JP2019173475A - Decorative material - Google Patents

Abstract

To provide a decorative material with high quality design property having realistic feeling and high-class impression.SOLUTION: A decorative material includes recess shape on a surface, in which edge of the recess shape in a plan view is constituted of repetition of irregular recess and protrusion.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative material.

  Building materials for interior and exterior, such as furniture and kitchen product cabinets, various types of countertops and desks, and residential building materials such as doors, have excellent properties in terms of scratch resistance, impact resistance, heat resistance, contamination resistance, etc. Therefore, thermosetting resin decorative boards such as high-pressure melamine resin decorative boards, low-pressure melamine resin decorative boards, diallyl phthalate (DAP) resin decorative boards, polyester decorative boards, guanamine resin decorative boards, and phenolic resin decorative boards are used. .

  With the recent increase in consumer preference for high-end products, these thermosetting resin decorative boards are desired to have realism and luxury that are closer to the real thing. As a method for improving the sense of realism and luxury, a method of imparting a concavo-convex shape to at least the surface layer of a cosmetic material, for example, a method of improving texture using embossing using an embossed plate, a shaping sheet, a transfer sheet, etc. Is mentioned. For example, Patent Document 1 discloses a shaped sheet that reproduces a desired pattern shape by providing an uneven shape with an ionizing radiation curable resin on the surface of a base sheet, and a polyester decorative board using the shaped sheet. Proposed.

JP 7-164519 A

  In order to improve the texture and improve the sense of quality, it is important to make the uneven shape more delicate. However, the decorative board described in Patent Document 1 is formed by forming a concavo-convex shape on the surface layer (unsaturated polyester resin layer) of the decorative board with the shaping sheet, and before the polyester resin of the surface layer is cured. In some cases, the uneven shape is distorted and a sufficient texture cannot be imparted. In addition, such a phenomenon becomes more prominent as an attempt is made to give a more delicate uneven shape. For this reason, there is an increasing number of cases where it is not possible to meet the recent demand for luxury goods by consumers, and there is a demand for a cosmetic material having a sense of quality and a high-quality design that has a sense of quality as well as a real feeling.

  The present invention has been made under such circumstances, and an object of the present invention is to provide a cosmetic material having a high quality and a high-quality design that has a sense of realism and high quality.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by an invention relating to a cosmetic material having the following configuration.

[1] A cosmetic material having a concave shape on the surface, and the edge of the concave shape in plan view is configured by repeating irregular irregularities.
[2] A first cured product layer formed of a substrate, a first pattern region, a second pattern region, and a curable resin, and the first pattern region is a part of one surface side of the substrate The second pattern region is formed on the remaining portion of the one surface side of the substrate, the first cured product layer is present immediately above the first pattern region, and the second pattern region The makeup according to the above [1], wherein the concave shape is formed in the first cured product layer by being not present directly above, and the bottom surface of the concave shape is formed by the surface immediately above the second pattern region. Wood.
[3] The cosmetic material according to the above [2], which has a second cured product layer formed of a curable resin immediately above the second pattern region.
[4] The cosmetic material according to [2] or [3], further including a decorative layer between the substrate and the first cured product layer.
[5] The cosmetic material according to [3], further including a decoration layer between the base material, the first cured product layer, and the second cured product layer.
[6] The method according to any one of [1] to [5], further including a surface property improving layer on the first cured product layer or between the base material and the first cured product layer. Cosmetic material

  ADVANTAGE OF THE INVENTION According to this invention, the decorative material which has a design feeling with high texture which has a sense of quality with a real feeling can be provided.

It is a model perspective view which shows the external appearance of an example of the decorative material of this invention. It is a schematic diagram which shows the layer structure of the cross sectional view of an example of the decorative material of this invention. It is a schematic diagram which shows the layer structure of the cross sectional view of an example of the decorative material of this invention. It is a schematic diagram which shows the layer structure of the cross sectional view of an example of the decorative material of this invention. The microscope enlarged image of the cross section of the decorative material of Example 1 is shown. The microscope enlarged image of the section of the cosmetics of comparative example 1 is shown.

[Cosmetics]
The decorative material of the present invention has a concave shape on the surface, and the edge of the concave shape in plan view is configured by repeating irregular irregularities. In the present invention, the “plan view” means that the decorative material of the present invention is viewed in the planar direction from the side having the concave shape (surface side). A typical example of the “plan view” will be described with reference to FIGS. 1 and 2. The line-of-sight direction of the surface having the concave shape 2 of the decorative material 1 (hereinafter sometimes simply referred to as “surface”). Although it is a case where it visually matches with the normal direction N, the “plan view” in the present invention is not limited to this form, and the decorative material of the present invention is originally from the side (surface) having the concave shape 2. It includes any case of visual observation in the assumed line-of-sight direction. Further, in the present invention, “cross-sectional view” means that as shown in FIG. 2, a cross-section extending in parallel with the normal direction N of the surface of the decorative material of the present invention and perpendicular to the extending direction L of the concave shape 2 is extended. It means that it is visually recognized from the direction L, and includes any case where it is visually observed from at least a direction in which the cross-sectional shape of the decorative material of the present invention can be visually recognized.

  Hereinafter, the structure of the decorative material of this invention is demonstrated using FIGS. FIG. 1 is a schematic perspective view showing the appearance of a decorative material 1 of the present invention. The decorative material 1 of the present invention has a concave shape 2 on the surface, and an edge 21 in the shape of the concave shape 2 in a plan view. It is shown that it is constituted by repeating irregular irregularities. The cape or peninsula-like protrusion part 21C which protruded toward the inner side of the recessed part shape 2 and the bay or cove-like recessed part 21B are alternately and adjacently arranged. In addition, the bottom surface 22 of the concave shape 2 is a non-curved surface, indicating that the shape in cross-sectional view is a trapezoid.

(Concave shape 2)
The concave shape requires that the edge of the shape in plan view is constituted by repeating irregular irregularities. If the edge of the concave shape in plan view is not configured by repeating irregular irregularities, the design property is monotonous, and a high-quality design with a sense of realism and high quality cannot be obtained. The irregular unevenness may be constituted by a straight line, may be constituted by a curve, or may be constituted by a combination of a straight line and a curve. From the viewpoint of obtaining a more textured design, the irregular unevenness is preferably constituted by a curve, or constituted by a combination of a straight line and a curve, that is, constituted by a line including at least a curve. It is more preferable that it is comprised by these. As a specific example of the irregular concavo-convex shape, for example, as shown in FIG. 1, capes or peninsula-shaped protrusions 21 </ b> C protruding toward the inside of the concave shape and bays or cove-shaped recesses 21 </ b> B alternately The shape arrange | positioned adjacently is mentioned.

  The shape of the concave shape in plan view is not particularly limited and may be appropriately determined according to the desired design.For example, in various shapes such as a circle, an ellipse, a square, a rectangle, and a triangle, the outer edge is not suitable. Examples of the shape include lines formed by repeating regular irregularities. For example, when a wood grain conduit pattern is desired, a shape in which the outer edge is constituted by a line formed by repeating irregular irregularities is preferably selected in a circular shape, an elliptical shape, and a combination shape thereof. In the decorative material shown in FIG. 1, the shape of the concave shape in plan view is often an elliptical shape in which the outer edge is constituted by lines formed by irregular irregularities.

  In the decorative material of the present invention, there is no particular limitation on the pattern that the concave shape exhibits, but, for example, a wood grain conduit pattern, a concave pattern on the surface of a marble plate (for example, a concave portion of a travertine marble pattern), a cleavage plane of a granite plate, etc. Stone pattern imitating the surface of the rock, textured pattern imitations that mimic the texture and cloth-like pattern, leather-like saddle-like depressions that represent leather grain, tiled patterns and brickwork patterns , Hairline ridges, line ridges, satin dents, grained cavities, letters, symbols, geometric pattern dents, etc. Can be mentioned. Further, as a composite pattern of these, for example, a crushed stone made of stone such as marble is mixed with white cement and hardened, and then polished and finished like a marble, a concave portion in a pattern like a so-called artificial marble. For example, as shown in FIG. 1, as a shape of the concave shape in plan view, a cosmetic material that frequently uses a shape in which an outer edge (that is, a contour line) of an ellipse is formed by lines of irregular irregularities is used. Since the shape of the concave portion in plan view matches the shape of the conduit groove on the surface of the wood plate, it is suitable for the wood conduit pattern that reproduces the appearance of the wood conduit groove.

