JP7521536B2 - Cosmetic materials - Google Patents

Description

The present invention relates to a cosmetic material.

Conventionally, decorative materials have been used for the surfaces of tables, counters, walls, floors, etc., by impregnating a porous substrate such as titanium paper with an uncured liquid of melamine resin, laminating it on phenol core paper, etc. as necessary, and then curing the impregnated resin liquid with a heat press. Such decorative materials impregnated and cured with melamine resin exhibit physical properties such as strength, hardness, and heat resistance.

Such decorative materials are required to have a design that gives off a sense of luxury, and a visual three-dimensional effect is imparted by forming an uneven surface.
As a decorative material having an uneven surface, there has been proposed a decorative material that is embossed using an embossed plate (a textured mirror plate) on which an uneven surface is formed (see, for example, Patent Documents 1 and 2).

However, when imparting a desired textured pattern to the surface of the decorative material described in Patent Documents 1 and 2, an embossing plate is required for each pattern, which is costly and difficult to manufacture. In addition, it is difficult to harmonize the textured shape with the underlying pattern, making it difficult to impart a high level of design.

On the other hand, Patent Document 3 proposes a decorative material having a surface irregularity that does not use an embossed plate.

JP 2015-193209 A JP 2017-87544 A International Publication No. 2016/148091

The decorative material of Patent Document 3 includes a paper base material, a release layer containing a cured product of an ionizing radiation curable resin provided on a portion of the surface of the paper base material, and a surface layer containing a cured product of a melamine resin provided on the remaining portion of the surface of the paper base material (the portion of the surface of the paper base material on which the release layer is not provided). The decorative board of Patent Document 3 is manufactured by a method including a step of providing a release layer on a portion of the surface of the paper base material, a step of impregnating the paper base material with an uncured product of melamine resin and covering the release layer with the uncured product of melamine resin, and then heating to thermally cure the uncured product of melamine resin, and a step of peeling off the cured resin film covering the release layer.
The decorative material of Patent Document 3 does not use an embossed plate, and therefore can solve the problems of Patent Documents 1 and 2. However, there have been many cases where the decorative material of Patent Document 3 deteriorates in design over time.
The present invention has been made under these circumstances, and has an object to provide a decorative material which has a visual three-dimensional effect and is also excellent in abrasion resistance.

As a result of intensive research, the inventors have found that the decorative material of Patent Document 3 cannot have a thick surface layer containing a cured melamine resin, and therefore the decorative layer on the substrate wears away over time, resulting in a loss of design.
The present inventors also found that the reason why the thickness of the surface layer of the decorative material of Patent Document 3 cannot be increased is because the thickness of the release layer is thin. This is because, when the thickness of the surface layer is increased in a case where the release layer is thin, the thickness of the cured resin film on the release layer increases, and the cured resin film undergoes cohesive failure when peeling off the cured resin film on the release layer.
Furthermore, the inventors discovered that the reason why the release layer of the decorative material in Patent Document 3 cannot be made thicker is that the components that make up the release layer seep into the substrate when the release layer is formed, and they solved the above problem by forming a permeation prevention layer on a part of the substrate.

The present invention aims to provide the following items [1] to [8].
[1] A decorative material having a substrate selected from a paper substrate and a fiber substrate, the decorative material having a first region and a second region in a plane, the decorative material in a portion corresponding to the first region having a permeation prevention layer and a first hardened material layer having a releasable surface, in that order, on the substrate, and the decorative material in a portion corresponding to the second region having a second hardened material layer on the substrate, wherein when the thickness of the permeation prevention layer is defined as t0, the thickness of the first hardened material layer is defined as t1, and the thickness of the second hardened material layer is defined as t2, the relationship t0 + t1 < t2 is satisfied.
[2] The decorative material described in [1], wherein the permeation prevention layer contains an ionizing radiation curable resin.
[3] The decorative material according to [1] or [2], wherein t1 is greater than 3.5 μm and less than or equal to 30.0 μm.
[4] The decorative material according to any one of [1] to [3], wherein t2-(t0+t1) is 2.0 μm or more and 50.0 μm or less.
[5] The decorative material in the area corresponding to the first region has a first decorative layer in at least a portion between the substrate and the permeation prevention layer, as described in any of [1] to [4].
[6] The decorative material according to any one of [1] to [5], wherein the decorative material in the area corresponding to the second region has a second decorative layer in at least a portion between the substrate and the second cured material layer.
[7] The decorative material according to any one of [1] to [6], wherein the first cured material layer contains a release agent.
[8] The decorative material according to any one of [1] to [7], wherein the second cured material layer contains a melamine resin.

According to the present invention, it is possible to provide a decorative material that has a visual three-dimensional effect and excellent abrasion resistance.

1 is a cross-sectional view showing one embodiment of a decorative material of the present invention. FIG. 2 is a cross-sectional view showing one step of the method for producing the decorative material of the present invention. FIG. 2 is a cross-sectional view showing one step of the method for producing the decorative material of the present invention. FIG. 2 is a cross-sectional view showing one step of the method for producing the decorative material of the present invention. FIG. 2 is a cross-sectional view showing one step of the method for producing the decorative material of the present invention.

[Cosmetic materials]
The decorative material of the present invention is a decorative material having a substrate selected from a paper substrate and a fiber substrate, the decorative material having a first region and a second region in a plane, the decorative material in a portion corresponding to the first region having a permeation prevention layer and a first hardened material layer having a releasable surface, in that order, on the substrate, and the decorative material in a portion corresponding to the second region having a second hardened material layer on the substrate, and when the thickness of the permeation prevention layer is defined as t0, the thickness of the first hardened material layer is defined as t1, and the thickness of the second hardened material layer is defined as t2, the relationship t0 + t1 < t2 is satisfied.

