviolet rays using a UV irradiator composed of LEDs (wavelength: 395 nm, amount of ultraviolet rays: 0.6 W / cm ² ), and then irradiate ultraviolet rays using an excimer light irradiator (wavelength). 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less), and then further irradiated with a high-pressure mercury lamp (wavelength: 365 nm, Ultraviolet output density: 200 W / cm), a matte-type layer was provided on the base material sheet, and a matte article having a base material (sheet) and a matte-type layer was obtained.

Next, on titanium paper base paper (“PM-602K (trade name”, manufactured by KJ Special Paper Co., Ltd., basis weight: 60 g / m ² , thickness: 100 μm)), 60 parts by mass of melamine formaldehyde resin, 35 parts by mass of water and A thermosetting uncured resin composition containing 5 parts by mass of isopropyl alcohol is impregnated with an impregnating device so that the uncured resin composition has ^{a ratio of 60 g / m 2} (when dried) and dried. Obtained a resin-impregnated decorative sheet.
The obtained resin-impregnated decorative sheet is impregnated with a reinforcing layer (kraft paper impregnated with a liquid uncured resin composition made of phenol resin, and obtained by impregnating the obtained resin-impregnated decorative sheet with a phenol resin-impregnated core paper ^{having a basis weight of 245 g / m 2 (“Ota Core”).} , Made by Ota Sangyo Co., Ltd.), laminated so that the titanium paper base paper and the reinforcing layer are in contact with each other, and further, the decorative layer of the resin-impregnated decorative sheet and the matting of the matte article. It was laminated so that it faces the mold layer. This is sandwiched between two mirror plates, heat-molded at a pressure of 0.98 MPa and a heating temperature of 150 ° C. for 10 minutes using a heat press machine, and the uncured resin composition is made into a thermosetting resin to form melamine. A cured resin layer containing a resin was formed. By peeling the matte article from the thermosetting resin layer, a resin decorative material (melamine resin decorative board) in which the shape (matte surface) of the matte type layer of the matte article was shaped was obtained. .. The 60 ° gloss value of the surface of the obtained matte decorative material on the side on which the matte surface was shaped was measured by the above method. The measurement results are shown in Table 1H.

[Example 2H]
In Example 1H, a matte article was obtained in the same manner as in Example 1H, except that the amount of the wrinkle formation stabilizer in the resin composition for forming the matte type layer was set as shown in Table 1H. Using the obtained matte article, a matte decorative material (melamine resin decorative board) was obtained in the same manner as in Example 1H. The 60 ° gloss value of the obtained matte decorative material is shown in Table 1H.

[Comparative Example 1H]
In Example 1H, an article was obtained in the same manner as in Example 1H, except that the amount of the wrinkle formation stabilizer used in the resin composition for forming a matte-type layer was 0 parts by mass. Using the obtained article, a decorative material (melamine resin decorative board) was obtained in the same manner as in Example 1H. The 60 ° gloss value of the obtained decorative material is shown in Table 1H.

[Comparative Example 2H]
In Example 1H, the amount of the wrinkle-forming stabilizer used in the resin composition for forming a matte-type layer was set to 0 parts by mass, and the amount of the matting agent (average particle size: 5.0 μm) was 15.0 parts by mass instead. An article was obtained in the same manner as in Example 1H, except that the particles used were irradiated with ultraviolet rays (wavelength: 365 nm, ultraviolet output density: 200 W / cm) using a high-pressure mercury lamp. Using the obtained article, a decorative material (melamine resin decorative board) was obtained in the same manner as in Example 1H. The 60 ° gloss value of the obtained decorative material is shown in Table 1H.

From the results in Table 1H, the matte article H of the present embodiment has a 60 ° gloss value of 1.4 to 1.8 of the matte decorative material obtained by using the matte article H, which is extremely excellent matte. It was confirmed that it is a matte article that can impart visibility of the effect.
In addition, since the standard deviation (σ) is less than 0.30, it has been confirmed that the formation of wrinkles is stable, and the stability of the formation of wrinkles leads to the visibility of the matte effect and the addition of texture. It is considered to be.