The number of irregularities on the edge is preferably 3 to 300, more preferably 10 to 200, and still more preferably 20 to 100 per 1 cm length of the edge. When the number of irregularities is within the above range, it is easy to stably produce a decorative board and it is easy to obtain a design with higher texture. The number of irregularities on the edge is the average value of the number of irregularities at any ten locations on the edge.
The width of the concave shape is not particularly limited, and may be appropriately determined according to a desired design. The average value is about 0.1 to 10 mm. From the viewpoint of obtaining high designability, it is preferably 0.05 to 2 mm, more preferably 0.1 to 1 mm. Let the average value of the width | variety of a recessed part shape be an average value of the measured value of the maximum width of arbitrary 10 recessed part shapes.
Further, the length of the concave shape is not particularly limited, and may be appropriately determined according to a desired design. The average value is about 1 to 300 mm, and in particular, when a wood grain conduit pattern is adopted, the texture is more textured. From the viewpoint of obtaining a high design property, it is preferably 2 to 50 mm, more preferably 3 to 45 mm. The average value of the length of the concave shape is the average value of the measured values of the length of any ten concave shapes.

Regarding the concave shape, the bottom surface is preferably a non-curved surface. By having such a bottom surface, the shape of the recess becomes clearer, so that a design with higher texture can be easily obtained. Here, the non-curved surface means that the average line of the roughness curve in the shape of the cross-sectional view of the bottom surface is constituted by a straight line and does not exhibit a curve. That is, it means that although there are fine irregularities on the bottom surface, the bottom surface when viewed as an overall shape without considering the fine irregularities is a non-curved surface.
For example, the shape of the concave shape of the decorative material of the present invention in a cross-sectional view is preferably a square, a rectangle, a trapezoid, not a shape having a bottom that is a curved surface such as a semicircle or a semi-elliptical, It is more preferable to exhibit. The cross-sectional shape of the concave shape of the decorative material shown in FIG. 1 is a trapezoid whose short side is the bottom surface side.

  In the sectional shape of the concave shape, the arithmetic surface roughness Ra of the bottom surface is not particularly limited, but the concave shape is visually recognized as a concave shape, and it is easy to obtain a design with higher texture. Considering it, it is preferably 0.2 to 0.6 μm, more preferably 0.3 to 0.5 μm. In this specification, the arithmetic surface roughness Ra is the arithmetic average roughness of JIS B0601: 2013 when the cutoff value is 0.8 mm, and the arithmetic surface roughness Ra at any ten locations on the bottom surface of the concave shape. And measure the average value.

  The maximum depth of the concave shape is not particularly limited, and may be appropriately determined according to a desired design. The average value is about 1 to 30 μm, and more particularly, when a wood grain conduit pattern is adopted, From the viewpoint of obtaining high designability, it is preferably 3 to 20 μm, more preferably 5 to 15 μm. In the present specification, the maximum depth of the concave shape is a value measured using a three-dimensional surface roughness measuring instrument in accordance with a method defined in JIS B0601: 2013, and more specifically, The maximum height roughness (Rz) of the surface at any ten locations is measured, and the average value is taken as the average value of the maximum depth of the recess shape.

  The shape of the decorative material of the present invention is not particularly limited and may be appropriately selected as desired. For example, a flat plate shape, a curved surface, or a corner may be used. It may be non-planar. FIG. 1 shows a flat decorative material, but the shape of the decorative material of the present invention is not limited to this. In consideration of ease of production of the decorative material, application, etc., a flat plate shape is preferred.

(About layer structure)
Next, a preferred embodiment of the layer structure of the decorative material of the present invention will be described taking the decorative material 1 shown in FIGS. The decorative material 1 shown in FIG. 2 is formed of a first pattern region 31 formed on a part of one surface side of the base material 5, a second pattern region 41 formed on the remaining portion, and a curable resin. The first cured product layer 3 is present, and the first cured product layer 3 is present immediately above the first pattern region 31 and is not present directly above the second pattern region 41. Thus, the concave shape 2 is formed in the first cured product layer 3. Further, the first cured product layer 3 has a concave-shaped edge 21, the bottom surface 22 of the concave shape 2 is formed by the surface immediately above the second pattern region 41, and the bottom surface 22 is the second It is the surface of the second cured product layer 4 that is preferably provided immediately above the pattern region 41. In addition, when not providing the 2nd hardened | cured material layer 4, one surface of the base material 5 turns into the surface of the directly upper part of a 2nd pattern area | region, and forms the bottom face 22. FIG.

The decorative material 1 shown in FIG. 3 is obtained by further providing a second cured product layer 4 and a decorative layer 6 on the decorative material 1 shown in FIG. The decoration layer is provided between the base material 5 and the first cured product layer 3 and the second cured product layer 4.
Further, the decorative material 1 shown in FIG. 4 is obtained by further providing a surface property improving layer 7 on the decorative material 1 shown in FIG. 3, and the surface property improving layer 7 is the first cured product layer 3. It is provided on the top (surface).

(Substrate 5)
The base material used for the decorative material of the present invention holds the first cured product layer and the layers such as the decorative layer and the second cured product layer that are preferably provided. The substrate is not particularly limited and may be appropriately selected depending on the desired performance. From the viewpoint of handleability, a paper substrate, a fiber substrate, a resin substrate and the like are preferably mentioned, and more excellent mechanical properties From the viewpoint of obtaining a decorative material having the above, a paper base material and a fiber base material having liquid permeability are more preferable, and a paper base material is still more preferable.
Examples of the paper substrate include craft paper, titanium paper, linter paper, resin-impregnated paper, thin paper, and Japanese paper. Examples of the fiber base material include non-woven fabrics and woven fabrics. For example, fiber base materials composed of inorganic fibers such as glass fibers, alumina fibers, silica fibers, and carbon fibers, polyester resins, acrylic resins, polyethylene resins, and polypropylene resins. Examples thereof include fiber base materials composed of organic fibers of various synthetic resins, and base materials such as composites thereof.

The thickness of the substrate is not particularly limited and may be appropriately selected depending on the desired performance. From the viewpoint of securing mechanical properties and handling properties, it is usually about 10 to 150 μm, preferably 20 to 120 μm, more preferably. 30-100 μm. Moreover, when using a paper base material as a base material, the basis weight is about 20-150 g / m < ² > normally from the same viewpoint as this, Preferably it is 30-100 g / m < ² >.

When the base material used for the decorative material of the present invention is a liquid-permeable base material, that is, a paper base material or a fiber base material, it is preferable that these base materials are impregnated with a curable resin. That is, a preferred embodiment of the decorative material of the present invention is a paper base or a fiber base impregnated with a liquid uncured material of a thermosetting resin as a base, and is subjected to pressure molding or heat pressure molding. It becomes the thermosetting resin decorative board obtained by applying.
As the curable resin, a curable resin such as a thermosetting resin or an ionizing radiation curable resin can be used, and the first cured product has high affinity with the curable resin forming the first cured product layer. Resins that can be integrated with the curable resin forming the layer are preferred. With this configuration, the mechanical strength of the decorative material of the present invention is improved.

  As the curable resin to be impregnated into the base material, from the viewpoint of obtaining a design with a higher texture of the decorative material of the present invention and improving mechanical strength, for example, melamine resin, urea resin, melamine-urea resin, Preferred examples include guanamine resin, diallyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, and the like. Melamine resin, urea resin, melamine-urea resin, guanamine resin, sulfonamide resin, etc. The thermosetting resin is preferably melamine resin, melamine-urea resin, and phenol resin, and melamine resin is particularly preferable.