FIG. 1 is a cross-sectional view showing one embodiment of a decorative material 100 of the present invention.
The decorative material 100 in Fig. 1 has a first region R1 and a second region R2 in a plane. The decorative material 100 in Fig. 1 also has a permeation prevention layer 31 and a first cured material layer 32 having a releasable surface, in this order, on the substrate 10 in a location corresponding to the first region R1. The decorative material 100 in Fig. 1 also has a second cured material layer 22 on the substrate 10 in a location corresponding to the second region R2.
In Fig. 1, t0 indicates the thickness of the permeation prevention layer 31, t1 indicates the thickness of the first hardened material layer 32 having releasability, and t2 indicates the thickness of the second hardened material layer 22. The decorative material 100 in Fig. 1 satisfies the relationship t0 + t1 < t2.
1 has a first decorative layer 33 between the substrate 10 and the permeation prevention layer 31 in a location corresponding to the first region R1. The decorative material 100 in Fig. 1 has a second decorative layer 23 between the substrate 10 and the second cured product layer 22 in a location corresponding to the second region R2.

In this specification, "planar" means the surface of the side of the cosmetic material of the present invention having the permeation prevention layer relative to the substrate (within the xy plane when the cosmetic material in FIG. 1 is viewed from the permeation prevention layer side relative to the substrate). In addition, in this specification, "planar view" means that the cosmetic material of the present invention is viewed perpendicularly from the side having the permeation prevention layer relative to the substrate.

<Substrate>
The substrate is selected from a paper substrate and a fiber substrate, with the paper substrate being preferred.
Paper substrates and fiber substrates are preferred in that they can be imparted with a curable resin to impart excellent mechanical properties, thereby increasing the pencil hardness of the surface of the decorative material and making the surface of the decorative material less susceptible to scratches.

Examples of paper substrates include kraft paper, titanium paper, linter paper, resin-impregnated paper, tissue paper, and Japanese paper.
Examples of the fiber substrate include a fiber substrate made of inorganic fibers such as glass fibers, alumina fibers, silica fibers, and carbon fibers, a fiber substrate made of organic fibers of various synthetic resins such as polyester resin, acrylic resin, polyethylene resin, and polypropylene resin, and a composite of these. The fiber substrate may be a nonwoven fabric or a woven fabric.

The thickness of the substrate is not particularly limited and may be appropriately selected depending on the desired performance, and is usually about 10 to 150 μm, preferably 20 to 120 μm, and more preferably 30 to 100 μm, from the viewpoints of ensuring mechanical properties and ease of handling. In addition, when a paper substrate is used as the substrate, the basis weight is usually about 20 to 150 g/ ^m2 , preferably 30 to 100 g/ ^m2 , from the same viewpoint.

The substrate is preferably impregnated with a curable resin. This structure can improve the mechanical strength of the cosmetic material, and in turn increase the pencil hardness of the surface of the cosmetic material, making the surface of the cosmetic material less susceptible to scratches.
As the curable resin, a thermosetting resin, an ionizing radiation curable resin, or the like can be used, with a thermosetting resin being preferred from the viewpoint of ease of handling.

As the curable resin to be impregnated into the substrate, from the viewpoint of enhancing the texture of the decorative material and improving the mechanical strength of the decorative material, preferred are melamine resin, urea resin, melamine-urea resin, guanamine resin, sulfonamide resin, diallyl phthalate resin, polyester resin, phenol resin, epoxy resin, aminoalkyd resin, silicon resin, polysiloxane resin, etc., of which thermosetting resins such as melamine resin, urea resin, melamine-urea resin, phenol resin, guanamine resin, and sulfonamide resin are preferred. Furthermore, among thermosetting resins, melamine resin, melamine-urea resin, and phenol resin are preferred, with melamine resin being particularly preferred.

An example of a method for impregnating a substrate with a thermosetting resin is to prepare an uncured thermosetting resin composition and impregnate the substrate with the composition (for example, step (4) described below).
The impregnated composition is heated at an appropriate time to be cured by a crosslinking reaction, a polymerization reaction or the like, to become a cured thermosetting resin (for example, step (6) described below).

In this specification, when simply referring to a "thermosetting resin", it means a cured product obtained by curing an uncured thermosetting resin. The same applies to other curable resins such as ionizing radiation curable resins.
In this specification, the terms "curable resin composition,""thermosetting resin composition," and "ionizing radiation curable resin composition" mean that the composition is uncured, unless otherwise specified.

The substrate may be one that has been subjected to a surface treatment such as a physical surface treatment such as an oxidation method or a roughening method, or a chemical surface treatment, or that has been formed with a primer layer, on one or both sides thereof, in order to improve interlayer adhesion with other layers that constitute the decorative material, or to strengthen adhesion with the adherend, etc.
Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone-ultraviolet light treatment, etc., and examples of the roughening method include sandblasting, solvent treatment, etc. These surface treatments are appropriately selected depending on the type of substrate, but generally, corona discharge treatment is preferably used in terms of the effect of the surface treatment, operability, etc.

<Area>
The decorative material of the present invention has, within a plane, a first region R1 and a second region R2.
When the thickness of the permeation prevention layer is defined as t0, the thickness of the first hardened material layer as t1, and the thickness of the second hardened material layer as t2, t2-(t0+t1) is an index of the elevation difference between the elevation of the first region R1 and the elevation of the second region R2.
Therefore, by satisfying the relationship t0 + t1 < t2, the first region R1 will be perceived as recessed and the second region R2 will be perceived as raised, and the contrast between the two regions can give the decorative material a good three-dimensional look.

t2-(t0+t1) is preferably 2.0 μm or more and 50.0 μm or less, more preferably 5.0 μm or more and 35.0 μm or less, and even more preferably 10.0 μm or more and 30.0 μm or less.
By setting t2-(t0+t1) to 2.0 μm or more, it is possible to easily achieve a good three-dimensional effect, and by setting t2-(t0+t1) to 50.0 μm or less, it is possible to easily and stably manufacture the first region and the second region.

t0, t1, and t2 are preferably calculated as the average thickness of 20 locations. The thickness can be calculated, for example, from a cross-sectional photograph of the decorative material. It is preferable to select the 20 locations for calculating the average thickness without bias.