On the other hand, in the article of Comparative Example 1H containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 46, stable visibility of the matting effect could not be obtained. It was not possible to give an excellent texture. The fact that it cannot be obtained stably can be seen from the fact that the standard deviation of the gross value is 0.30 or more.
The article of Comparative Example 2H containing a matting agent contained 15.0 parts by mass, which is larger than the content of the wrinkle forming stabilizer in the examples, but wrinkles were formed on the surface layer corresponding to the matting type layer. There was no formation, and the 60 ° gloss value of the decorative material obtained using this was 8.3, which is the matte of the example despite the fact that a larger amount of the matting agent was used than the wrinkle formation stabilizer in the example. It was confirmed that the gloss value of the fixed sheet was inferior and that the texture was also inferior.

Further, according to the optical microscope images of Examples 1H to 3H (FIGS. 43 to 45, respectively), it can be confirmed that the matte type sheets of these Examples have irregular wrinkles uniformly on the surface thereof. .. On the other hand, according to the optical microscope image of Comparative Example 1H (FIG. 46), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 47) of Comparative Example 2H, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, the matte article H of the present embodiment exhibits extremely excellent visibility of the matte effect due to wrinkles on the surface thereof, and the excellent visibility and texture of the matte effect on the surface. It was confirmed that it is possible to grant.

[Example 1I]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. , Resin composition for forming a matte layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle size: 3 μm): 3 By mass, photopolymerization initiator (benzophenone type): 0.8 parts by mass) is applied by the gravure method (application amount: 5 g / m ² (when dried)), and then a UV irradiation device composed of LEDs is used. Irradiate with ultraviolet rays (wavelength: 395 nm, amount of ultraviolet rays: 6 W / cm ² ), and then irradiate with ultraviolet rays using an excima light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm, integrated light amount: Perform the irradiation treatment of (1) in a nitrogen atmosphere (oxygen concentration 200 ppm or less) at 10 to 100 mJ / cm ² , and then irradiate with an electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (Mrad)) (2). ) Was carried out, a matte layer was provided on the base material, and a matte article having the base material and the matte layer was obtained. The gloss value of the obtained matte article was measured at 60 ° from the matte layer side and found to be 1.5.

[Examples 2I and 3I]
In Example 1I, a matte article was obtained in the same manner as in Example 1I, except that the wrinkle formation stabilizer in the resin composition for forming a matte layer was used in the amount shown in Table 1I. Table 1I shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side.

[Example 4I]
In Example 1I, a matte article was obtained in the same manner as in Example 1I, except that the electron beam was changed to ultraviolet rays (wavelength: 365 nm, ultraviolet output density: 200 W / cm) using a high-pressure mercury lamp. Table 1I shows the evaluation of the 60 ° gloss value and texture of the obtained matte article on the matte layer side.

[Comparative Example 1I]
In Example 1I, the amount of the wrinkle formation stabilizer used in the resin composition for forming the matte layer was set to 0 parts by mass, that is, the same as in Example 1I except that the wrinkle formation stabilizer was not used. , Got the goods. Table 1I shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

[Comparative Example 2I]
In Example 1I, the amount of the wrinkle formation stabilizer used was 0 parts by mass, 15.0 parts by mass of a matting agent (average particle size: 8.0 μm) was used, the irradiation treatment of (1) was not performed, and the electrons were used. Articles were obtained in the same manner as in Example 1I, except that only the line (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) was irradiated. Table 1I shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

[Comparative Example 3I]
An article was obtained in the same manner as in Example 1I, except that the irradiation treatment (irradiation with an electron beam) of (2) was not performed in Example 1I. Table 1I shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

[Comparative Example 4I]
Articles were obtained in the same manner as in Example 1I, except that the irradiation treatment of (1) was not performed in Example 1I. Table 1I shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

[Comparative Example 5I]
Articles were obtained in the same manner as in Example 4I, except that the irradiation of the irradiation treatment of (1) was not performed in Example 4I. Table 1I shows the evaluation of the 60 ° gloss value and texture of the obtained article on the matte layer side.

* 1, The surface layer did not harden, the gloss value could not be measured, and the texture could not be evaluated.

From the results in Table 1I, the matte article of the example has a 60 ° gloss value of 2.0 or less on the matte layer side, and is extremely excellent in visibility of the matte effect and excellent in texture. It was confirmed that. From the above, it was confirmed that the matte article I obtained by the manufacturing method I of the present embodiment has excellent surface characteristics and excellent visibility of the matting effect, and the manufacturing of the present embodiment. It was also confirmed that the matte article I could be easily produced according to the method I.