  In order to impregnate these thermosetting resins into a substrate having liquid permeability, an uncured resin composition containing a liquid uncured product of the thermosetting resin is prepared, and the uncured resin composition is prepared. What is necessary is just to impregnate the base material in this base material. The impregnated uncured resin composition becomes a cured product of a thermosetting resin by being heated and cured by a reaction such as a crosslinking reaction or a polymerization reaction at an appropriate time. In the present specification, the simple term “thermosetting resin” means a cured product obtained by curing an uncured product of the thermosetting resin. The same applies to other curable resins such as ionizing radiation curable resins.

The base material is a physical layer such as an oxidation method or a concavo-convex method on one or both sides in order to improve interlayer adhesion between the base material and other layers, or to enhance adhesion to various adherends. Surface treatment such as surface treatment or chemical surface treatment can be performed.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet treatment method, and the like. Examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected according to the type of the substrate, but generally, a corona discharge treatment method is preferably used from the viewpoint of the effect of surface treatment and operability.
In addition, in order to improve the interlaminar adhesion between the substrate and other layers, and to enhance the adhesion to various adherends, a treatment such as forming a primer layer and a back primer layer on the substrate is performed. Also good.

(First pattern region 31 and second pattern region 41)
The decorative material of the present invention has a first pattern region on a part of one surface side of the substrate and a second pattern region on the remaining part of the surface side. Here, “the remainder on the surface side” means a region where the first pattern region is not provided on one surface side of the base material.
The decorative material of the present invention has one surface side of the base material, that is, one side of the base material, and, in the case of having a decorative layer to be described later, a part of one side of the decorative layer as the first pattern region and the remaining part. The second pattern region has a concave shape when the first cured product layer is present immediately above the first pattern region and the first cured product layer is not present immediately above the second pattern region. It can be said that the region where the first cured product layer is provided is the first pattern region, and the region where the first cured product layer is not provided is the second pattern region. Therefore, it can be said that the various patterns expressed by the decorative material of the present invention are formed corresponding to the first pattern region and the second pattern region. Therefore, even if one of the first pattern region and the second pattern region is missing, the high decorative board having high texture and design of the present invention cannot be obtained.

Each of the first pattern area and the second pattern area may be one continuous area or a plurality of discontinuous areas. For example, the first pattern area may form one continuous area together with the second pattern area, or the first pattern area may be formed so as to surround a part or all of the second pattern area. Conversely, the second pattern region may be formed so as to surround a part or all of the first pattern region, or a combination thereof. The decorative material shown in FIG. 1 has a concave shape forming a closed region surrounded by an edge, that is, has a second pattern region surrounded by a first pattern region. For example, when a wood grain conduit pattern is desired, since the conduit groove portion forms a closed region, the decorative material shown in FIG. 1 having a concave shape that forms a closed region surrounded by an edge is a wood grain. It can be suitably used as a cosmetic material having a conduit pattern.
The ratio between the area of the first pattern area and the area of the second pattern area is preferably 1: 9 to 7: 3, more preferably 2: 8 to 5: 5, from the viewpoint of obtaining a design with higher texture. .

(First cured product layer 3)
A 1st hardened | cured material layer is a hardened | cured material layer formed with curable resin provided in the just upper part of the 1st pattern area | region provided in the one surface side of a base material. The first cured product layer is provided directly above the first pattern region and is not provided directly above the second pattern region, thereby forming a concave shape immediately above the second pattern region, It can also be said that the portion where the first cured product layer is provided forms a convex shape. Moreover, a 1st hardened | cured material layer is also a layer which has a shape where the irregular curve of the edge of a recessed part repeats, and is a layer which expresses the design property with a high texture in the cosmetics of this invention.

The first cured product layer is a layer formed of a curable resin, more specifically, a layer formed of a cured product of a liquid uncured product of the curable resin. Preferred examples of the curable resin include a thermosetting resin and an ionizing radiation curable resin, and a thermosetting resin is more preferable from the viewpoint of obtaining a design with a higher texture. These curable resins may be used alone or in combination of a plurality of types, for example, a thermosetting resin and an ionizing radiation curable resin may be used in combination, or these curable resins and thermoplastics. You may use together with resin.
As the thermosetting resin, the same ones as those exemplified above as the thermosetting resin capable of impregnating the substrate with a liquid uncured material as described above can be preferably exemplified, and the various thermosetting resins described above. It is the same that the resin is preferable, and that the melamine resin is particularly preferable. By using such a curable resin, a design with a higher texture can be obtained, adhesion with the base material can be improved, and more excellent mechanical strength can be obtained. The ionizing radiation curable resin will be described later as a resin that can be used for the second cured product layer. When using together curable resin and a thermoplastic resin, content of curable resin with respect to the sum total of these resin is about 50-100 mass% normally, Preferably it is 60-90 mass%.

The first cured product layer is a layer formed of an uncured resin composition containing a liquid uncured product of a curable resin, more specifically, an uncured resin containing a liquid uncured product of a curable resin. It may be a layer formed by a cured product of the composition. Examples of the uncured resin composition include liquid uncured products of the above curable resins, weathering agents such as ultraviolet absorbers and light stabilizers, and other additives as desired, such as crosslinking agents and polymerization. Examples of the resin composition include various curing agents such as an initiator and a polymerization accelerator, and various additives such as a catalyst.
As the UV absorber, UV absorbers widely used for cosmetic materials can be used without particular limitation. For example, benzotriazole UV absorbers, benzophenone UV absorbers, triazine UV absorbers, hydroxyphenyl triazine UV absorbers Agents and the like. As the light stabilizer, an ultraviolet absorber widely used for a cosmetic material can be used without particular limitation, and examples thereof include hindered amine light stabilizers such as piperidinyl sebacate light stabilizers. These weathering agents 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 from the viewpoint of improving the strength of the first cured product layer. There may be.

  The thickness of the first cured product layer is not particularly limited as long as the concave shape can be formed, and is usually about 1 to 50 μm, and preferably 3 to 40 μm, more preferably from the viewpoint of easily obtaining a high-quality design. Is 5-30 μm.

(Second cured product layer 4)
A 2nd hardened | cured material layer is a hardened | cured material layer formed with curable resin provided in the just upper part of the 2nd pattern area | region provided in the one surface side of a base material. By providing the second cured product layer, it becomes easier to configure the edge of the concave shape in plan view by repeating irregular irregularities, and the bottom surface of the concave shape in cross section is more likely to be non-curved, so the texture is more High designability will be obtained.

  The second cured product layer is a layer formed of a curable resin, more specifically, a layer formed of a cured product of a liquid uncured product of the curable resin. Preferred examples of the curable resin include a thermosetting resin and an ionizing radiation curable resin, and an ionizing radiation curable resin is more preferable from the viewpoint of obtaining a higher quality design and superior surface characteristics. As a thermosetting resin, the same thing as what was illustrated as a thermosetting resin which can be impregnated to the said base material can be illustrated preferably.

The ionizing radiation curable resin is a resin that crosslinks and cures when irradiated with ionizing radiation, and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group that crosslinks and cures upon irradiation with ionizing radiation, and preferably includes a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group, and an allyl group. It is done. The ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. Also included are electromagnetic waves such as X-rays and γ-rays, and charged particle beams such as α-rays and ion beams.
Specifically, the ionizing radiation curable resin can be appropriately selected from polymerizable monomers and polymerizable oligomers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth) acrylate monomer having a radical 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. An acrylate monomer having an acryloyl group is preferred from the viewpoint of obtaining a higher quality design and superior surface properties.
From the viewpoint of obtaining a higher texture design and superior surface properties, the number of functional groups is preferably 2 or more, and the upper limit is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and particularly preferably 3 It is as follows. These polyfunctional (meth) acrylates may be used alone or in combination.

  Examples of such polymerizable monomers include bifunctional (meth) acrylates such as ethylene glycol di (meth) acrylate, bisphenol A tetraethoxydiacrylate, bisphenol A tetrapropoxydiacrylate, and 1,6-hexanediol diacrylate; trimethylol Propanetri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, Preferred are trifunctional or higher functional (meth) acrylates such as isocyanuric acid-modified tri (meth) acrylate. Among them, dipentaerythritol such as dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like from the viewpoint of obtaining a higher quality design and superior surface characteristics. Type polymerizable monomers are preferred, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are more preferred, and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are used in combination Is particularly preferred.

