JP6736844B2 - Decorative sheet and veneer - Google Patents

Description

The present invention relates to a resin decorative sheet and decorative plate. In particular, the present invention relates to a decorative sheet having excellent cleanability, which can be used as a floor material or its periphery by being attached to a base material such as a wood-based material, and a decorative plate thereof.

Decorative sheets have been developed and have been developed in the process of housing construction as an industry. It can be said that prefabricated buildings have played a leading role in apartments, condominiums, and individual houses, which are housing complexes.
Since ancient times, houses used materials that depend on local characteristics such as wood and stone, and people's homes had a style that was rooted in a unique culture.However, with the development of the housing industry, industrialization progressed, and the conversion from natural materials to artificial materials Has been done. Further, in recent years, the heavy use of high-grade wood and stone materials may lead to deforestation and environmental problems, which is one of the factors that increase the demand for decorative sheets.

For example, in recent years, a so-called sheet flooring material in which a decorative sheet is attached to the surface of a wood base material such as plywood, MDF (medium fiber version) or particle board has been widely used as a floor material (Patent Document 1). reference).
Also, after the completion of the interior decoration work for apartments, condominiums, and private houses, there will be room cleaning by the management company and beautifying companies. Gypsum board, putty such as putty, dust, etc. scattered on the floor are wiped and cleaned using water or detergent.
When wiping and cleaning the sheet flooring floor material, if the dry wiping property after wiping with water is heavy or if unevenness is apt to occur during wiping, there may occur a problem that it takes time to clean.

Japanese Patent No. 5045180

The present invention has been made in view of the above points, the lightness of the wiping property at the time of cleaning, has the visibility of uneven wiping, and a decorative sheet having excellent cleaning properties as a cosmetic material and The purpose is to provide a veneer.

In order to solve the problem, the decorative sheet which is one embodiment of the present invention has a pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer formed in this order on a resin-made base sheet, At least the outermost layer located on the outermost surface of the surface protective layer contains silicone beads and an ionizing radiation curable resin, and has a 60-degree specular gloss of 5 or more and 35 or less in accordance with JIS Z 8741. ..

According to the aspect of the present invention, it is possible to provide a decorative sheet that easily wipes off gypsum board, adhesive, putty, and other debris and dust that accumulate during indoor construction, and that has a cleanability as a decorative material.

It is a figure explaining the cross-sectional schematic diagram of the decorative sheet which concerns on embodiment based on this invention.

Embodiments of the present invention will be described below with reference to the drawings.
In the present embodiment, the decorative sheet and decorative plate for the floor will be described as an example, but the decorative sheet and decorative plate used for other parts may be used.
Here, the drawings are schematic, and the relationship between the thickness and the plane dimension, the thickness ratio of each layer, and the like are different from the actual ones. In addition, the embodiments described below exemplify a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the constituent parts are as follows. It is not specific to one. Various changes can be added to the technical idea of the present invention within the technical scope defined by the claims described in the claims.

As shown in FIG. 1, the decorative sheet 10 of the present embodiment has a pattern layer 2, a transparent adhesive layer 3, a transparent thermoplastic resin layer 4, and a surface protective layer 7 on a resin base sheet 1. It is formed by sequentially stacking. The present embodiment is an example in which the surface protective layer 7 is composed of two layers, a first surface protective layer 5 and a second surface protective layer 6.
A backside resin coat layer 8 made of a resin layer is provided on the surface (backside) of the base sheet 1 opposite to the pattern layer 2.

[Veneer]
Further, the decorative board 20 is configured by laminating the decorative sheet 10 on a base material 11, as shown in FIG.
[Base material 11]
As the base material 11, South Sea wood plywood, particle board, medium density fiberboard (hereinafter MDF), and ordinary plywood specified in Japanese Agricultural Standards can be used. Further, a base material made of an olefin resin added with wood powder can also be used. The thickness of the base material 11 is preferably about 3 to 25 mm. The base material 11 may be a metal plate such as aluminum or a composite plate made of metal.

[Base material sheet 1]
The resin base sheet 1 is made of, for example, a colored thermoplastic resin. As the thermoplastic resin, for example, vinyl chloride resin, acrylic resin, polyolefin-based polypropylene resin or polyethylene resin can be used. Of these, polyolefin resins can be preferably used in view of environmental compatibility, processability, and price. In addition, the grade and composition of the resin can be selected in consideration of ease of sheeting, printability and suitability for bending.

When the base material sheet 1 is colored, the base material to which the decorative sheet 10 is attached can be hidden, and the hue can be appropriately selected as the base color of the pattern layer 2. For example, coloring can be performed by mixing and kneading a colorant such as a pigment during sheeting of the thermoplastic resin. Alternatively, a colored layer may be provided as a solid ink layer before providing the pattern layer 2 by using a coating or printing method under the pattern layer 2.