When the area of the first region R1 of the decorative material is defined as S1 and the area of the second region R2 is defined as S2, it is preferable that S2/S1 is 0.5-20, and more preferably 1.0-10.
By making S2/S1 0.5 or more, the proportion of high elevations in the plane of the decorative material increases, making it easier to improve the abrasion resistance of the decorative material. Also, by making S2/S1 20 or less, the balance between the proportion of areas that are visible as recessed and areas that are visible as raised can be set in an appropriate range, making it easier to improve the design.

First Zone
The first region is an area that is visually perceived as being recessed compared to the second region.
The first region has, on a substrate, a permeation preventing layer and a first cured material layer having a releasable surface, in this order.

It is preferable that the surface of the first region is roughened. By roughening the surface of the first region, the first region is more likely to appear recessed, which makes it easier to achieve a better three-dimensional effect.

- Penetration prevention layer -
The permeation prevention layer is disposed between the substrate and the first cured material layer. With this configuration, the composition constituting the first cured material layer is prevented from permeating into the substrate, the thickness of the first cured material layer is ensured, and the thickness of the second cured material layer can be increased, which makes it easier to improve the abrasion resistance of the decorative material.
It is essential that the permeation prevention layer is formed on a part of the substrate, not on the entire substrate. If the permeation prevention layer is formed on the entire substrate, the substrate is difficult to be impregnated with the curable resin. Therefore, when the total area of the permeation prevention layer when the decorative material is viewed in a plane is 100, the area of the permeation prevention layer present in the first region is preferably 90 or more, more preferably 95 or more, even more preferably 97 or more, and even more preferably 99 or more. In other words, it is preferable that the permeation prevention layer is not substantially present in any place other than the first region in the plane of the decorative material.

The permeation-preventing layer preferably contains a curable resin. In other words, the permeation-preventing layer preferably contains a cured product of an uncured curable resin composition.
In addition, the content of the curable resin is preferably 50 mass% or more of the total solid content constituting the permeation prevention layer, more preferably 70 mass% or more, even more preferably 80 mass% or more, and even more preferably 90 mass% or more.
When the permeation preventing layer contains a curable resin, the permeation preventing layer can improve the sealing effect of the first cured product layer.

In order to make it difficult for the composition forming the permeation prevention layer to permeate into the substrate, the composition forming the permeation prevention layer preferably contains a thermoplastic resin. The content of the thermoplastic resin is preferably 2 to 30 parts by mass, more preferably 5 to 15 parts by mass, relative to 100 parts by mass of the curable resin.
Examples of the thermoplastic resin include general-purpose thermoplastic resins such as acrylic resins, polyester resins, and cellulose resins.

Preferred examples of the curable resin for the permeation prevention layer include thermosetting resins and ionizing radiation curable resins, with ionizing radiation curable resins being more preferred.

Preferred examples of the thermosetting resin include the same as those exemplified as the thermosetting resin that can be impregnated into the substrate.
The ionizing radiation curable resin is a resin that is crosslinked and cured by irradiation with ionizing radiation, and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group that is crosslinked and cured by irradiation with ionizing radiation, and preferred examples include functional groups having an ethylenic double bond such as (meth)acryloyl group, vinyl group, and allyl group. In addition, the ionizing radiation means electromagnetic waves or charged particle beams that have an energy quantum capable of polymerizing or crosslinking molecules, and generally includes ultraviolet rays (UV) or electron beams (EB), but also includes electromagnetic waves such as X-rays and gamma rays, charged particle beams such as alpha rays, and ion beams.
Specifically, the ionizing radiation curable resin may be appropriately selected from polymerizable monomers and polymerizable oligomers that have been conventionally used as ionizing radiation curable resins. From the viewpoint of easily suppressing the permeation of the composition forming the permeation prevention layer into the substrate, the ionizing radiation curable resin is preferably a polymerizable oligomer.

As the polymerizable monomer, a (meth)acrylate monomer having a radically polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth)acrylate monomer is preferable. Here, "(meth)acrylate" means "acrylate or methacrylate".
Examples of polyfunctional (meth)acrylate monomers include (meth)acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group. From the viewpoint of obtaining design properties with a higher texture and better surface properties, acrylate monomers having an acryloyl group are preferred.
From the viewpoint of obtaining a design with a higher texture and better surface properties, the number of functional groups is preferably 2 or more, more preferably 3 or more, and even more preferably 4 or more, and the upper limit is preferably 8 or less, more preferably 6 or less. These polyfunctional (meth)acrylates may be used alone or in combination of two or more kinds.

Preferred 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; and trifunctional or higher (meth)acrylates such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and isocyanuric acid-modified tri(meth)acrylate. Among these, from the viewpoint of obtaining a design with a higher quality texture and more excellent surface characteristics, dipentaerythritol-based polymerizable monomers such as dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate are preferred, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are more preferred, and it is particularly preferred to use dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate in combination.

Examples of polymerizable oligomers include (meth)acrylate oligomers having two or more ionizing radiation curable functional groups in the molecule and having at least a (meth)acryloyl group as the functional group. Examples include urethane (meth)acrylate oligomers, epoxy (meth)acrylate oligomers, polyester (meth)acrylate oligomers, polyether (meth)acrylate oligomers, polycarbonate (meth)acrylate oligomers, acrylic (meth)acrylate oligomers, polycaprolactone urethane (meth)acrylate oligomers, polycaprolactone diol urethane (meth)acrylate, etc.

In order to obtain a design with a higher quality texture and better surface characteristics, the number of functional groups of these polymerizable oligomers is preferably 2 or more, more preferably 3 or more, with the upper limit being preferably 8 or less, more preferably 6 or less.

The weight average molecular weight of the polymerizable oligomer is preferably 500 or more, more preferably 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 the average molecular weight measured by GPC analysis and converted into standard polystyrene.