  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, polycaprolactone urethane (meta ) Acrylate oligomer, polycaprolactone diol urethane (meth) acrylate, and the like.

  From the viewpoint of obtaining a higher quality design and superior surface properties, the number of functional groups of these polymerizable oligomers is preferably 2 or more, and preferably 8 or less, more preferably 6 or less, and even more preferably as an upper limit. 4 or less, particularly preferably 3 or less.

  The weight average molecular weight of these polymerizable oligomers is preferably 500 or more, more preferably, in view of obtaining a higher texture design and superior surface properties, ease of formation of the second cured product layer, and the like. Is 1,000 or more, and the upper limit is preferably 80,000 or less, more preferably 50,000 or less. In this specification, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted with standard polystyrene.

It is preferable that a 2nd hardened | cured material layer contains a mold release agent. By including a release agent, it becomes easier to configure the edge of the concave shape in plan view by repeating irregular irregularities, and the bottom surface of the concave shape in cross section is more likely to be non-curved, so the texture is higher Designability will be obtained.
Examples of the release agent include a fluorine-based release agent and a silicone-based release agent, and a silicone-based release agent is preferable from the viewpoint of obtaining a design with a higher texture.
Examples of the silicone-based release agent include those having a polysiloxane structure as a basic structure. Among them, a modified silicone oil in which an organic group is introduced into at least one of its side chain and terminal is preferable, and organic groups are present at both terminals. The introduced modified silicone oil is more preferable. As an organic group, a reactive functional group such as a (meth) acryl group, an amino group, an epoxy group, a mercapto group, a carbinol group, a phenol group, a carboxyl group, or a polyether group, from the viewpoint of obtaining a design with a higher texture. Preferred examples include non-reactive group functional groups such as an aralkyl group, a fluoroalkyl group, an alkyl group, a fatty acid amide group, and a phenyl group. Among them, a reactive functional group is preferable, and a (meth) acryl group is particularly preferable, that is, a (meth) acryl-modified silicone oil is particularly preferable. Further, these organic groups may have a substituent such as a nitrogen atom, a sulfur atom, a hydroxyl group, or 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 still more preferably 100 parts by mass of the curable resin forming the second cured product layer. 1 to 2 parts by mass. When the content of the release agent is within the above range, an effect of adding the release agent can be obtained efficiently.

The second cured product layer preferably contains an inorganic filler. By including an inorganic filler, the edge of the concave shape in plan view can be easily formed by repeating irregular irregularities, and the bottom surface of the concave shape in sectional view can be easily made non-curved. Therefore, a design with a higher texture can be obtained.
Examples of inorganic fillers include oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, zinc oxide, and zirconia; hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; magnesium carbonate, carbonic acid Examples thereof include particles made of inorganic materials such as carbonates such as calcium; sulfates such as calcium sulfate and barium sulfate; and silicates such as magnesium silicate, aluminum silicate, calcium silicate and aluminosilicate. Among these, oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, and zinc oxide are preferable, and silica is particularly preferable.

  The average particle diameter of the inorganic filler is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, from the viewpoint of obtaining a design with higher texture. In the present specification, the average particle diameter of the filler is a value measured by a laser diffraction scattering method.

  These inorganic fillers are preferably surface-treated. Surface treatment agents for surface treatment of inorganic fillers include alkoxysilane, (meth) acryloyloxy groups, epoxy groups, vinyl groups, styryl groups, amino groups, isocyanate groups, ureido groups, sulfide groups, mercapto groups, etc. Examples thereof include a silane coupling agent having a group. From the viewpoint of obtaining a design with a higher texture, a silane coupling agent having a (meth) acryloyloxy group, an epoxy group, a vinyl group, or an amino group, that is, a (meth) acryloyloxy silane coupling agent or an epoxy silane coupling Agents, vinyl silane coupling agents, and amino silane coupling agents are preferred. These surface treatment agents may be used alone or in combination of two or more.

Alkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, Trialkoxysilanes such as decyltrimethoxysilane and dodecyltrimethoxysilane are preferred.
In addition, as the (meth) acryloyloxy silane coupling agent, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxy Silane, 3- (meth) acryloyloxypropyltriethoxysilane, and the like are preferable. As the epoxy-based silane coupling agent, diethoxy (glycidyloxypropyl) methylsilane, 2- (3,4 epoxyepoxycyclohexyl) ethyltrimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and the like are preferable. Vinyl-based silane coupling Preferred examples include vinyltrimethoxysilane, vinyltriethoxysilane and the like, and amino-based silane coupling agents include N-2 (aminoethyl) 3-aminopropylmethyldimethoxysilane, N-2 (aminoethyl) 3. -Aminopropyltrimethoxysilane, N-2 (aminoethyl) 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3 -Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane and the like are preferred.

  Among these, from the viewpoint of obtaining a design with a higher texture, surface-treated silica particles obtained by surface-treating silica particles with a silane coupling agent are preferable. The affinity with the silicone-based mold release agent preferably used for the second cured product layer is high, and the synergistic effect of the mold release agent and the inorganic filler can provide a particularly excellent high-quality design improvement effect.

  The content of the inorganic filler is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, and still more preferably 20 to 35 parts by mass with respect to 100 parts by mass of the curable resin forming the second cured product layer. It is. When the content of the inorganic filler is within the above range, the effect of adding the inorganic filler can be obtained efficiently.

When the second cured product layer includes a silicone release agent and an inorganic filler, the second cured product layer is formed of a liquid uncured product of the curable resin, an uncured resin composition containing a silicone release agent and an inorganic filler. It can be said that. That is, the second cured product layer is a layer formed of an uncured resin composition containing at least a liquid uncured product of a curable resin, more specifically, at least a liquid uncured product of a curable resin. The layer formed by the hardened | cured material of the uncured resin composition containing this may be sufficient.
As the uncured resin composition, in addition to the liquid uncured product of the curable resin, preferably used silicone release agents, inorganic fillers, weathering agents such as UV absorbers and light stabilizers, and other as desired Various additives such as UV shielding agents, polymerization inhibitors, crosslinking agents, infrared absorbers, antistatic agents, adhesion improvers, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, Examples thereof include an uncured resin composition containing various additives such as an antiblocking agent, a lubricant and a solvent. These weathering agents and other additives may be used alone or in combination.

  The thickness of the second cured product layer is not particularly limited as long as a concave shape can be formed in relation to the first cured product layer, that is, the surface of the second cured product layer is lower than the surface of the first cured product layer. The thickness of the second cured product layer is not particularly limited as long as the surface forms a concave bottom surface, and is usually about 0.1 to 20 μm, from the viewpoint of more easily obtaining a high-quality design. The thickness is preferably 0.5 to 10 μm, more preferably 1 to 5 μm.

(Decoration layer 6)
The decorative material of the present invention preferably has a decorative layer in order to express design with higher texture and to cope with various design properties. The decorative layer may be, for example, a colored layer (so-called solid colored layer) covering the entire surface, a pattern layer formed by various patterns, or a combination of these. Also good. For example, when coloring and concealing the background color of a substrate or the like, by using a solid colored layer, it is possible to obtain a design with a higher texture while concealing the coloring, and to express correspondence to various design characteristics Therefore, the solid colored layer and the pattern layer may be combined. On the other hand, when the ground pattern of the adherend is used, only the pattern layer is provided without using the solid colored layer.

  When the decorative layer has a pattern layer, the pattern exhibited by the decorative layer includes the patterns exemplified as the pattern expressed by the concave shape, for example, a wood grain conduit pattern, a marble pattern (for example, a travertine marble pattern), a cleavage plane of a granite plate, etc. Stone pattern imitating the surface of the rock, cloth pattern imitating cloth or cloth-like pattern, leather pattern expressing leather grain, tiled pattern, brickwork pattern, hairline, all-line groove, pear texture, sand Examples include eyes, letters, symbols, geometric patterns, patterns such as parquets, patchwork, etc. that combine these, and patterns such as the above-mentioned artificial marble.