[Pattern layer 2]
The picture pattern layer 2 can be provided using a known printing method. When the base material sheet 1 can be prepared in a wound state, printing for forming the pattern layer 2 can be performed by a roll-to-roll printing device. The printing method is not particularly limited, but if productivity and the quality of the pattern are taken into consideration, for example, the gravure printing method can be used.

As the design pattern, any design pattern may be adopted in consideration of the design as a flooring material, and in the case of wood-based design, various wood grain is often used. Can also be For example, if it is an image of a floor of a stone material such as marble, it may be used as a pattern pattern such as marble stones. Further, in addition to the picture patterns of natural materials, artificial picture patterns such as artificial picture patterns and geometric patterns using them as motifs can also be used.

The printing ink is not particularly limited, but an ink corresponding to the printing method can be appropriately selected. In particular, it is preferable to select it in consideration of adhesion to the resin base sheet 1, printability, and weather resistance as a floor material.
In addition, if necessary, an adhesive layer (non-adhesive layer) is formed on the pattern pattern layer 2 for the purpose of improving the adhesiveness between the pattern pattern layer 2 and the transparent adhesive layer 3, and between the transparent adhesive layer 3 and the transparent thermoplastic resin layer 4. (Illustration) may be provided. The resin used for this adhesive layer (not shown) is not particularly limited, but, for example, a two-component curing type urethane resin or the like can be used, and can be provided by using, for example, a coating device or a gravure printing device.

[Transparent adhesive layer 3]
The transparent adhesive layer 3 is provided for the purpose of strengthening the adhesion between the base sheet 1 and the pattern layer 2 and the transparent thermoplastic resin layer 4. By virtue of this strong adhesion, it is possible to give the decorative sheet 10 bendability that follows a curved surface or a right-angled surface.
[Transparent thermoplastic resin layer 4]
For the transparent thermoplastic resin layer 4, for example, vinyl chloride resin, acrylic resin, polyolefin-based polypropylene resin or polyethylene resin, or the like can be used. Of these, polyolefin resins can be preferably used in view of environmental compatibility, processability, and price.

In addition, the grade and composition of the resin can be selected in consideration of ease of sheeting, printability and suitability for bending. In particular, in terms of bending workability, it is important to select in consideration that whitening or cracking of the bent portion does not occur.
The transparent adhesive layer 3 and the transparent thermoplastic resin layer 4 can be formed, for example, by co-extruding both.
By the transparent thermoplastic resin layer 4, the decorative sheet 10 has an effect of having a thickness and a depth in design, and can also improve weather resistance and abrasion resistance of the decorative sheet 10.

[Surface protection layer 7]
A surface protection layer 7 is provided on the transparent thermoplastic resin layer 4. The surface protective layer 7 may be a single layer, or a plurality of layers may be stacked to form the surface protective layer 7. In the decorative sheet 10 of the present embodiment, as shown in FIG. 1, as the surface protective layer 7, two layers of a first surface protective layer 5 and a second surface protective layer 6 are provided. The surface protective layer 7 may be composed of one layer. In this case, the second surface protective layer 6 becomes the surface protective layer 7.

In order to provide the surface protective layer 7 composed of the first surface protective layer 5 and the second surface protective layer 6, the respective layers are formed by known coating devices, heat drying devices, and ultraviolet irradiation devices depending on the type of curable resin. Can be used for coating and curing of the coating film.
The surface protective layer 7 plays an important role in determining the superiority and inferiority of bending workability, scratch resistance, and cleanability. The surface protective layer 7 contains a curable resin as a main component. That is, it is preferable that the resin component is substantially composed of a curable resin. Substantially means, for example, 80 parts by mass or more when the entire resin is 100 parts by mass. The surface protective layer 7 may contain a weathering agent, a plasticizer, a stabilizer, a filler, a dispersant, a dye, a colorant such as a pigment, a solvent, or the like, if necessary.

Irregularities may be formed on the surface of the surface protective layer 7 in order to impart a given design property. Usually, an uneven pattern is formed by embossing. The embossing method is not particularly limited. A known sheet-fed or rotary embossing machine is used for the embossing. Examples of the concavo-convex shape include a wood grain board conduit groove, a stone board surface irregularity (granite cleaved surface, etc.), a cloth surface texturer, a satin finish, a sand grain, a hairline, a line groove, etc.

[Second surface protective layer 6]
The second surface protective layer 6 is the outermost layer located on the outermost surface of the surface protective layer 7. The second surface protective layer 6 contains silicone beads and ionizing radiation curable resin. Further, the second surface protective layer 6 is added with a matting agent such as silica in order to adjust the 60-degree specular gloss to a desired gloss.