From the viewpoint of facilitating the formation of the first cured material layer, it is preferable that the permeation prevention layer does not substantially contain a release agent. "Substantially does not contain a release agent" means that the content of the release agent is less than 0.1% by mass of the total solid content of the permeation prevention layer, preferably 0.01% by mass or less, and more preferably 0% by mass (no release agent is contained).

It is preferable that the permeation prevention layer does not substantially contain a filler. Substantially not containing a filler means that the filler content is less than 0.1% by mass of the total solid content of the permeation prevention layer, preferably 0.01% by mass or less, and more preferably 0% by mass (no filler).

The thickness t0 of the permeation preventing layer is preferably 0.1 to 10.0 μm, and more preferably 0.5 to 5.0 μm.
By setting t0 to 0.1 μm or more, it is possible to easily suppress the uncured curable resin composition contained in the ink for forming the first cured product layer from permeating into the substrate side. Also, by setting t0 to 10.0 μm or less, it is possible to stably form a permeation prevention layer without affecting other regions.

--First hardened layer--
The first cured material layer is formed on at least a part of the permeation prevention layer, and has a releasable surface. Since the first cured material layer has a releasable surface, most of the second cured material layer on the first cured material layer is peeled off. It is preferable that the second cured material layer on the first cured material layer is completely peeled off from the viewpoint of improving the three-dimensional effect due to the surface unevenness, but there are many cases where the second cured material layer cannot be completely peeled off from the first cured material layer. Therefore, a small amount of the second cured material layer may remain on the first cured material layer as long as it does not impair the effects of the present invention.
By forming the first hardened material layer on the permeation prevention layer, the thickness of the first hardened material layer can be ensured, and thus the thickness of the second hardened material layer in the second region can be increased, making it easier to improve the abrasion resistance of the decorative material.
The first cured material layer is preferably formed in accordance with the pattern of the permeation preventing layer. For example, when the total area of the first cured material layer in a plan view of the decorative material is taken as 100, the area of the first cured material layer present on the permeation preventing layer is preferably 90 or more, more preferably 95 or more, even more preferably 97 or more, and even more preferably 99 or more.

The thickness t1 of the first cured product layer is preferably more than 3.5 μm and not more than 30.0 μm, more preferably 5.0 μm or more and 25.0 μm or less, and even more preferably 7.0 μm or more and 20.0 μm or less.
By making t1 greater than 3.5 μm, even if the thickness of the second cured material layer is increased, it is possible to suppress cohesive failure of the second cured material layer in the first region R1 when peeling the second cured material layer from the first region R1 (see step (8) described below). In other words, by making t1 greater than 3.5 μm, it is possible to increase the thickness of the second cured material layer, and as a result, it is possible to easily improve the abrasion resistance of the decorative material.
Furthermore, by setting t1 to 30.0 μm or less, the first cured product layer can be formed stably.

The first cured product layer is a layer formed from a curable resin, more specifically, a layer formed from a cured product of an uncured curable resin composition.
As the curable resin, from the viewpoint of obtaining a design with a higher quality texture and more excellent surface characteristics, thermosetting resins and ionizing radiation curable resins are preferred, and ionizing radiation curable resins are more preferred.

Preferred examples of the thermosetting resin include the same as those exemplified as the thermosetting resin that can be impregnated into the substrate.
Preferred examples of the ionizing radiation curable resin include the same resins as those exemplified for the permeation preventing layer.

The first cured material layer preferably contains a release agent. By containing a release agent, even if another resin is laminated on the surface of the releasable ink decoration layer (the surface of the first cured material layer), it can be peeled off, while the other resin adheres to the second region and is not peeled off, making it easier to impart an elevation difference between the first region and the second region.

Examples of the release agent include fluorine-based release agents and silicone-based release agents. From the viewpoint of obtaining a design with a higher quality texture, silicone-based release agents are preferred.
Examples of silicone-based release agents include those having a polysiloxane structure as a basic structure, and among them, modified silicone oils having an organic group introduced at least in one of the side chain and the end are preferred, and modified silicone oils having an organic group introduced at both ends are more preferred.As the organic group, from the viewpoint of obtaining a design with a higher texture, reactive functional groups such as (meth)acrylic groups, amino groups, epoxy groups, mercapto groups, carbinol groups, phenol groups, and carboxyl groups, and non-reactive functional groups such as polyether groups, aralkyl groups, fluoroalkyl groups, alkyl groups, fatty acid amide groups, and phenyl groups are preferred.Among them, reactive functional groups are preferred, and (meth)acrylic groups are particularly preferred, that is, (meth)acrylic modified silicone oils are particularly preferred.In addition, these organic groups may have substituents such as nitrogen atoms, sulfur atoms, hydroxyl groups, and alkyl groups.

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 even more preferably 1 to 2 parts by mass, relative to 100 parts by mass of the curable resin that forms the first cured material layer. When the content of the release agent is within the above range, the effect of adding the release agent can be efficiently obtained.

The first cured material layer preferably contains an inorganic filler. By containing an inorganic filler in the first cured material layer, the surface of the first region can be roughened, which makes it easier to improve the visual three-dimensional effect of the decorative material.
Examples of the inorganic filler include particles made of inorganic materials such as oxides such as aluminum oxide, magnesium oxide, silica, calcium oxide, titanium oxide, zinc oxide, and zirconia oxide, hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide, carbonates such as magnesium carbonate and calcium carbonate, 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 preferred, and silica is particularly preferred.

The average particle size of the inorganic filler is preferably 0.3 to 20 μm, more preferably 0.5 to 10 μm, from the viewpoint of making it easier to set Ra1 within the range described below. In this specification, the average particle size of the filler is a value measured by a laser diffraction scattering method.

From the viewpoint of making it easier to set Ra1 within the range described below, the content of the inorganic filler is preferably 1 to 50 parts by mass, more preferably 10 to 40 parts by mass, and even more preferably 20 to 35 parts by mass, relative to 100 parts by mass of the curable resin that forms the first cured product layer. When the content of the inorganic filler is within the above range, the effect of adding the inorganic filler can be efficiently obtained.