  Among these patterns, considering the characteristics of the decorative material of the present invention having a high-quality design, a wood grain conduit pattern is preferable as the pattern. In the case of adopting a wood grain conduit pattern, more specifically, an area that is synchronized with a conduit groove portion that is darker in the wood grain conduit pattern of the decoration layer is set as the second pattern area so as to be synchronized with the pattern of the decoration layer. When the second cured product layer is provided on the upper portion, the conduit groove portion matches the concave shape, so that the conduit groove portion becomes a physical recess and is visually perceived as darker. A high-quality design with a feeling of luxury. For example, in the decorative material shown in FIGS. 3 and 4, a second pattern region is provided so as to synchronize with the pattern of the decoration layer, and a second cured product layer is provided immediately above the second pattern region. It corresponds to the concave shape. Therefore, in the decorative material shown in FIGS. 3 and 4, if the pattern of the decoration layer is a wood grain conduit pattern, the pattern of the decoration layer and the second pattern region, the second cured product layer and the concave shape provided immediately above the pattern Therefore, the conduit groove part of the decorative layer pattern will be physically recessed, and will be visually perceived as darker. And a decorative material with a high texture and design.

  The thickness of the decoration layer may be appropriately selected according to the desired pattern, but is preferably 0.5 to 20 μm from the viewpoint of coloring and concealing the background color of the base material and the like and obtaining a higher quality design. 1 μm to 10 μm is more preferable, and 2 to 5 μm is still more preferable.

(Surface property improving layer 7)
Since the cosmetic material of the present invention has the effect of improving surface properties such as scratch resistance, impact resistance, and contamination resistance, it is on the first cured product layer (surface) or the substrate and the first curing. It is preferable to provide a surface property improving layer between the physical layer. In addition, by providing the surface property improving layer, the difference between the height directly above the first pattern area and the height directly above the second pattern area is physically increased, and the depth of the concave shape is increased, so that the texture is further improved. High designability can also be obtained. The surface property improving layer is preferably provided on the first cured product layer (surface) as shown in FIG. 4 from the viewpoint of obtaining superior surface properties.

  As the surface property improving layer, either a thermoplastic resin or a curable resin may be used. From the viewpoint of obtaining superior surface properties, a layer formed from a curable resin, more specifically, curing. It is preferably a layer formed of a cured product of a liquid uncured product of a functional resin. Preferred examples of the curable resin include a thermosetting resin and an ionizing radiation curable resin from the viewpoint of obtaining superior surface characteristics, and a thermosetting resin is more preferable. Examples of the thermosetting resin used for forming the surface property improving layer include vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, acrylic resin, polyester resin, polyamide resin, butyral resin, alkyd resin, and cellulose acetate resin. Etc. In addition, two-component curable resins containing various polyols such as polyether polyols, acrylic polyols, polyester polyols, urethane acrylic polyols and the like as main ingredients and various isocyanates such as aromatic isocyanates and aliphatic (or alicyclic) isocyanates as curing agents. Are also preferred. Among these thermosetting resins, a two-component curable resin is preferable because an effect of improving surface characteristics can be obtained and a design with a higher texture can be easily obtained.

In addition, as a resin material for forming the surface property improving layer, the effect of improving the surface property is obtained, and the design quality with higher texture is easily obtained, so that the water of the thermoplastic resin obtained by dispersing the thermoplastic resin in water. Dispersions are also preferred. Examples of the thermoplastic resin of the thermoplastic resin aqueous dispersion include urethane resins, polyester resins, olefin resins, styrene resins, and the like, among which urethane resins are preferable.
The average particle size of the aqueous dispersion is usually about 5 to 500 nm, preferably 10 to 250 nm, and more preferably 15 to 100 nm. In this specification, the average particle size of the aqueous dispersion is measured at 25 ° C. for a dispersion diluted with water so that the concentration of the particles to be measured is 5 × 10 ⁻³ mass% using a laser particle analyzer. The angle between the incident light and the detector is 90 °, the number of integration is 100 times, and the value measured under the condition of the refractive index of water (1.333) as the refractive index of the dispersion solvent.

The surface property improving layer preferably contains various fillers such as an inorganic filler and an organic filler from the viewpoint of improving the surface properties, particularly improving the wear resistance.
Examples of the inorganic filler include those exemplified as the inorganic filler that can be used in the second cured product layer, and examples of the organic filler include polyolefin resin, acrylic resin, styrene resin, epoxy resin, urea resin, polyester resin, and phenol resin. And particles made of organic materials such as

There is no restriction | limiting in particular in the shape of these fillers, Any of spherical shape, polyhedron shape, etc. may be sufficient.
The average particle size of the filler is preferably 3 to 50 μm, more preferably 5 to 30 μm, from the viewpoint of improving the wear resistance. In the present specification, the average particle diameter of the filler is a value measured by a laser diffraction scattering method.
Further, the content of the filler is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass with respect to 100 parts by mass of the resin.

  When the surface property improving layer contains the filler, it can be said that the surface property improving layer is formed using a liquid composition of the resin and a resin composition containing the filler. As the resin composition for forming the surface property improving layer, in addition to the above liquid resin, preferably used fillers, weathering agents such as ultraviolet absorbers and light stabilizers, and other various additives as desired, for example, , UV shielding agent, polymerization inhibitor, crosslinking agent, infrared absorber, antistatic agent, adhesion improver, leveling agent, thixotropic agent, coupling agent, plasticizer, antifoaming agent, filler, antiblocking agent , Resin compositions containing various additives such as lubricants and solvents. These additives such as weathering agents may be used alone or in combination of two or more.

  The thickness of the surface property improving layer is preferably 1 to 30 μm, more preferably 3 to 20 μm, from the viewpoint of easily improving the wear resistance and easily obtaining a design with a higher texture.

(Reinforcing layer)
A reinforcement layer is a layer which reinforces the decorative material of this invention, and is a layer provided as needed in the surface (back surface side) on the opposite side to the surface which provides layers, such as a 1st hardened | cured material layer of a base material. . In particular, when the decorative material of the present invention is a thermosetting resin decorative board, a reinforcing layer is usually provided in many cases. The reinforcing layer can be made of various materials and materials constituting various layers according to the type and use of the decorative material. Especially when the decorative material is a thermosetting resin decorative board, the reinforcing layer is impregnated with the thermosetting resin. It is preferable to be formed by a sheet. When a fiber base material or paper base material impregnated with a thermosetting resin is adopted as the base material, a thermosetting property that is superior in mechanical properties by combining a reinforcing layer formed by a thermosetting resin impregnated sheet. A resin decorative board is obtained.

Examples of the thermosetting resin impregnated sheet include a fiber base material impregnated with an uncured resin composition containing a liquid uncured product of a thermosetting resin, a paper base material, and the like. The type of fiber base material and paper base material used in the thermosetting resin impregnated sheet is not particularly limited as long as it is exemplified as the base material fiber base material and paper base material, and the basis weight is preferably 100 to 300 g. / M ² , more preferably 150 to 250 g / m ² . Further, as the thermosetting resin, the same ones as those exemplified as the thermosetting resin that can be impregnated into the substrate in the state of a liquid uncured resin composition can be preferably exemplified. The liquid uncured resin composition of the curable resin is also preferable. Among these thermosetting resins, a phenol resin is preferable, and as the reinforcing layer, a phenol resin-impregnated paper, which is widely used as a core paper such as a melamine resin decorative board, is preferable.
As the phenol resin impregnated paper, for example, it is produced by impregnating a kraft paper having a basis weight of 150 to 250 g / m ² with a phenol resin so that the impregnation rate is about 20 to 60% and drying at about 100 to 140 ° C. Are preferably used.

(Primer layer)
In the decorative material of the present invention, in order to improve the adhesion of each layer, for example, between the substrate and the first cured product layer and the second cured product layer, between the first cured product layer and the surface property improving layer, A primer layer can be provided between the base material and the reinforcing layer.
Examples of the resin material forming the primer layer include urethane resin, polyester resin, acrylic resin, acrylic urethane resin, and vinyl chloride-vinyl acetate copolymer resin. Moreover, the thickness of a primer layer is about 0.1-15 micrometers normally from a viewpoint which obtains the outstanding adhesiveness efficiently, Preferably it is 1-10 micrometers.