The second surface protective layer 6 may further contain a thermosetting resin. However, even in this case, the content ratio of the curable resin is 50% or more of the total amount of the ionizing radiation curable resin.
Here, it is important to make a selection especially in consideration of cleanability. As a result of intensive studies on this point, we were able to find the following findings.
That is, the main component of the second surface protective layer 6, which is the outermost layer of the surface protective layer 7, is a mixture of an ultraviolet curable resin and a thermosetting resin, so that scratch resistance when used for a floor is satisfied. At the same time, it was found that whitening and cracking of the surface protective layer 7 are less likely to occur during bending.

From this knowledge, it is preferable that at least the second surface protective layer 6, which is the outermost layer, of the surface protective layer 7 is made of a mixture of an ultraviolet curable resin and a thermosetting resin. Of course, other additives may be appropriately added to the mixture. In particular, the mixing ratio of the ultraviolet curable resin and the thermosetting resin is set to be in the range of 7:3 to 9:1 by mass ratio, that is, the ultraviolet curable resin is 80 to 90% in the mixture. It is the mass, and the thermosetting resin is preferably 10 to 20% by mass. The above-mentioned main component refers to, for example, 70% or more of the total amount of the mixture of the ultraviolet curable resin and the thermosetting resin.
In this way, the main component of the second surface protective layer 6 corresponding to the outermost layer of the surface protective layer 7 is a mixture of the ultraviolet curable resin and the thermosetting resin, so that the scratch resistance when used for the floor is improved. At the same time, the surface protection layer 7 is less likely to be whitened or cracked during bending.

[Ionizing radiation curable resin]
Here, the ionizing radiation curable resin is not particularly limited, and a prepolymer (including an oligomer) and/or a radically polymerizable double bond in the molecule capable of undergoing a polymerization and crosslinking reaction by irradiation with ionizing radiation such as ultraviolet rays or electron beams, and/ Alternatively, a transparent resin containing a monomer as a main component can be used. These prepolymers or monomers may be used alone or in combination of two or more. The curing reaction is usually a crosslinking curing reaction.

Specifically, the prepolymer or the monomer is a compound having a (meth)acryloyl group, a radically polymerizable unsaturated group such as a (meth)acryloyloxy group, or a cationically polymerizable functional group such as an epoxy group in the molecule. Are listed. A polyene/thiol-based prepolymer obtained by combining polyene and polythiol is also preferable. Here, the (meth)acryloyl group means an acryloyl group or a methacryloyl group.

Examples of the prepolymer having a radically polymerizable unsaturated group include polyester (meth)acrylate, urethane (meth)acrylate, epoxy (meth)acrylate, melamine (meth)acrylate, triazine (meth)acrylate, and silicone (meth)acrylate. Etc. The molecular weight of these is preferably about 250 to 100,000.

Examples of the monomer having a radically polymerizable unsaturated group include, as monofunctional monomers, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, phenoxyethyl (meth)acrylate and the like. Examples of polyfunctional monomers include diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide tri(meth)acrylate, dipentaerythritol tetra( Examples thereof include (meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of bisphenol type epoxy resins, epoxy resins such as novolac type epoxy compounds, and vinyl ether resins such as fatty acid vinyl ethers and aromatic vinyl ethers. Examples of thiols include polythiols such as trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate. Examples of the polyene include those obtained by adding allyl alcohol to both ends of polyurethane made of diol and diisocyanate.

As the ionizing radiation used to cure the ionizing radiation curable resin, electromagnetic waves or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) are used. Usually, ultraviolet rays or electron rays may be used, but visible rays, X-rays, ion rays or the like may be used.
As the ultraviolet ray source, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp can be used. The wavelength of ultraviolet rays is usually preferably 190 to 380 nm.

As the electron beam source, for example, various electron beam accelerators such as Cockcroft-Walton type, Van de Graft type, resonance transformer type, insulating core transformer type, linear type, dynamitron type, high frequency type and the like can be used. Among them, those capable of irradiating with an electron having an energy of 100 to 1000 keV, preferably 100 to 300 keV are preferable.
The two-component curing type urethane resin is not particularly limited, but among them, a polyol component having an OH group as a main component (acrylic polyol, polyester polyol, polyether polyol, epoxy polyol, etc.) and an isocyanate component as a curing agent component (tolylene diene) Isocyanate, hexamethylene diisocyanate, meta-xylene diisocyanate, etc.) can be used.

[Silicone beads]
Further, the content of the silicone beads may be adjusted within a range of 0.1 parts by mass or more and 30 parts by mass or less when the resin component is 100 parts by mass. The range of 0.1 parts by mass or more and 20 parts by mass or more is more preferable, and the range of 1 parts by mass or more and 20 parts by mass or more is even more preferable.
When the curable resin forming the second surface protective layer 6 is an ionizing radiation curable resin, the silicone forming the silicone is preferably an ionizing radiation reactive modified silicone.