-First decorative layer-
The decorative material of the present invention preferably has a first decorative layer in at least a portion between the substrate and the permeation preventing layer in a location corresponding to the first region.

The first decorative layer may be formed in any pattern within the first region, the pattern being determined depending on the design desired to be imparted to the entire decorative material.
For example, when the design to be applied to the entire decorative material is a wood pattern, the first decorative layer is preferably formed with one or more patterns selected from vessels, autumn wood, and knots. In other words, the first region is preferably formed with one or more patterns selected from vessels, autumn wood, and knots of wood. Vessels are cylindrical cells that serve as a passage for moisture, and when minute vessels are arranged, a dark pattern appears to be formed along the arrangement to the human eye. Autumn wood is a narrow grain width and dark color part formed from summer to autumn. Note that the wide grain width part formed from spring to summer is called spring wood, and the spring wood and autumn wood are alternately repeated to form the annual rings of wood. Knots are traces of branches that have been incorporated into the trunk, and are circular or nearly elliptical in shape and darker in color than the surrounding tissue.
In addition, when the design to be imparted to the entire decorative material is a stone pattern such as travertine, the first decorative layer is preferably a recessed pattern. In other words, the first region is preferably formed with a stone recessed pattern.
In addition, when the design to be imparted to the entire decorative material is a tile pattern or a brick pattern, the first decorative layer preferably has a joint pattern. In other words, the first region preferably has a tile or brick joint pattern formed thereon.
By providing the design by the first decorative layer as described above, the first region becomes easily visible as a recess, and the visual three-dimensional effect can be improved.

The first decorative layer can be formed, for example, by printing using a first decorative layer forming ink containing a colorant and a binder resin.

Examples of the colorant for the first decorative layer include inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, red iron oxide, cadmium red, ultramarine blue, cobalt blue, etc., organic pigments such as quinacridone red, isoindolinone yellow, phthalocyanine blue, etc., or dyes, etc. It is preferable that the colorant for the first decorative layer does not contain a luster pigment.
The binder resin of the first decorative layer is not particularly limited, and examples thereof include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, cellulose derivatives, rubber resins, and the like.

The thickness of the first decorative layer can be adjusted appropriately within the range of approximately 0.1 to 20 μm, taking into account the desired design.

- Surface shape -
The arithmetic mean roughness Ra of the surface of the first region according to JIS B0601:1994 at a cutoff value of 0.8 mm is preferably 1.0 to 5.0 μm, and more preferably 1.0 to 3.0 μm.
By making the Ra of the first region 1.0 μm or more, it is possible to make the first region appear concave. Also, by making the Ra of the first region 5.0 μm or less, it is possible to prevent the first region from appearing whitish, and it is possible to easily improve the design.

The Ra of the first region can be adjusted, for example, by roughening the substrate or by roughening a layer formed on the substrate (such as the first hardened material layer described below).

Second Zone
The second region is a region that is visually recognized as being higher than the first region.
The second region has a second cured material layer on the substrate.

--Second hardened layer--
The second cured product layer is a layer formed from a curable resin, more specifically, a layer formed from a cured product of an uncured curable resin composition.

As the curable resin of the second cured material layer, from the viewpoint of obtaining a design with a higher texture, a thermosetting resin or an ionizing radiation curable resin is preferably mentioned, and a thermosetting resin is more preferable. These curable resins may be used alone or in combination of two or more kinds, for example, a thermosetting resin and an ionizing radiation curable resin may be used in combination, or these curable resins may be used in combination with a thermoplastic resin.
As the thermosetting resin, the same ones as those exemplified as the thermosetting resin that can be impregnated into the substrate can be preferably exemplified, and the above-mentioned various thermosetting resins are also preferred, and it is also the same that melamine resins are particularly preferred. By using such a curable resin, a design with a higher texture can be obtained, and adhesion to the substrate can be improved, resulting in better mechanical strength. As the ionizing radiation curable resin, the same ones as those exemplified for the penetration prevention layer can be used.
When a curable resin and a thermoplastic resin are used in combination, the content of the curable resin relative to the total of these resins is usually about 50 mass % or more and less than 100 mass %, and preferably 60 mass % or more and 90 mass % or less.

It is preferable that the second hardened material layer does not contain particles in order to reduce diffusion.

The thickness t2 of the second cured product layer is preferably 5.0 μm or more and 50.0 μm or less, more preferably 10.0 μm or more and 40.0 μm or less, and even more preferably 25.0 μm or more and 35.0 μm or less.
By setting t2 to 5.0 μm or more, the abrasion resistance of the decorative material can be easily improved. Also, by setting t2 to 50.0 μm or less, stable production is possible.

-Second decorative layer-
The second decorative layer can be formed, for example, by printing using a second decorative layer forming ink that contains a colorant and a binder resin.
Examples of the colorant and binder resin of the second decorative layer include the colorants and binder resins exemplified for the first decorative layer described below.

The second decorative layer may be formed, for example, in any desired pattern on the substrate.
The arbitrary pattern varies depending on the design to be imparted. For example, the arbitrary pattern is preferably a wood grain pattern (parts other than the vessel groove pattern and/or knot pattern) when a wood grain pattern is to be imparted to the entire decorative material, is preferably a pattern other than the recessed parts when a stone pattern such as travertine is to be imparted to the entire decorative material, and is preferably a tile or brick part when a tile or brick pattern is to be imparted to the entire decorative material.

The thickness of the second decorative layer can be adjusted appropriately within the range of approximately 0.1 to 20 μm, taking into account the desired design.

- Surface shape -
The arithmetic mean roughness Ra of the surface of the second region according to JIS B0601:1994 at a cutoff value of 0.8 mm is preferably 2.0 μm or less, and more preferably 0.5 to 1.5 μm.