(Manufacturing method of cosmetic material)
About the manufacturing method of the decorative material of the present invention, which is one of the preferred embodiments as the decorative material of the present invention, the base material, the decorative layer, the first cured product layer, the second cured product layer, and the surface property improvement shown in FIG. Taking a decorative material having a layer as an example, the production method will be described.

(One manufacturing method of cosmetics)
The decorative material of the present invention includes, for example, a step of providing a decorative layer on a substrate, a step of providing a first cured product layer and a second cured product layer on the decorative layer, and surface characteristics on the first cured product layer. It can manufacture by passing through the process of providing an improvement layer in order.

  The decorative layer is formed by applying an ink used for forming the decorative layer on a base material to provide a desired colored layer and pattern layer. The ink is applied 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, preferably a gravure printing method.

  Further, when the surface treatment is applied to the base material, a decoration layer is formed. When a primer layer is provided between the base material and the decoration layer, the primer layer may be provided before the formation of the decoration layer. Moreover, when providing a back surface primer layer in the surface (back surface) on the opposite side to the decoration layer side of a base material, you may provide in any before and after formation of a decoration layer. The primer layer can be formed using, for example, any of the known methods exemplified as the method for applying the ink for the decorative layer, for example, the resin composition constituting the primer layer.

Next, the first cured product layer and the second cured product layer are provided on the decorative layer. For example, an uncured resin composition containing a liquid uncured curable resin that forms the second cured material layer is applied on the decorative layer to form a coating film, and the coating film is cured and cured. A second cured product layer is formed as a product, and then an uncured resin composition containing a liquid uncured product of a curable resin that forms the first cured product layer is provided with the second cured product layer. A coating film may be formed by applying to the region, and the coating film may be cured to form a first cured product layer as a cured product.
When the decorative layer is a wood grain conduit pattern, the conduit groove portion of the decorative layer pattern is a second pattern region, a second cured product layer is provided immediately above the second pattern region, and other than the second pattern region By setting the region as the first pattern region and providing the first cured product layer immediately above the first pattern region, the conduit groove portion and the second pattern region, the second cured product layer provided directly above and the concave shape Will be synchronized. With such a configuration, the conduit groove portion is physically a concave portion and is visually perceived darker, and the decorative material of the present invention has a sense of quality and a sense of quality close to a real wood board. Thus, it becomes a decorative material having a high-quality design.

In forming the first cured product layer and the second cured product layer, the application method of the uncured resin composition containing the liquid uncured product of the curable resin is exemplified as the method of applying the ink of the decorative layer. Any known method may be employed.
Moreover, what is necessary is just to select the hardening method of the uncured resin composition containing the liquid uncured material of curable resin according to the kind of curable resin contained in this uncured resin composition. For example, when the uncured resin composition is a resin composition containing a liquid uncured product of a thermosetting resin, it may be cured by performing a heat treatment according to the thermosetting resin to be used.

When using an uncured resin composition containing a liquid uncured product of an ionizing radiation resin, the uncured resin layer formed by applying the uncured resin composition is irradiated with ionizing radiation such as an electron beam or ultraviolet light. A cured product may be used. Here, when an electron beam is used as the ionizing radiation, the acceleration voltage can be appropriately selected according to the resin used and the thickness of the layer, but the uncured resin layer is usually cured at an acceleration voltage of about 70 to 300 kV. preferable. The irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and for example, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp, etc. are used.

  Moreover, about the laminated body which formed the 1st hardened | cured material layer and the 2nd hardened | cured material layer, the location corresponding to a 2nd hardened | cured material layer is a convex part, and the location corresponding to a 1st hardened | cured material layer is a recessed part. It is also possible to form the first cured product layer and the second cured product layer by sandwiching between the mirror plate and the mirror surface plate and applying heat and pressure molding using a hot press machine or the like. By applying heat and pressure molding, a design with higher texture can be obtained.

Moreover, a 1st hardened | cured material layer can also be formed with the following method. For example, after the second cured product layer is formed by the above-described method, the base material on which the second cured product layer is formed is in a liquid state of a thermosetting resin that forms the first cured product layer using an impregnation apparatus. A liquid uncured resin composition containing an uncured product is impregnated so that the uncured resin composition is about 80 to 130 g / m ² (at the time of drying) and dried to obtain a liquid form of a thermosetting resin. The base material which formed the 2nd hardened | cured material layer which the uncured resin composition containing this uncured material impregnated was produced. A laminate obtained by laminating a kraft paper (core paper) impregnated with a phenol resin as a reinforcing layer as necessary is prepared, and the portion corresponding to the second cured product layer is a convex portion. The first cured product layer and the second cured product are sandwiched between an embossed plate and a mirror plate where the portion corresponding to the first cured product layer is a recess, and subjected to heat and pressure molding using a hot press machine or the like. Layers can also be formed.

The embossed plate used for heat and pressure molding can be replaced with a mirror plate and a shaping sheet. By using the embossed plate or the shaping sheet, the edge of the first cured product layer is configured with irregular irregularities, whereby the edge of the concave shape in plan view is configured with irregular irregularities. It will be a thing.
The conditions for the heat and pressure molding may be appropriately adjusted according to the type of the thermosetting resin to be used, and are not particularly limited. Usually, the temperature is 100 to 200 ° C., and the pressure is 0.1 to 9.8 MPa. The time is from 10 seconds to 120 minutes.
Moreover, the fiber base material and paper base material which impregnated the thermosetting resin used as a reinforcement layer may use one sheet, or may use multiple sheets.

Next, it is a step of providing a surface property improving layer on the first cured product layer. On the 1st hardened | cured material layer formed by the said process, the resin composition which forms a surface characteristic improvement layer is apply | coated, and it is made to harden as needed, and a surface characteristic improvement layer is formed. When the thermoplastic resin aqueous dispersion is used for forming the surface property improving layer, it is preferable to perform a drying treatment for about 1 to 10 minutes under a temperature condition of about 80 to 130 ° C.
The heat and pressure molding using the embossed plate may be performed after the surface property improving layer is formed. In the case where the resin composition for forming the first cured product layer is impregnated using an impregnation apparatus, the emulsified plate is impregnated. The resin composition that forms the surface property improving layer on the resin composition is subjected to heat and pressure molding using an embossed plate and a mirror surface plate to obtain a first cured product layer and a surface property improving layer. You may form simultaneously.

  According to the above manufacturing method, the substrate has a decorative layer, the first cured product layer and the second cured product layer on the decorative layer, and the surface property improving layer on the first cured product layer. A decorative material having a concave shape formed in the first cured product layer is obtained by the cured product layer and the second cured product layer not provided with the first cured product layer. When the above manufacturing method is adopted, the edge of the first cured product layer is constituted by repeating irregular irregularities by further etching, etc., and it is also possible to obtain a design with a higher texture. it can. In this way, the decorative material of the present invention can be manufactured.

(Manufacturing method of other cosmetics)
The cosmetic material of the present invention includes, in addition to the above-described method for producing a cosmetic material, for example, a step of providing a decorative layer on a substrate, a step of forming a second cured product layer on the decorative layer, a first cured product A step of impregnating an uncured resin composition containing a liquid uncured product of a curable resin for forming a layer, and applying a resin composition for forming a surface property improving layer on the impregnated uncured resin composition It is also manufactured by sequentially passing through a step, a step of laminating a release sheet on the coating film of the resin composition forming the surface property improving layer, a step of heating and pressing, and a step of peeling the release sheet. Can do.

A method of providing a decorative layer on a substrate, a method of forming a second cured product layer on the decorative layer, and impregnating an uncured resin composition containing a liquid uncured product of a curable resin forming the first cured product layer The method for applying and the method for applying the resin composition for forming the surface property improving layer are the same as those described in the above-mentioned method for producing a decorative material.
The step of laminating the release sheet is an uncured resin composition obtained by these methods, in which a decorative layer is provided on a substrate, a second cured product layer is provided on the decorative layer, and a first cured product layer is formed. Resin that forms the surface property improving layer of a laminate in which a coating film of the resin composition that forms the surface property improving layer is formed on the uncured resin composition that is impregnated with the product and forms the first cured material layer It is a step of laminating a release sheet on the coating film of the composition.