Further, when the curable resin forming the second surface protective layer 6 is a mixture of an ionizing radiation curable resin and a thermosetting resin, the silicone constituting the silicone beads has ionizing radiation reactivity and heat reactivity. A modified silicone composed of at least one is preferable.
Here, a silicone resin or a fluororesin can be set on the outermost surface as a measure for improving the stain resistance. In particular, when a silicone resin is used, it is preferable to use a modified silicone because of the problems of adhesion and compatibility with the surroundings. That is, the silicone constituting the silicone beads is preferably modified silicone.

Modified silicones can be classified into reactive modified silicones and non-reactive silicones. Examples of the heat-reactive modified silicone include monoamine-modified silicone, diamine-modified silicone, epoxy-modified silicone, carbinol-modified silicone, carboxy-modified silicone, mercapto-modified silicone, silanol-modified silicone, alcohol-modified silicone and diol-modified silicone. Examples of the ionizing radiation-reactive modified silicone include acrylic modified silicone and methacrylic modified silicone. Further, non-reactive modified silicones such as polyether modified silicone, aralkyl modified silicone, long chain alkyl modified silicone and higher fatty acid ester modified silicone can be exemplified.
Examples of manufacturers of these modified silicones include Shin-Etsu Chemical Co., Ltd., Toray Dow Corning Co., Ltd., Momentive Performance Materials Japan LLC, and Asahi Kasei Wacker Silicone Co., Ltd.

[60 degree specular gloss]
Further, silica or other matting agent is added to the second surface protective layer 6, and the matting agent to be added and the amount thereof are adjusted so that the second surface protective layer 6 has a temperature of 60 degrees in accordance with JIS Z 8741. The value of the specular gloss is adjusted so as to have a desired gloss level according to the purpose of the decorative sheet 10. In the present embodiment, the desired 60-degree specular gloss is in the range of 5 or more and less than 20, or in the range of 20 or more and 35 or less.

In this way, by setting the value of the 60-degree specular gloss of the second surface protective layer 6 according to JIS Z 8741 to 5 or more and 35 or less, unevenness after wiping during cleaning becomes conspicuous as described later. ..
Here, as the glossiness becomes higher, the wiping-off property is improved, but the designability is impaired accordingly. The value of the 60-degree specular gloss is set to 5 or more and 35 or less in consideration of improving the wiping-off property and imparting a design property more than required. At this time, when relatively importance is attached to the design property, it may be adjusted to 5 to 20, and when relatively importance is attached to the improvement of the wiping property, it may be adjusted to 20 to 35.

[First surface protective layer 5]
For the first surface protective layer 5, a resin having the same composition as that of the second outer surface protective layer 6, which is the outermost layer, may be used, or different types, compositions, and ratios of the resins may be used. ..
The decorative pattern layer 2 side of the decorative sheet 10 is as described above, but when the decorative sheet 10 is attached to a wooden base material to be used as the decorative board 20 or further processed into a member, a resin base material sheet is used. The back surface resin coat layer 8 which is a resin layer containing silica powder may be provided on the surface opposite to the pattern layer 2 of both the front and back surfaces of No. 1 to improve the adhesive strength with the wooden base material 11. As the adhesive used for this bonding, for example, an emulsion type adhesive of ethylene vinyl acetate copolymer can be used.

The decorative sheet 10 of the present embodiment having the above-described material configuration has cleanability, scratch resistance and bending workability as a floor material, and is particularly suitable as the decorative sheet 10 for a floor material. is there. The decorative sheet 10 of the present embodiment is not limited to being applied to a floor material, but can be applied as a decorative sheet for a decorative material used around the floor surface such as a step board of stairs.
This embodiment has the following effects.

(1) Of the surface protective layer 7, at least the outermost second surface protective layer 6, which is the outermost layer, contains silicone beads and an ionizing radiation curable resin, and is a 60-degree mirror surface conforming to JIS Z 8741. The gloss is 20 or more and 35 or less.
According to this configuration, the decorative sheet 10 that is easy to wipe off dust and dust such as gypsum board, adhesive, putty, etc. accumulated on the floor during indoor construction while having scratch resistance and having a cleaning property as a cosmetic material is provided. It becomes possible to provide. In particular, by providing silicone beads in the second surface protective layer 6 and specifying a 60-degree specular gloss to a gloss level of 20 or more and 35 or less, a decorative sheet 10 and a decorative sheet with improved cleaning properties are provided. You can

(2) Of the surface protective layer 7, at least the outermost second surface protective layer 6, which is the outermost layer, contains silicone beads and an ionizing radiation curable resin, and is a 60-degree mirror surface in accordance with JIS Z 8741. The gloss is 5 or more and less than 20.
According to this configuration, the decorative sheet 10 that is easy to wipe off dust and dust such as gypsum board, adhesive, putty, etc. accumulated on the floor during indoor construction while having scratch resistance and having a cleaning property as a cosmetic material is provided. It becomes possible to provide. In particular, by including silicone beads in the second surface protective layer 6 and specifying a specular gloss of 60 degrees to a gloss level of 5 or more and less than 20, the decorative sheet has low gloss and high designability while improving cleanability. 10 can be provided.