On the other hand, in the article of Comparative Example 1I containing no wrinkle formation stabilizer, although some wrinkles were generated on the surface as shown in FIG. 51, stable visibility of the matting effect could not be obtained. There was a part where the gloss value was the same as that of the example, but there was a part where the gloss value was high and the surface condition was unstable (not uniform), and it could not be said that the texture was excellent. Even if the article of Comparative Example 2I containing a matte agent contains 15.0 parts by mass, which is larger than the content of the wrinkle formation stabilizer in the example, wrinkles are formed in the surface layer corresponding to the matte layer. It was confirmed that the 60 ° gloss value was 8.3, which was inferior to the gloss value of the matte article of the example, and was also inferior to the texture. In Comparative Example 3I in which the irradiation treatment of (2) was not performed, wrinkles were formed and cured only on the outermost surface, but the 60 ° gloss value could not be measured because the inside of the surface layer was uncured, and the surface characteristics were improved. It was inferior and the texture could not be evaluated. Further, Comparative Example 4I in which the irradiation treatment of (1) was not performed and the irradiation treatment of the electron beam of (2) was performed, and the comparison in which the irradiation treatment of (1) was not performed and the irradiation treatment of ultraviolet rays of (2) was performed. In the article of Example 5I, since no wrinkles were formed, the gloss value was extremely high, and the visibility of the matte effect could not be obtained. It was inconspicuous and gave good results.

According to the optical microscope images of Examples 1I to 3I (FIGS. 48 to 50, respectively), it can be confirmed that the matte articles of these examples have irregular wrinkles on the surface thereof. On the other hand, according to the optical microscope image of Comparative Example 1I (FIG. 51), as described above, some wrinkles are generated on the surface thereof, and although there is a region having the same wrinkles as in the example, there is a region. It can be seen that the formation of wrinkles is unstable (not uniform) and is mixed with the wrinkle-free region. Further, according to the optical microscope image (FIG. 52) of Comparative Example 2I, wrinkles like the matte article of Example were not confirmed, and a convex shape corresponding to the contour shape of the matting agent was confirmed. From this result, it was confirmed that the matte article I obtained by the production method I of the present embodiment exhibited an extremely excellent matte effect due to the wrinkles on the surface thereof.

[Example 1J]
A polypropylene sheet (thickness: 100 μm) subjected to corona discharge treatment is used as a base material, and printing ink (binder resin: two-component curable acrylic-urethane resin) is applied to one surface of the base material by a gravure method. A colored layer (thickness: 3 μm) is provided, and a resin composition containing an acrylic resin and a urethane resin as a binder resin is applied onto the colored layer to provide a primer layer (thickness: 2 μm) on the primer layer. , Resin composition for forming surface wrinkle layer (polyfunctional urethane (meth) acrylate oligomer): 65 parts by mass, monofunctional acrylate monomer: 35 parts by mass, wrinkle formation stabilizer (silica particles, average particle size: 3 μm): 3 (Mass part) is coated by the gravure method (coating amount: 5 g / m ² (when dried)) and irradiated with ultraviolet rays using an excima light irradiation device (wavelength: 172 nm (Xe ₂ ), ultraviolet output density: 1 W / cm. , Integrated light amount: 10 to 100 mJ / cm ² , nitrogen atmosphere (oxygen concentration 200 ppm or less)), the irradiation treatment of (1) is performed, and then electron beam (acceleration voltage: 75 kV, irradiation dose: 30 kGy (3Mrad)) is irradiated. Then, the irradiation treatment of (2) was carried out to provide a surface wrinkle layer on the base material, and an article having the base material and the surface wrinkle layer was obtained. The 60 ° gloss value of the obtained article was measured from the surface wrinkle layer side and found to be 1.5.

[Examples 2J and 3J]
In Example 1J, an article was obtained in the same manner as in Example 1J, except that the wrinkle formation stabilizer in the resin composition for forming the surface wrinkle layer was used in the amount shown in Table 1J. Table 1J shows the 60 ° gloss value on the surface wrinkle layer side of the obtained article.