As the release sheet, an easily adhesive resin sheet, a resin sheet having a cured product layer of a curable resin, or the like is preferably used from the viewpoint of obtaining a design with a higher texture.
Examples of the easily adhesive resin sheet used for the release sheet include polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resins such as polyethylene and polypropylene; sheets of various resins such as acrylic resins. The easy adhesion layer provided on the resin sheet is preferably a resin sheet formed of a thermoplastic resin such as an acrylic resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, or urethane resin.

The easy-adhesive resin sheet may further have an easy-adhesive layer. The easy-adhesion layer may have the same configuration as the primer layer.
In addition, the resin sheet can be subjected to a physical surface treatment such as an oxidation method or a roughening method, or a surface treatment such as a chemical surface treatment.

  The resin sheet used for the resin sheet which has the hardened | cured material layer of the liquid uncured material of curable resin, The resin sheet which can be used for the said easily-adhesive resin sheet is mentioned preferably. Preferred examples of the curable resin include curable resins such as thermosetting resins and ionizing radiation curable resins. Examples of these thermosetting resins and ionizing radiation curable resins include the thermosetting resins and ionizations exemplified as the resins that can be used for forming the first cured product layer, the second cured product layer, and the surface property improving layer. A radiation curable resin is preferred. Among these, from the viewpoint of obtaining a design with higher texture, an ionizing radiation curable resin is preferable, and a polymerizable monomer is more preferable. The polymerizable monomer may be selected from the polymerizable monomers that can be used for forming the second cured product layer, and from the viewpoint of obtaining a more textured design, in particular, trimethylolpropane tri (meth) acrylate, Trifunctional (meth) acrylate monomers such as pentaerythritol tri (meth) acrylate are preferred, and trimethylolpropane tri (meth) acrylate is more preferred. Further, the curable resin used for the release sheet may have been subjected to various modifications such as alkylene oxide modification such as ethylene oxide modification and propylene oxide modification.

For the cured product layer provided on the release sheet, in principle, the release agent is used from the viewpoint of stabilizing the adhesion between the first cured product layer and the second cured product layer and obtaining a design with a higher texture. Is preferably not included, but a release agent may be included for adjusting and optimizing adhesion. Preferred examples of the release agent include a fluorine-based release agent and a silicone-based release agent, and a silicone-based release agent is more preferable. Examples of the silicone mold release agent include those exemplified as the silicone mold release agent that can be used in the second cured product layer.
The content of the release agent in the cured product layer provided in the release sheet is from the viewpoint of efficiently obtaining a higher quality design, with respect to 100 parts by mass of the curable resin forming the cured product layer. 0.1-5 mass parts is preferable, 0.5-4 mass parts is more preferable, and 1-3 mass parts is still more preferable.

Moreover, it is preferable that the hardened | cured material layer provided in the sheet | seat for peeling contains the inorganic filler. As an inorganic filler, what was illustrated as an inorganic filler which can be used for said 2nd hardened | cured material layer is mentioned, What is necessary is just to select and use from these.
The content of the inorganic filler in the cured product layer provided on the release sheet is 0 with respect to 100 parts by mass of the curable resin forming the cured product layer, from the viewpoint of efficiently obtaining a higher quality design. 0.1-30 mass parts is preferable, 1-20 mass parts is more preferable, and 5-15 mass parts is still more preferable.

  The step of heat and pressure forming is a step of heat and pressure forming the laminate in which the peeling sheets are laminated. Specifically, after laminating the release sheet, a laminate in which a kraft paper (core paper) impregnated with a phenolic resin as necessary is laminated as a reinforcing layer is prepared, and two laminates are produced. And is subjected to heat and pressure molding using a hot press machine or the like. The method and conditions for heat and pressure molding using a hot press machine or the like are the same as those for the heat and pressure molding described in the formation of the first cured product layer.

The laminate obtained through heat-pressure molding is a curable resin that forms a base material, a decorative layer, a second cured product layer, and a first cured product layer formed on one side so as to cover the second cured product layer It is the laminated body which the hardened | cured material layer of the composition, the surface characteristic improvement layer, and the peeling sheet laminated | stacked. The step of peeling the peeling sheet is a step of peeling the peeling sheet from the laminate to obtain the decorative material of the present invention.
The peeling method of a peeling sheet will not be restrict | limited especially if it can peel so that a peeling sheet may not remain.

The cured product layer of the uncured resin composition containing the liquid uncured product of the curable resin forming the first cured product is provided immediately above the second cured product layer and in contact with the decorative layer. When the release sheet is peeled from the laminate obtained through the heat and pressure molding, the cured product layer portion provided in contact with the decorative layer having higher adhesion remains and becomes the first cured product layer, which is more closely adhered. The cured product layer provided in contact with the second cured product layer having low properties and the surface property improving layer on the cured product layer are peeled off, and the first cured product layer is directly above the second cured product layer. Will not exist. Moreover, in the laminate obtained through the thermo-press molding, curing of the uncured resin composition including the liquid uncured material of the curable resin that forms the first cured material layer existing over the entire surface. Since the edge of the cured product layer that is not peeled and becomes the first cured product layer is formed by repeating irregular irregularities by partially peeling the physical layer, the resulting concave shape The edge is constituted by repeating irregular irregularities. Further, according to the other method for producing a decorative material, the shape of the bottom portion in the sectional shape of the concave shape is a shape having a bottom surface that is a non-curved surface because the surface of the bottom portion becomes the surface of the second cured product layer. It becomes easy.
Therefore, according to the other method for manufacturing a decorative material, it is easy to obtain a decorative material having a higher texture and design.

(Use of cosmetic materials)
The decorative material of the present invention is a decorative material having a sense of quality and a design with a sense of quality and a high-class feeling. Therefore, the decorative material of the present invention can be used for various applications as it is or after being subjected to a predetermined molding process. For example, it is laminated on a substrate such as a flat plate of various materials, a curved plate, a sheet (or film), etc., and a building plate for interior and exterior, such as a cabinet for furniture and kitchen products, various counters, desks, etc. It can be used for building materials for residential use.

  As the substrate, for example, as a plate material such as timber veneer, timber plywood, particle board, MDF (medium density fiberboard) such as cedar, straw, pine, lawan, etc. Wood members used: Metal members used as plate materials such as iron and aluminum, steel plates, three-dimensional articles, or sheets; Non-cement ceramic materials such as glass, ceramics such as ceramics, and plaster; ALC (lightweight cellular concrete) plates Ceramic materials used as plate materials such as non-ceramic ceramic materials such as ceramic materials, etc .; polyolefin resins such as acrylic resin, polyester resin, polystyrene resin, polypropylene, ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenol Resin, vinyl chloride resin, cellulose resin, rubber and other plate materials, three-dimensional shaped articles, Rui resin member or the like used as a sheet and the like. Moreover, these members can be used individually or in combination of multiple types.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation and observation method)
(1) Evaluation of design property About the decorative material obtained by each Example and the comparative example, arbitrary 20 adults were made to evaluate visually about the design property about whether it has a design property with a high texture.
A: There were 18 or more people out of 20 who answered that they had a high-quality design.
B: There were 15 or more people out of 20 who answered that they had a high-quality design.
C: There were 14 or less people out of 20 who answered that it had a design with a high texture.
(2) Observation of surface shape About the decorative material obtained by each Example and the comparative example, a cross-sectional piece was produced with the microtome, and the scanning electron microscope (The Hitachi High-Technologies company make, "S-4800 TYPE2") was used. The cross section was observed under the conditions of acceleration voltage: 1 kV, acceleration current: 10 μA, working distance: 8 mm.