(3) When the resin component constituting the outermost layer is 100 parts by mass, the modified silicone is contained in an amount of 0.1 parts by mass or more and 30 parts by mass or less.
With this configuration, it is possible to reliably impart stain resistance to the decorative sheet 10.
(4) As the silicone constituting the silicone beads, a modified silicone having the same reactivity as the curing type of the curable resin contained in the second surface protection layer 6 is adopted.
According to this configuration, it is possible to provide the decorative sheet 10 having improved cleaning performance and long-lasting effects.

Hereinafter, the present invention will be described more specifically and in detail with reference to Examples, but the present invention is not limited to these Examples.
<Example 1>
A decorative sheet 10 having the same layer structure as in FIG. 1 was prepared by the following material structure and procedure.
(1) As the base sheet 1, a colored polyethylene film (FZ manufactured by RIKEN TECHNOS CORPORATION) was used.

(2) A grain pattern was printed on the surface of the substrate sheet 1 as a pattern layer 2 by using a gravure ink (Lamister (registered trademark) manufactured by Toyo Ink Co., Ltd.) by a gravure printing machine.
(3) On the back surface of the substrate sheet 1, a two-component urethane primer resin containing silica powder was formed as a back surface resin coating layer 8 by gravure printing so that the thickness after drying was 1 μm.
(4) As an adhesive layer (not shown in FIG. 1), a two-component urethane resin adhesive containing polyester polyol as a main component and isophorone diisocyanate as a curing agent is applied on the pattern layer 2 at a coating amount of 2 g/m ² after drying. It was applied so that

(5) As the transparent adhesive layer 3 (thickness 10 μm), a maleic acid-modified polypropylene resin is used, and as the transparent thermoplastic resin layer 4 (thickness 115 μm), polypropylene having a main component isotactic pentad fraction of 95% ( Prime Polymer Co., Ltd.) was used.
At this time, the transparent adhesive layer 3 and the transparent thermoplastic resin layer 4 were laminated by co-extruding both of them with an extruder so that the transparent adhesive layer 3 was on the side of the pattern layer 2.

(6) As the first surface protective layer 5, a thermosetting acrylic urethane resin (manufactured by DIC Graphics) in which silica is internally added on the transparent thermoplastic resin layer 4 and an isocyanate-based curing agent (DIC Graphics). A coating solution containing a mixture of the above) was applied to a thickness of 9 μm after drying to form a first surface protective layer 5.
Further, as the second surface protective layer 6, an ultraviolet curable urethane acrylate resin, a thermosetting acrylic urethane resin internally containing silica (manufactured by DIC Graphics) on the first surface protective layer 5, and silicone beads. Was prepared to have a mixing ratio of 7:3:1, and a coating solution obtained by mixing an isocyanate curing agent (manufactured by DIC Graphics Co., Ltd.) therewith was applied at a thickness of 6 μm after drying, and the second surface The protective layer 6 was formed. The silicone constituting the silicone beads was acrylic modified silicone.

At that time, the above-mentioned thermosetting type containing a matting agent made of silica is added to the first surface protective layer 5 and the second surface protective layer 6 so that the 60-degree specular gloss value according to JIS Z 8741 becomes 20. The content of the acrylic urethane resin was adjusted.
(7) Subsequently, the ultraviolet curable urethane acrylate resin and the acrylic modified silicone were cured by ultraviolet irradiation (high pressure mercury lamp, 200 mJ/cm ² ) to obtain the decorative sheet 10 of Example 1.

<Example 2>
The decorative sheet 10 of Example 2 was manufactured by making the following changes in the procedure after (6) described in Example 1.
That is, (6) as the formation of the first surface protective layer 5, a coating in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics) in which silica is internally added and an isocyanate-based curing agent (manufactured by DIC Graphics) are mixed. The liquid was applied in a thickness of 9 μm after drying.