<Reinforcing layer>
The decorative material of the present invention preferably has a reinforcing layer on the surface of the substrate opposite to the surface having the permeation-preventing layer in order to reinforce the decorative material.
In particular, when a fiber substrate or paper substrate impregnated with a thermosetting resin is used as the substrate, by combining a reinforcing layer, a thermosetting resin decorative board having superior mechanical properties can be obtained.

The reinforcing layer may be a sheet impregnated with a thermosetting resin.
The type of fiber substrate and paper substrate used in the thermosetting resin-impregnated sheet is not particularly limited as long as it is one of the examples of the fiber substrate and paper substrate of the substrate, and the basis weight is preferably 100 to 300 g/m ² , more preferably 150 to 250 g/m ^2. The thermosetting resin can be any resin that can be impregnated into the substrate in the form of a thermosetting resin composition, and is preferably a phenolic resin. That is, the reinforcing layer is preferably a phenolic resin-impregnated paper.
As the phenol resin-impregnated paper, for example, one produced by impregnating craft paper having a basis weight of 150 to 250 g/ ^m2 with phenol resin to an impregnation rate of about 20 to 60% and drying at about 100 to 140°C is preferably used.

<Primer layer>
In the decorative material of the present invention, a primer layer can be provided between each of the layers in order to improve the adhesion between the layers.
Examples of the resin material for forming the primer layer include urethane resin, polyester resin, acrylic resin, acrylic urethane resin, vinyl chloride-vinyl acetate copolymer resin, etc. The thickness of the primer layer is usually about 0.1 to 15 μm, preferably 1 to 10 μm, from the viewpoint of efficiently obtaining excellent adhesion.

<Adherend>
The decorative material of the present invention may be formed by laminating and integrating an adherend onto the back surface of a substrate (the surface of the substrate opposite to the surface having the permeation-preventing layer).

The substrate may be, for example, wood boards such as wood veneer, wood plywood, particle board, MDF (medium density fiberboard), laminated lumber, etc.; gypsum-based boards such as gypsum boards and gypsum slag boards; cement boards such as calcium silicate boards, asbestos slate boards, lightweight foamed concrete boards, and hollow extruded cement boards; fiber cement boards such as pulp cement boards, asbestos cement boards, and wood chip cement boards; ceramic boards such as pottery, porcelain, earthenware, glass, and enamel; metal boards such as iron boards, galvanized steel boards, polyvinyl chloride sol-coated steel boards, aluminum boards, and copper boards; polyolefin resin boards, acrylic resin boards, ABS boards, poly Examples of such resins include thermoplastic resin plates such as carbonate plates; thermosetting resin plates such as phenolic resin plates, urea resin plates, unsaturated polyester resin plates, polyurethane resin plates, epoxy resin plates, and melamine resin plates; and so-called FRP plates obtained by impregnating and curing a resin such as phenolic resin, urea resin, unsaturated polyester resin, polyurethane resin, epoxy resin, melamine resin, and diallyl phthalate resin into a glass fiber nonwoven fabric, cloth, paper, or other various fibrous base material. These may be used alone, or two or more of these may be laminated together to form a composite substrate.

There are no particular limitations on the method of laminating the substrate and various adherends, and it is possible to employ a method in which, for example, a sheet is attached to the adherend with an adhesive. The adhesive may be appropriately selected from known adhesives depending on the type of adherend, etc. Examples include polyvinyl acetate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ionomer, etc., as well as butadiene-acrylonitrile rubber, neoprene rubber, natural rubber, etc.

<Applications>
The decorative material of the present invention is used, for example, for tops of various counters and desks, furniture, cabinets for kitchen products, building materials for homes such as doors, etc. Among these, members used in locations including horizontal surfaces such as tops used for counters and desks, etc., are preferred in that they are more likely to exhibit the effects of the decorative board of the present invention than members used on vertical surfaces because they require a visual three-dimensional effect and are also required to be abrasion resistant since they are rubbed by various items such as clothing, cleaning supplies, and watches.

[Method of manufacturing cosmetic material]
The decorative material of the present invention can be produced, for example, by the following steps (1) to (8).
(1) A step of preparing a substrate.
(2) A step of forming a permeation prevention layer on a portion of the substrate.
(3) A step of obtaining a laminate A by forming a first cured material layer having a releasable surface on at least a portion of the permeation prevention layer.
(4) A step of impregnating the laminate A with a curable resin composition to form an uncured curable resin composition layer on the entire surface of the side of the laminate A having the permeation prevention layer, thereby obtaining a laminate B.
(5) A step of obtaining a laminate C by disposing a release film on the uncured curable resin composition layer side of the laminate B.
(6) A step of hot pressing both sides of the laminate C between mirror plates to form a second cured material layer by curing the uncured curable resin composition layer.
(7) A step of removing the laminate C from between the mirror plates.
(8) A process in which, when peeling and removing the release film from the laminate C, the second cured material layer on the first cured material layer of the second cured material layer is removed together with the release film, thereby forming a concave first region and a second region in which the second cured material layer remains.

Step (1) is a step of preparing a substrate 10 .
Step (2) is a step of forming a permeation prevention layer 31 on a part of the substrate 10 (FIG. 2). The curable resin composition used to form the permeation prevention layer is preferably cured at this stage.

When the decorative material 100 has a first decorative layer 33 and/or a second decorative layer 23, it is preferable to have a step of forming the first decorative layer 33 and/or the second decorative layer 23 between steps (1) and (2) (Figure 2).

Step (3) is a step of obtaining a laminate A (71) by forming a first cured material layer 32 having a releasable surface on a part of the permeation prevention layer 31 ( FIG. 3 ). The curable resin composition used to form the first cured material layer 32 is preferably cured at this stage.
The area where the first hardened material layer 32 is formed on the permeation-preventing layer 31 corresponds to the first region R1 of the decorative material obtained by the manufacturing method of the present invention.