Example 1
Titanium paper base paper for building materials (KJ Special Paper Co., Ltd., “PM-67P”, basis weight: 80 g / m ² , thickness: 100 μm), printing ink (DIC Graphics Co., Ltd., “Ode SPTI”) Is used to form a decorative layer exhibiting a 3 μm-thick wood grain conduit pattern by gravure printing, and a liquid uncured product of the following curable resin for forming a second cured product layer is included on the decorative layer The uncured resin composition is printed with a pattern having a plurality of linear patterns having a width of 10 μm and a length of 50 mm, cured by irradiation with an electron beam (pressurized voltage: 165 KeV, 3 Mrad (30 kGy)), and second cured. A physical layer (thickness: 2 μm) was formed. Next, an uncured resin composition containing a liquid uncured product of a curable resin that forms the following first cured product layer using the impregnation apparatus on the base material on which the decorative layer and the second cured product layer are formed. The uncured resin composition is impregnated at 80 g / m ² (when dried), and a release film prepared by the following method is laminated on the dried one, and this is applied to kraft paper. A base material on a reinforcing layer in which three sheets of phenol resin-impregnated core paper (Ota Sangyo Co., Ltd., manufactured by Ota Sangyo Co., Ltd.) having a basis weight of 245 g / m ² obtained by impregnating a liquid uncured resin composition made of a phenol resin. A laminated body was prepared so that the reinforcing layer and the reinforcing layer were opposed to each other. The obtained laminate was sandwiched between two mirror plates and subjected to heat and pressure molding at a molding temperature of 150 ° C. and a molding pressure of 100 kg / cm ² for 10 minutes using a hot press machine, and then for peeling. A decorative board was produced by peeling off the film. Said evaluation was performed about the obtained decorative board, and the result is shown in Table 1. Moreover, said observation is performed about the obtained decorative board and the microscope enlarged image is shown in FIG.

(Uncured resin composition containing liquid uncured product of curable resin for forming second cured product layer)
The following components were stirred for 1 hour at a rotational speed of 2000 rpm using a process homogenizer (manufactured by SMT Co., Ltd., “PH91”) to obtain a resin composition.
60 parts by mass of ionizing radiation curable resin (dipentaerythritol penta (hexa) acrylate (pentaacrylate content: 40 to 50% by mass), manufactured by Toagosei Co., Ltd., “Aronix M400”) Silicone release agent (both ends) Methacryloyloxyalkyl-modified organopolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., “X-22-164B”) 0.9 parts by mass Silane coupling-treated silica 18 parts by mass Methyl ethyl ketone (Maruzen Petrochemical Co., Ltd.) 40 parts by mass (first curing) Curable resin composition for physical layer formation)
Melamine formaldehyde resin 60 parts by weight Water 35 parts by weight Isopropyl alcohol 5 parts by weight (Preparation of film for peeling)
On the easy-adhesion surface of a polyethylene terephthalate film (thickness: 50 μm, manufactured by Toyobo Co., Ltd., “Cosmo Shine A4100”), an ionizing radiation curable resin (modified ethylene bottom oxide of trimethylolpropane triacrylate, manufactured by Toagosei Co., Ltd.) "Aronix M350") 100 parts by mass, silicone release agent (both ends methacryloyloxyalkyl-modified organopolysiloxane, manufactured by Shin-Etsu Chemical Co., Ltd., "X-22-164B"), silica particles (Fuji Silysia Chemical Ltd.) An uncured resin composition containing a liquid uncured product of an ionizing radiation curable resin containing 8 parts by mass of “Silicia 450”, average particle size: 5.2 μm) and 50 parts by mass of ethyl acetate was applied. , Irradiated with an electron beam (pressurized voltage: 165 KeV, 5 Mrad (50 kGy)) And to form a cured product layer having a thickness of 5 [mu] m, to prepare a release film.

Example 2
In Example 1, an uncured resin composition containing a liquid uncured product of a curable resin for forming a second cured product layer was applied so as to synchronize with the conduit groove portion in the wood grain conduit pattern of the decorative layer. Made a cosmetic material in the same manner as in Example 1. Said evaluation was performed about the obtained decorative board, and the result is shown in Table 1.

Comparative Example 1
In Example 1, the second cured product layer and the release sheet are not formed, and one mirror surface plate is replaced with an embossed plate in heat and pressure molding, and the embossed plate and the surface provided with the decorative layer are opposed to each other. As described above, the laminated body was sandwiched and subjected to heat and pressure molding to produce an embossed decorative board. Said evaluation was performed about the obtained decorative board, and the result is shown in Table 1. Moreover, said observation is performed about the obtained decorative board and the microscope enlarged image is shown in FIG.

From the results of Examples 1 and 2, the cosmetic material of the present invention was evaluated as a cosmetic material having a sense of quality and a high-quality design with a sense of realism. Further, the makeup of Example 2 in which the second pattern region is synchronized with the pattern of the decorative layer (wooden conduit pattern), more specifically, the second hardened material layer is provided in synchronization with the conduit groove portion of the woody conduit pattern. It was evaluated that the material was superior in design to the decorative material of Example 1.
On the other hand, the decorative material of Comparative Example 1 that did not have the second cured product layer was not evaluated as a decorative material having a high-quality design, although embossed.
The microscope enlarged image of the decorative material of Example 1 in FIG. 5 shows that the edge of the shape of the concave shape in plan view is configured by repeating irregular irregularities, and the bottom surface of the concave shape is a non-curved surface (plane). It was also confirmed that the cross-sectional shape was substantially rectangular (substantially trapezoidal). On the other hand, according to the microscope magnified image of the decorative material of Comparative Example 1 in FIG. 6, the edge of the concave shape in plan view is gentle and smooth, the bottom surface of the concave shape has a curved surface, and the shape in cross section is It was composed of a gentle and smooth curve, and was confirmed to be a substantially semi-elliptical shape.

1. Cosmetic material2. Concave shape 21. Recessed edge 21B. Recessed portion 21C. Projection 22. 2. Recessed bottom surface First cured product layer 31. First pattern area 4. Second cured product layer 41. Second pattern area 5. Base material 6. Decorative layer Surface property improving layer Extension direction Normal direction

Claims (18)

  A cosmetic material having a concave shape on the surface, and the edge of the concave shape in plan view is configured by repeating irregular irregularities.   The decorative material according to claim 1, wherein the shape of the concave portion is a shape having a bottom surface that is a non-curved surface.   The cosmetic material according to claim 1 or 2, wherein the concave shape includes a concave shape having an average width of 0.1 to 10 mm and an average maximum depth of 1 to 30 µm.   The decorative material according to claim 3, wherein the concave shape includes a concave shape having an average length of 2 to 50 mm.   A first cured region formed of a base material, a first pattern region, a second pattern region, and a curable resin, wherein the first pattern region is formed on a part of one surface side of the base material; The second pattern region is formed on the remaining portion of the one surface side of the substrate, the first cured product layer is present immediately above the first pattern region, and directly above the second pattern region. In any one of Claims 1-4 by which this recessed part shape is formed in this 1st hardened | cured material layer by not existing, and the bottom face of this recessed part shape is formed by the surface immediately above this 2nd pattern area | region. The cosmetic material described.   The cosmetic material according to claim 5, further comprising a second cured product layer formed of a curable resin immediately above the second pattern region.   The decorative material according to claim 6, wherein the curable resin forming the second cured product layer is an ionizing radiation curable resin.   The cosmetic material according to any one of claims 5 to 7, wherein the second cured product layer contains a release agent.   The cosmetic material according to claim 8, wherein the release agent is a silicone-based release agent.   The cosmetic material according to any one of claims 5 to 9, wherein the second cured product layer contains an inorganic filler.   The decorative material according to claim 10, wherein the inorganic filler is silica particles.   The curable resin which forms said 1st hardened | cured material layer is a thermosetting resin, The cosmetic material of any one of Claims 5-11.   The decorative material according to any one of claims 5 to 12, further comprising a decorative layer between the base material and the first cured product layer.   The cosmetic material according to any one of claims 6 to 12, further comprising a decorative layer between the base material, the first cured product layer, and the second cured product layer.   The decorative material according to claim 13 or 14, wherein the decorative layer has a wood grain conduit pattern.   The decorative material according to any one of claims 13 to 15, wherein the second pattern region and the pattern of the decoration layer are synchronized.   The decorative material according to any one of claims 1 to 16, wherein the concave shape forms a wood grain conduit pattern.   The cosmetic material according to any one of claims 5 to 17, further comprising a surface property improving layer on the first cured product layer or between the substrate and the first cured product layer.