Further, as the second surface protective layer 6, an ultraviolet-curable urethane acrylate resin (manufactured by DIC Graphics), a thermosetting acrylic urethane resin containing silica internally added (manufactured by DIC Graphics), and silicone beads are used. The coating liquid was prepared so that the mixing ratio was 3:3:1, and an isocyanate curing agent (manufactured by DIC Graphics Co., Ltd.) was mixed therein to apply the dried coating liquid in a thickness of 6 μm. The silicone constituting the silicone beads was alcohol-modified silicone.

At that time, a thermosetting acrylic urethane containing a matting agent made of silica for the first surface protective layer 5 and the second surface protective layer 6 so that the 60-degree specular gloss value according to JIS Z 8741 becomes 20. The resin content was adjusted.
(7) Subsequently, the ultraviolet curable urethane acrylate resin was cured by irradiation with ultraviolet rays (high pressure mercury lamp, 200 mJ/cm ² ) to obtain a decorative sheet 10 of Example 2.

<Example 3>
The decorative sheet 10 of Example 3 was manufactured by making the following changes in the procedure after (6) described in Example 1.
That is, (6) as the formation of the first surface protective layer 5, a coating in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics) in which silica is internally added and an isocyanate-based curing agent (manufactured by DIC Graphics) are mixed. The liquid was applied in a thickness of 9 μm after drying.

Further, as the second surface protective layer 6, an ultraviolet-curable urethane acrylate resin (manufactured by DIC Graphics), a thermosetting acrylic urethane resin containing silica internally added (manufactured by DIC Graphics), and silicone beads are used. The coating liquid was prepared so that the mixing ratio was 3:3:1, and an isocyanate curing agent (manufactured by DIC Graphics Co., Ltd.) was mixed therein to apply the dried coating liquid in a thickness of 6 μm. The silicone constituting the silicone beads was polyether modified silicone.

At that time, a thermosetting acrylic urethane containing a matting agent made of silica for the first surface protective layer 5 and the second surface protective layer 6 so that the 60-degree specular gloss value according to JIS Z 8741 becomes 20. The resin content was adjusted.
(7) Subsequently, the ultraviolet curable urethane acrylate resin was cured by irradiation with ultraviolet rays (high pressure mercury lamp, 200 mJ/cm ² ) to obtain a decorative sheet 10 of Example 3.

<Example 4>
The decorative sheet 10 of Example 4 was produced by making the following changes in the procedure after (6) described in Example 1.
That is, (6) as the formation of the first surface protective layer 5, a coating in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics) in which silica is internally added and an isocyanate-based curing agent (manufactured by DIC Graphics) are mixed. The liquid was applied in a thickness of 9 μm after drying.

Further, as the formation of the second surface protection layer 6, a coating liquid prepared by mixing silica-internally added UV curable urethane acrylate resin (manufactured by DIC Graphics) and silicone beads in a mixing ratio of 10:1 is dried. The subsequent coating was performed with a thickness of 6 μm. The silicone constituting the silicone beads was acrylic modified silicone.
At that time, a thermosetting acrylic urethane resin in which a matting agent made of silica is internally added to the first surface protective layer 5 and the second surface protective layer 6 so that the 60-degree specular gloss value according to JIS Z 8741 becomes 20. On the other hand, the content of the ultraviolet curable urethane acrylate resin containing the matting agent made of silica was adjusted.
(7) Subsequently, the ultraviolet curable urethane acrylate resin and the acrylic modified silicone were cured by irradiation with ultraviolet rays (high pressure mercury lamp, 200 mJ/cm ² ) to obtain a decorative sheet 10 of Example 4.

<Example 5>
The decorative sheet 10 of Example 5 was manufactured by making the following changes in the procedure after (6) described in Example 1.
That is, (6) as the formation of the first surface protective layer 5, a coating in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics) in which silica is internally added and an isocyanate-based curing agent (manufactured by DIC Graphics) are mixed. The liquid was applied in a thickness of 9 μm after drying.

Further, as the formation of the second surface protection layer 6, a coating liquid prepared by mixing silica-internally added UV curable urethane acrylate resin (manufactured by DIC Graphics) and silicone beads in a mixing ratio of 10:1 is dried. The subsequent coating was performed with a thickness of 6 μm. The silicone constituting the silicone beads was an alcohol-modified silicone.
At that time, a thermosetting acrylic urethane resin containing a matting agent made of silica in the first surface protection layer 5 and the second surface protection layer 6 so that the 60-degree specular gloss value according to JIS Z 8741 becomes 20. Each content of the ultraviolet curable urethane acrylate resin containing a matting agent made of silica was adjusted.
(7) Subsequently, the ultraviolet curable urethane acrylate resin was cured by irradiation with ultraviolet rays (high pressure mercury lamp, 200 mJ/cm ² ) to obtain a decorative sheet 10 of Example 5.