[Example 4J]
An article was obtained in the same manner as in Example 1J, except that the electron beam was changed to ultraviolet rays (wavelength: 365 nm, ultraviolet output density: 200 W / cm) using a high-pressure mercury lamp in Example 1J. Table 1J shows the 60 ° gloss value on the surface wrinkle layer side of the obtained article.

[Comparative Example 1J]
An article was obtained in the same manner as in Example 1J except that (2) irradiation treatment was not performed in Example 1J. Table 1J shows the 60 ° gloss value on the surface wrinkle layer side of the obtained article.

[Comparative Example 2J]
In Example 1J, an article was obtained in the same manner as in Example 1J except that (1) irradiation treatment was not performed. Table 1J shows the 60 ° gloss value on the surface wrinkle layer side of the obtained article.

[Comparative Example 3J]
In Example 4J, an article was obtained in the same manner as in Example 4J except that (1) irradiation treatment was not performed. Table 1J shows the 60 ° gloss value on the surface wrinkle layer side of the obtained article.

* 1, The gloss value could not be measured.

From the results in Table 1J, in the article of the example, the resin composition for forming the surface wrinkle layer was cured to form the surface wrinkle layer, and the 60 ° gloss value on the surface wrinkle layer side was 2.0 or less. It was confirmed that the article was excellent in surface characteristics and extremely excellent in visibility of the matte effect. From the above, it was confirmed that the article J obtained by the manufacturing method J of the present embodiment has excellent surface characteristics and excellent visibility of the matting effect, and the manufacturing method J of the present embodiment. It was also confirmed that the article could be easily manufactured.

On the other hand, in the article of Comparative Example 1J which was not subjected to the irradiation treatment of (2), wrinkles were formed only on the outermost surface and cured, but the inside of the surface layer was uncured, so that the 60 ° gloss value could be measured. There wasn't. The article of Comparative Example 2J which was not subjected to the irradiation treatment of (1) did not have wrinkles and did not have a surface wrinkle layer (see also FIG. 56), and had a 60 ° gloss value of 47.2, which was a matte effect. Did not have. The article of Comparative Example 3J in which the irradiation treatment of (1) was not performed and the irradiation treatment of (2) was performed with ultraviolet rays did not form wrinkles and did not harden, so that the 60 ° gloss value could be measured. There wasn't. Further, as described above, Comparative Examples 1J and 3J did not have excellent surface characteristics because the surface layer was uncured.
From the comparison between Example 4J and Comparative Example 3J, by performing (1) irradiation treatment, the surface wrinkle layer is cured only by irradiating with wavelength light in the ultraviolet region without containing a photopolymerization initiator. The peculiar effect of forming was confirmed.

According to the optical microscope images of Examples 1J to 3J (FIGS. 53 to 55, respectively), the articles of these Examples have irregular wrinkles on the surface thereof, and from this result, the production method of the present embodiment. It was confirmed that the article J obtained by J exhibited extremely excellent visibility of the matting effect due to the wrinkles on the surface thereof. Further, in the optical microscope image of Comparative Example 2J (FIG. 56), the wrinkle formation stabilizer can be confirmed in the form of particles, but the wrinkles are not formed and the surface wrinkle layer is not formed. Compared with FIGS. 53 to 55 of 3J, the morphology of the surface thereof was completely different, and it was confirmed that the wrinkle formation stabilizer did not function as a wrinkle formation stabilizer.

The matte articles of the present embodiment, the matte articles obtained by the manufacturing method of the present embodiment, and the like have various uses, for example, interior members of buildings such as walls, ceilings, and floors, outer walls, eaves ceilings, and roofs. , Fences, fences and other exterior members, window frames, doors, door frames, handrails, skirts, rims, moldings and other fittings or construction members, as well as general furniture such as stools, shelves, desks, dining tables, sinks, etc. Various furniture and parts used around water such as kitchen furniture, kitchens, toilets, bathrooms, wash basins, surface decorative boards such as cabinets for home appliances and OA equipment, vehicle interiors, exterior parts, etc. It is preferably used as.
Further, in addition to the above-mentioned various members, the matte article or the like may be a packaging material, an antiglare film for a display, a white board or a blackboard, a credit card, etc. It can be used for cash cards, telephone cards, various cards such as various certificates, keys for various keyboards, transparent plates (window glass, etc.) for windows, doors, partitions, artificial leather, and the like.