Step (4) is a step of impregnating the laminate A with a curable resin composition to form an uncured curable resin composition layer 22a on the entire surface of the side of the laminate A having the permeation prevention layer 31, thereby obtaining a laminate B (72) (Figure 4).
During the step (4), the substrate 10 can be impregnated with the curable resin composition.

Step (5) is a step of obtaining a laminate C (73) by disposing a release film 80 on the uncured curable resin composition layer 22a side of the laminate B (FIG. 5).
The release film 80 has a role of removing the second cured material layer on the first cured material layer 32 having a releasable surface, among the second cured material layers obtained by curing the uncured curable resin composition layer 22a, in the step (7) described below. That is, when the adhesive strength between the release film 80 and the second cured material layer is A1, and the adhesive strength between the second cured material layer and the layer located on the substrate 10 side of the cured material layer (the first cured material layer 32 in the first region R1, and the second decorative layer 23 or the substrate 10 in the second region R2) is A2, the material of the release film 80 is not particularly limited as long as it satisfies the relationship of A1>A2 in the first region R1 and A1<A2 in the second region R2.

Examples of the release film 80 include a single layer of a sheet of various resins such as polyester resins such as polyethylene terephthalate and polybutylene terephthalate; polyolefin resins such as polyethylene and polypropylene; and acrylic resins, or a resin layer formed on one of these resin sheets.

When the decorative material 100 has a reinforcing layer 60, in step (5), it is preferable to place the reinforcing layer 60 on the substrate 10 side of the laminate B.

Step (6) is a step of hot pressing the laminate C (73) with both sides of the laminate C (73) sandwiched between mirror plates to form a second cured material layer 22 by curing the uncured curable resin composition layer 22a.
During step (6), the curable resin composition impregnated in the substrate 10 can also be cured.

The heat pressing conditions can be adjusted appropriately depending on the type of thermosetting resin used, and there are no particular restrictions, but typically the temperature conditions are 100 to 200°C, the pressure is 0.1 to 9.8 MPa, and the time is 10 seconds to 120 minutes.

Step (7) is a step of removing the laminate C from between the mirror plates.
In step (8), when the release film 80 is peeled off from the laminate C, the second cured material layer on the first cured material layer 32 of the second cured material layer is removed together with the release film 80, thereby forming a concave first region R1 and a second region R2 in which the second cured material layer 22 remains ( FIG. 1 ).
In the method for producing a decorative material of the present invention, the thickness of the first hardened material layer can be increased by having a permeation prevention layer. Therefore, even if the thickness of the second hardened material layer is increased, the second hardened material layer on the first region R1 can be peeled off cleanly in step (8) without cohesive failure.

Next, the present invention will be described in more detail using examples, but the present invention is not limited to these examples in any way.

1. Evaluation 1-1. Abrasion resistance The abrasion resistance of the decorative materials obtained in the examples and comparative examples was evaluated in accordance with "6.2 Abrasion resistance B method" of JIS K6902:2008 using a product name "Rotary Abrasion Tester" manufactured by Toyo Seiki Seisakusho Co., Ltd. The abrasion resistance of the decorative materials obtained in the examples and comparative examples was evaluated in accordance with "6.2 Abrasion resistance B method" of JIS K6902:2008. The abrasive material used was abrasive paper "Product number: S-42, 3M company" conforming to JIS R6252. The number of rotations of the rotating disk when 50% of the printed pattern of the decorative material was erased is shown in Table 1.

1-2. Peelability of the second cured material layer The peelability of the second cured material layer was visually evaluated for the decorative materials obtained in the Examples and Comparative Examples. Those in which no second cured material layer remained on the first region were rated "A," and those in which the second cured material layer underwent cohesive failure on the first region when the release film was peeled off, leaving the second cured material layer in part on the first region, were rated "C." The results are shown in Table 1.

The cosmetic materials obtained in the Examples and Comparative Examples were visually evaluated by 20 random adults under fluorescent lighting to determine whether or not they had a three-dimensional effect. The results are shown in Table 1.
A: 18 or more people answered that it has a highly three-dimensional design.
B: 15 to 17 people answered that it has a highly three-dimensional design.
C: 14 or less people answered that the design has a high three-dimensional effect.

2. Preparation of decorative material [Example 1]
A first decorative layer (vascular portion of the wood grain) and a second decorative layer (wood grain surface portion) having a thickness of 3 μm were formed on a substrate (titanium paper base paper for building materials, product name "PM-67P" manufactured by KJ Specialty Paper Co., Ltd., basis weight: 80 g/m ² , thickness: 100 μm) by gravure printing using printing ink ("Ode SPTI" manufactured by DIC Graphics Corporation).
Next, the following curable resin composition for forming a permeation prevention layer was printed on the first decorative layer, and cured by irradiating with an electron beam (voltage applied: 165 KeV, 3 Mrad (30 kGy)) to form a permeation prevention layer having a thickness t0 of 1.0 μm.
Next, the following curable resin composition for forming a first cured material layer was printed on the permeation preventing layer, and cured by irradiation with an electron beam (applied voltage: 165 KeV, 3 Mrad (30 kGy)), to obtain a laminate A having a first cured material layer with a thickness t1 of 10.0 μm.
Next, the laminate A was impregnated with the curable resin composition for forming the second cured material layer described below, and dried to obtain a laminate B (impregnation was performed so that the amount of the cured resin composition when dried was 80 g/ ^m2 ).
Next, the following release film was laminated on the surface of Laminate B opposite the substrate (the surface having the uncured second cured material layer), and a reinforcing layer (three sheets of phenolic resin-impregnated core paper (Ohta Core, manufactured by Ohta Sangyo Co., Ltd.) having a basis weight of 245 g/ ^m2 obtained by impregnating craft paper with a liquid uncured resin composition made of phenolic resin) was laminated on the surface of Laminate B facing the substrate, thereby obtaining Laminate C.
Next, both sides of the laminate C were sandwiched between mirror plates (the mirror plate was placed on the reinforcing layer side, and the embossed plate was placed on the release film side), and heat-pressure molding was performed using a hot press at a molding temperature of 150° C. and a molding pressure of 100 kg/cm ² for 10 minutes. After molding, the laminate C was removed from between the two mirror plates, and the release film was peeled off from the laminate C to obtain the decorative board of Example 1.
When the release film was peeled off and removed from the laminate C, the second cured material layer on the first cured material layer was removed together with the release film, forming a concave first region. Also, a second region in which the second cured material layer remained was formed in a portion not having the first cured material layer.
The decorative material of Example 1 had a thickness t0 of 1.0 μm, t1 of 10.0 μm, and t2 of 30 μm. The ratio (S2/S1) of the area S1 of the first region to the area S2 of the second region was approximately 5.0.