<Example 6>
The decorative sheet 10 of Example 6 was produced by making the following changes in the procedure after (6) described in Example 1.
That is, (6) as the formation of the first surface protective layer 5, a coating in which a thermosetting acrylic urethane resin (manufactured by DIC Graphics) in which silica is internally added and an isocyanate-based curing agent (manufactured by DIC Graphics) are mixed. The liquid was applied in a thickness of 9 μm after drying.

Further, as the formation of the second surface protection layer 6, a coating liquid prepared by mixing an ultraviolet-curable urethane acrylate resin (manufactured by DIC Graphics) containing silica internally and silicone beads in a mixing ratio of 10:1 is dried. The subsequent coating was performed with a thickness of 6 μm. The silicone constituting the silicone beads was polyether modified silicone.
At that time, a thermosetting acrylic urethane resin in which a matting agent made of silica is internally added to the first surface protective layer 5 and the second surface protective layer 6 so that the 60-degree specular gloss value according to JIS Z 8741 becomes 20. Each content of the UV-curable urethane acrylate resin in which a matting agent made of silica was internally added was adjusted.
(7) Subsequently, the ultraviolet curable urethane acrylate resin was cured by irradiation with ultraviolet rays (high pressure mercury lamp, 200 mJ/cm ² ) to obtain a decorative sheet 10.

<Example 7>
Example 7 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer 5 and the second surface protective layer 6 was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 5. The decorative sheet 10 was prepared.
<Example 8>
Example 8 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer 5 and the second surface protective layer 6 was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 8. The decorative sheet 10 was prepared.

<Example 9>
Example 9 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer 5 and the second surface protective layer 6 was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 27. The decorative sheet 10 was prepared.
<Example 10>
Example 10 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer 5 and the second surface protective layer 6 was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 35. The decorative sheet 10 was prepared.

<Comparative Example 1>
Comparative Example 1 in the same manner as in Example 1 except that the composition of the first surface protective layer 5 and the second surface protective layer 6 was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 3. The decorative sheet 10 was prepared.
<Comparative example 2>
Comparative Example 2 in the same manner as in Example 1 except that the composition of the first surface protective layer 5 and the second surface protective layer 6 was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 40. The decorative sheet 10 was prepared.

<Creating a decorative flooring board for evaluation>
The decorative sheet 10 prepared in each of Examples 1 to 10, Comparative Example 1 and Comparative Example 2 was attached to the surface of an MDF (hardwood) having a thickness of 3 mm to form a decorative board for evaluation.
A two-component aqueous emulsion adhesive (Ricabond (registered trademark) BA-10L/BA-11B=100:2.5 manufactured by Chuo Rika Kogyo Co., Ltd.) was used as an adhesive for bonding, and 100 g/m ^{2 in} a wet state. It was pasted with the coating amount of. Then, it was aged for 24 hours to obtain a decorative board (a decorative board for evaluation).

<Evaluation item and evaluation method>
The decorative sheets using the decorative sheet 10 produced by the material configurations and procedures of Examples 1 to 10 and Comparative Examples 1 and 2 were tested and evaluated by the following evaluation items and evaluation methods.
(1) Measurement of 60-degree specular gloss value The test method was performed according to JIS Z 8741.

(2) Wipeability test "Tiger putty 120" made by Yoshino Gypsum (also used as a base and finish) was hand-painted on each decorative plate, cured for 1 hour, wiped with a mop that was squeezed hard, and then wiped with a dry wipe.
Then, a sensory test was carried out by 10 testers as confirmation of uneven wiping.
The evaluation indicators are as follows.
○: Good people 7 to 10 △: Good people 1 to 6
×: 0 people

(3) Design test A luster design property of each decorative board as a decorative material was subjected to a sensory test with 10 testers.
The evaluation indicators are as follows.
○: Good people 7 to 10 △: Good people 1 to 6
×: 0 good people

(4) Slipper Sliding Test A slipper made of a vinyl chloride material was subjected to 200,000 reciprocating sliding motions under a load of 45 g/cm ² . After that, it was contaminated with black magic and wiped off with a dry wipe. The evaluation indicators are as follows.
○: All surfaces can be wiped out △: Partially wiped off ×: Not wiped off

(5) Comprehensive evaluation The evaluations (2) to (4) were combined. The indicators are as follows.
◎: ○ 3 evaluations ○: ○ 2 evaluations and 1 △ evaluation △: ○ 1 evaluation and 2 △ evaluations ×: 1 or more × evaluation

<Evaluation result>
The evaluation results are shown in Table 1.

In Examples 1 to 10, the evaluation was “Δ” or more in (5) comprehensive evaluation, and good results were shown in the range of 5 to 35 in the 60-degree specular gloss value.
It was confirmed that in Comparative Example 1 in which the specular gloss of 60 degrees was relatively 3, unevenness after wiping was easily noticeable. This indicates that the gloss value has an effect on the noticeability of uneven wiping.