Claims

A cured product of a resin composition having a matte layer, wherein the matte layer contains a wrinkle formation stabilizer in an amount of 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. Consists of
At least one surface of the matte layer has an uneven shape composed of irregular wrinkles.
A matte article having a 60 ° gloss value of 5.0 or less in the matte layer.
The wrinkle-forming stabilizer 1 comprises a wrinkle-forming stabilizer 1 having an average particle size of 1 μm or more and an upper limit of 100% or less or 30 μm or less of the thickness of the matte layer, whichever is smaller. Matte goods.
The matte article according to claim 1 or 2, wherein the wrinkle formation stabilizer contains a wrinkle formation stabilizer 2 having an average particle size of less than 1 μm.
Any one of claims 1 to 3, wherein the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions. The matte article according to item 1.
The matte article according to any one of claims 1 to 4, wherein the matte layer does not contain a matting agent.
The matte article according to any one of claims 1 to 5, wherein the matte layer is provided over the entire surface.
The matte article according to any one of claims 1 to 6, wherein the resin is an ionizing radiation curable resin.
The matte article according to any one of claims 1 to 7, further comprising a base material.
The matte article according to claim 8, wherein the surface of the matte layer opposite to the base material side has an uneven shape composed of irregular wrinkles.
The matte article according to claim 8 or 9, wherein the base material is a synthetic resin sheet.
The matte article according to any one of claims 8 to 10, further comprising a transparent resin layer between the base material and the matte layer.
Gloss value when the 60 ° gloss value on the matte layer side before the following rubbing test is G 0 and the 60 ° gloss value on the matte layer side after the rubbing test is G 1. The matte article according to any one of claims 1 to 11, wherein the rate of change (| (G 1 − G 0 ) | / G 0 × 100) is 20% or less.
(Rubbing test)
Place the matte article on the base of the abrasion tester type II (JIS L0849: 2013), set steel wool # 0000 so as to contact the matte layer of the matte article, load 1500 g / cm 2 , move. It was reciprocated 30 times at a speed of 100 mm / sec and a reciprocating movement distance of 100 mm.
The matte article according to any one of claims 1 to 12, which is used for flooring materials or fitting members.
The adherend and the matte article according to any one of claims 1 to 12 are provided so that the adherend and the base material of the matte article face each other via an adhesive layer. Flooring material.
The adherend and the matte article according to any one of claims 1 to 12 are provided so that the adherend and the base material of the matte article face each other via an adhesive layer. Joinery members.
The matte article according to any one of claims 1 to 11, wherein the matte layer is an easy matte decontamination layer.
The matte article according to claim 16, wherein the matte easy decontamination layer contains at least one easy decontamination agent selected from a fluororesin, a silicone resin, and a fluorine-silicone copolymer resin.
The matte article according to claim 17, wherein the easy decontamination agent is contained in an amount of 0.5 parts by mass or more and 25.0 parts by mass or less with respect to 100 parts by mass of the resin.
The matte according to any one of claims 1 to 11, wherein the matte layer is a matte light-resistant layer, and the resin composition constituting the matte light-resistant layer further contains a hydroxyphenyltriazine-based ultraviolet absorber. Goods.
The matte article according to claim 19, wherein the hydroxytriazine-based ultraviolet absorber is represented by the following general formula (1).