<Curable resin composition for forming permeation prevention layer>
Hexafunctional acrylate oligomer 90 parts by weight Cellulose polymer 10 parts by weight Dilution solvent appropriate amount

<Curable resin composition for forming first cured product layer>
The following components were stirred for 1 hour at 2000 rpm using a process homogenizer (manufactured by SMT Corporation, "PH91") to obtain a resin composition.
Ionizing radiation curable resin (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, trade name "Aronix M400" manufactured by Toagosei Co., Ltd.) 60 parts by mass Silicone-based release agent (organopolysiloxane modified with methacryloyloxyalkyl at both ends, trade name "X-22-164B" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.9 parts by mass Silane coupling-treated silica 18 parts by mass (average particle size 3.0 μm)
Methyl ethyl ketone 40 parts by mass

<Curable resin composition for forming second cured product layer>
Melamine formaldehyde resin 60 parts by weight Water 35 parts by weight Isopropyl alcohol 5 parts by weight

<Preparation of Release Film>
The following ionizing radiation curable resin composition was applied to the adhesive surface of a 50 μm thick polyethylene terephthalate film (manufactured by Toyobo Co., Ltd. under the trade name "Cosmoshine A4100") and cured by irradiation with an electron beam (applied voltage: 165 KeV, 5 Mrad (50 kGy)) to form a 5 μm thick cured layer, and a release film was obtained.
<<Ionizing radiation curable resin composition>>
Ionizing radiation curable resin (trimethylolpropane triacrylate modified with ethylene bottom oxide, trade name "Aronix M350" manufactured by Toagosei Co., Ltd.) 100 parts by mass Silicone-based release agent (organopolysiloxane modified with methacryloyloxyalkyl at both ends, trade name "X-22-164B" manufactured by Shin-Etsu Chemical Co., Ltd.) 2 parts by mass Silica particles (Fuji Silysia Chemical Ltd. trade name "Silisia 450", average particle size: 5.2 μm) 8 parts by mass Ethyl acetate 50 parts by mass

[Examples 2 to 4]
The decorative materials of Examples 2 to 4 were obtained in the same manner as in Example 1, except that t0, t1, and t2 were changed to the values shown in Table 1.

[Comparative Example 1]
Except for not forming a permeation prevention layer and forming a first hardened material layer on the first decorative layer, the decorative material of Comparative Example 1 was obtained in the same manner as in Example 1. The reason why the t1 of the decorative material of Comparative Example 1 is smaller than that of Example 1 is that in Comparative Example 1, the material for forming the first hardened material layer permeated into the substrate.

[Comparative Example 2]
A decorative material of Comparative Example 2 was obtained in the same manner as Comparative Example 1, except that t1 and t2 were changed to the values shown in Table 1.

From the results in Table 1, it can be confirmed that the decorative materials of Examples 1 to 4 have a visual three-dimensional effect and are excellent in abrasion resistance.
In addition, since t1 was small in Comparative Example 1, when the second cured material layer was peeled off from the first region R1, the second cured material layer underwent cohesive failure within the first region, and the second cured material layer remained in the first region, resulting in a small step between the first region and the second region.

Reference Signs List 10: Substrate 20: Second region forming layer 22: Second cured material layer 22a: Curable resin composition layer 23: Second decorative layer 30: First region forming layer 31: Permeation preventing layer 32: First cured material layer 33: First decorative layer 60: Reinforcing layer 71: Laminate A
72: Laminate B
73: Laminate C
80: Release film 100: Decorative material

Claims (8)

A decorative material having a substrate selected from a paper substrate and a fiber substrate,
The decorative material has a first region and a second region in a plane,
The decorative material in a portion corresponding to the first region has, on the base material, a permeation preventing layer and a first cured material layer having a releasable surface, in this order;
The decorative material in a portion corresponding to the second region has a second cured product layer on the base material,
The permeation prevention layer contains a hardening resin and a cellulose resin,
the permeation preventing layer is formed on a portion of the substrate, and when the total area of the permeation preventing layer when the decorative material is viewed in a plan view is taken as 100, the area of the permeation preventing layer present in the first region is 90 or more;
A decorative material, wherein when the thickness of the permeation preventing layer is defined as t0, the thickness of the first hardened material layer is defined as t1, and the thickness of the second hardened material layer is defined as t2, the relationship of t0+t1<t2 is satisfied. The decorative material according to claim 1, wherein the permeation prevention layer contains an ionizing radiation curable resin. The cosmetic material according to claim 1 or 2, in which t1 is greater than 3.5 μm and less than or equal to 30.0 μm. The decorative material according to any one of claims 1 to 3, in which t2-(t0+t1) is 2.0 μm or more and 50.0 μm or less. The decorative material according to any one of claims 1 to 4, wherein the decorative material in the area corresponding to the first region has a first decorative layer at least in a portion between the base material and the permeation prevention layer. The decorative material according to any one of claims 1 to 5, wherein the decorative material in the area corresponding to the second region has a second decorative layer at least in a portion between the substrate and the second cured material layer. The decorative material according to any one of claims 1 to 6, wherein the first cured material layer contains a release agent. The decorative material according to any one of claims 1 to 7, wherein the second cured material layer contains a melamine resin.

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