In Comparative Example 2 in which the second surface protective layer 6 has a 60-degree specular gloss of 40, the pattern has an excellent wiping resistance, but on the other hand, the pattern tends to be difficult to see due to light reflection, and the design is unacceptable. It can be seen that the value of 60° gloss is 35 or less in order to satisfy the design property.
Collecting these results, it can be seen that the outermost surface having a 60-degree specular gloss of 5 or more and 35 or less makes it possible to provide a decorative sheet 10 having cleanability and designability as a decorative material. ..

In addition, in Examples 1 to 6, 9 and 10 in which the 60-degree specular gloss of the outermost surface was 20 or more and 35 or less, the evaluation in the wiping test was better than that of the other Examples. This indicates that there is a difference in how easily stains stand out depending on the gloss value.
Here, in Examples 7 and 8 in which the 60-degree specular gloss is 5 or more and less than 20, the wiping-off property is slightly lowered as compared with the other Examples, but the designability is slightly better than the other Examples. I have confirmed that it had become.

Further, in Examples 1, 2, 4, 9, 10 in which the silicone constituting the silicone beads to be added is a combination containing the component constituting the second surface protective layer 6 and the one forming a crosslinked structure after curing The slipper slidability was evaluated to be better than that of the example. This shows that the one in which the modified silicone constituting the silicone beads adheres well to the second surface protective layer 6 has a high durability against the cleaning property.
From the above results, it was possible to verify that the present invention can provide a decorative sheet 10 having cleanability and designability as a decorative material.

DESCRIPTION OF SYMBOLS 1... Substrate sheet 2... Design pattern layer 3... Transparent adhesive layer 4... Transparent thermoplastic resin layer 5... First surface protection layer 6... Second surface protection layer 7... ..Surface protective layer 8... Backside resin coat layer (resin layer)
11... Base material 10... Decorative sheet 20... Decorative board

Claims (9)

A pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are formed in this order on a resin base sheet,
The outermost layer positioned on the outermost surface of the surface protective layer contains a matting agent made of silica , silicone beads and an ionizing radiation curable resin, and has a 60-degree specular gloss of 20 or more and 35 or less in accordance with JIS Z 8741. ,
The surface protective layer other than the outermost layer contains a matting agent made of silica and a thermosetting resin,
The silicone constituting the silicone beads is alcohol-modified silicone or polyether-modified silicone,
The transparent adhesive layer contains a maleic acid-modified polypropylene resin, which is a decorative sheet. A pattern layer, a transparent adhesive layer, a transparent thermoplastic resin layer, and a surface protective layer are formed in this order on a resin base sheet,
The outermost layer located on the outermost surface of the surface protective layer contains a matting agent made of silica , silicone beads and an ionizing radiation curable resin, and has a 60-degree specular gloss of 5 or more and less than 20 in accordance with JIS Z 8741. ,
The surface protective layer other than the outermost layer contains a matting agent made of silica and a thermosetting resin,
The silicone constituting the silicone beads is alcohol-modified silicone or polyether-modified silicone,
The transparent adhesive layer contains a maleic acid-modified polypropylene resin, which is a decorative sheet. The decorative sheet according to claim 1 or 2, wherein the silicone beads contain 0.1 part by mass or more and 30 parts by mass or less, when 100 parts by mass of the resin component forming the outermost layer is included. .. The decorative sheet according to any one of claims 1 to 3, wherein the silicone constituting the silicone beads contains a modified silicone reactive with ionizing radiation. The ionizing radiation curable resin is an ultraviolet curable resin,
The outermost layer is formed of a mixture of the ultraviolet curable resin and thermosetting resin,
The content of the mixture is 70% by mass or more based on the total amount of the outermost layer,
In the mixture, the content of the ultraviolet curable resin is in the range of 80% by mass or more and 90% by mass or less, and the content of the thermosetting resin is in the range of 10% by mass or more and 20% by mass or less. And
The decorative sheet according to any one of claims 1 to 4, wherein the silicone constituting the silicone beads includes a heat-reactive modified silicone. The thermosetting resin is a thermosetting acrylic urethane resin,
The decorative sheet according to claim 5, wherein the ionizing radiation curable resin is an ultraviolet curable urethane acrylate resin. The decorative sheet according to any one of claims 1 to 6 , wherein a layer thickness of the outermost layer is thinner than a layer thickness of the surface protective layer other than the outermost layer. The transparent thermoplastic resin layer, the decorative sheet described in any one of claims 1 to 7, characterized in that it comprises an isotactic pentad fraction of 95% of polypropylene. A decorative board produced using the decorative sheet according to any one of claims 1 to 8 .

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