(In the general formula (1), R 11 is a single-bonded or divalent organic group, and R 12 is a hydrocarbon group or an ester group represented by -C (= O) OR 15, -OC (= O). ) The acyloxy group represented by R 16 or the alkoxy group represented by −OR 17 , and R 13 , R 14 , R 15 , R 16 and R 17 are independently monovalent organic groups, and n 11 and n 12 is an independently integer from 0 to 5).
The matte article according to any one of claims 1 to 11, wherein the matte layer is a matte writing layer.
The matte article according to claim 21, wherein the base material has a base material sheet and a colored layer.
The matte article according to claim 21 or 22, which is used for a writing board.
The matte article according to any one of claims 1 to 11, wherein the matte layer is a matte type layer and is used for shaping.
A method for manufacturing a matte article, which is formed by using the matte article according to claim 24.
The method for manufacturing a matte article according to claim 25, wherein the shaping is performed using an embossed roller in which the matte article is arranged on a roller.
The base material impregnated with the resin composition and the matte article are arranged so that the matte type layer of the matte article and the base material face each other, and heat and pressure molding is performed to form the resin composition. The method for producing a matte article according to claim 26, wherein the matte article is peeled off after curing.
The method for producing a matte article according to claim 27, wherein the resin composition contains a melamine resin or a diallyl phthalate resin (DAP).
The resin composition containing 0.5 parts by mass or more and 6.0 parts by mass or less of the wrinkle formation stabilizer with respect to 100 parts by mass of the resin and containing the photopolymerization initiator is irradiated with the following (1) and (2). The treatment is carried out in order, and the step of curing the resin composition to form a matte layer is included.
At least one surface of the matte layer has an uneven shape composed of irregular wrinkles.
The 60 ° gloss value of the matte layer is 5.0 or less.
A method for manufacturing a matte article.
(1) Irradiation treatment of wavelength light of 100 nm or more and less than 200 nm (2) Irradiation treatment of at least one of electron beam and wavelength light of 200 nm or more and 400 nm or less
The method for manufacturing a matte article according to claim 29, wherein the wavelength light of (1) is light having a wavelength of 100 nm or more and 185 nm or less.
The method for producing a matte article according to claim 29 or 30, wherein the irradiation treatment of (2) is an electron beam irradiation treatment.
The method for producing a matte article according to any one of claims 29 to 31, wherein (3) an irradiation treatment for pre-curing is performed before the irradiation treatment.
The method for producing a matte article according to claim 32, wherein the irradiation treatment for (3) pre-curing is an irradiation treatment of wavelength light of more than 320 nm and 400 nm or less.
The method for producing a matte article according to any one of claims 29 to 33, wherein the content of the photopolymerization initiator is 0.1 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the resin.
23. The method for producing a matte article according to any one item.
The method for producing a matte article according to any one of claims 29 to 35, wherein the wrinkle formation stabilizer contains a wrinkle formation stabilizer 2 having an average particle size of less than 1 μm.
The gloss according to any one of claims 29 to 36, wherein the resin composition is applied to at least one main surface side of the base material, and the matte layer is formed on at least one main surface side of the base material. Manufacturing method of erasable goods.
Any one of claims 29 to 37, wherein the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions. The method for manufacturing a matte article according to the section.
A method for producing an article, which comprises a step of sequentially performing the irradiation treatments (1) and (2) below on a resin composition containing no photopolymerization initiator and curing the resin composition to form a surface wrinkle layer. ..
(1) Irradiation treatment of wavelength light of 100 nm or more and less than 200 nm (2) Irradiation treatment of at least one of electron beam and wavelength light of 200 nm or more and 400 nm or less
The resin composition contains 0.5 mass by mass of a wrinkle formation stabilizer having an average particle diameter of 100% or less or 30 μm or less of the thickness of the surface wrinkle layer, whichever is smaller, as the upper limit. It contains more than 6.0 parts by mass and has an uneven shape in which at least one surface of the surface wrinkle layer is composed of irregular wrinkles, and the 60 ° gloss value of the surface wrinkle layer is 5. The method for producing an article according to claim 39, which is 0 or less.
The method for producing an article according to claim 39 or 40, wherein the irradiation treatment of (2) is an irradiation treatment of light having a wavelength of 200 nm or more and 400 nm or less.
Claim 40 or 41, wherein the wrinkle formation stabilizer comprises a wrinkle formation stabilizer 1 having an average particle diameter of 1 μm or more and an upper limit of 100% or less or 30 μm or less of the thickness of the surface wrinkle layer, whichever is smaller. The method for manufacturing the article described in.
The method for producing an article according to any one of claims 40 to 42, wherein the wrinkle formation stabilizer contains a wrinkle formation stabilizer 2 having an average particle size of less than 1 μm.
The article according to any one of claims 39 to 43, wherein the resin composition is applied to at least one main surface side of the base material, and the surface wrinkle layer is formed on at least one main surface side of the base material. Manufacturing method.
The method for manufacturing an article according to claim 44, wherein the surface of the surface wrinkle layer opposite to the base material side has an uneven shape composed of irregular wrinkles.
The production of the article according to claim 45, wherein the irregular wrinkles are composed of a plurality of convex portions formed by a plurality of linear protrusions and a concave portion formed by being surrounded by the plurality of linear protrusions. Method.