JP6707820B2 - Decorative sheets and boards - Google Patents

Description

The present invention relates to a resin decorative sheet and a decorative plate. In particular, the present invention relates to a decorative sheet excellent in 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 developing residential construction as an industry. It can be said that prefabricated architecture has played a leading role in apartments, condominiums, and individual houses, which are especially collective housing.
Traditionally, 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, but with the development of the housing industry, industrialization progressed and the conversion from natural materials to artificial materials was Has been done. Alternatively, in recent years, the frequent use of high-grade wood and stone materials may lead to deforestation and environmental problems, which is one of the factors increasing 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).
In addition, after the completion of interior decoration work for apartments, condominiums, and private homes, there will be room cleaning by the management company and beautifying companies. Gypsum board, putty such as putty, dust, etc. scattered on the floor will be wiped and cleaned using water or detergent.
When the sheet flooring floor material is wiped and cleaned, if the dry wiping property after wiping with water is heavy or if unevenness is apt to occur during wiping, a problem such as time-consuming cleaning may occur.

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 decorative board.

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 base sheet, The outermost layer positioned at least on the outermost surface of the surface protective layer contains a fluororesin and 60 parts by mass or more of 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. Is characterized in that

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 cleaning property 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.

Hereinafter, embodiments of the present invention will be described with reference to the drawings.
In the present embodiment, the decorative sheet and decorative plate for 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. Further, 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. The technical idea of the present invention can be modified in various ways 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 laminating in order. 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 bonding the decorative sheet 10 to 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 defined by Japanese Agricultural Standards can be used. A base material made of wood powder-added olefin resin 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. Among them, 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 bending workability.
In the case of coloring the base material sheet 1, the base material to which the decorative sheet 10 is attached is 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 below the design pattern layer 2 as a solid ink layer by using a coating or printing method before providing the design pattern layer 2.

[Pattern layer 2]
The picture pattern layer 2 can be provided by 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 designs, various wood grain patterns are often used. It can also be For example, if it is an image of a floor made of stone 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 layer 2 for the purpose of improving the adhesiveness between the 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, 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. Among them, 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 bending workability. In particular, regarding bending workability, it is important to select it in consideration that whitening or cracking of a 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 the weather resistance and abrasion resistance of the decorative sheet 10 can be improved.

[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, each layer is formed by a known coating device, heat drying device, and ultraviolet irradiation device 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 or 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 wood grain board conduit grooves, stone board surface irregularities (granite cleaved surface, etc.), cloth surface texturer, satin, sand, hairline, line groove, and the like.

[Second surface protective layer 6]
The second surface protection layer 6 is the outermost layer located on the outermost surface of the surface protection layer 7. The second surface protective layer 6 contains a fluororesin and an 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 60 parts by mass or more of the ionizing radiation curable resin in the whole 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 on 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, at least the second surface protective layer 6, which is the outermost layer, of the surface protective layer 7 is preferably 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 so as to be in the range of 7:3 to 9:1 by mass ratio, that is, the ultraviolet curable resin is 80 to 90% of 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 on the floor 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 prepolymer (including an oligomer) containing a radically polymerizable double bond capable of undergoing a polymerization cross-linking reaction in the molecule by irradiation of ionizing radiation such as ultraviolet rays or electron beams, 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, as the prepolymer or monomer, 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 a molecule. Is mentioned. 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 usually 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, trimethylol propane tri(meth)acrylate, trimethylol propane 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 epoxy resins such as bisphenol type epoxy resins and novolac type epoxy compounds, and vinyl ether type 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, an electromagnetic wave or charged particles having energy capable of causing a curing reaction of molecules in the ionizing radiation curable resin (composition) is used. Usually, ultraviolet rays or electron beams may be used, but visible rays, X-rays, ion beams or the like may be used.
As the ultraviolet ray source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc lamp, a black light, a metal halide lamp or the like 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, and high frequency type 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 particularly 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.

[Fluorine resin]
Here, a silicone resin or a fluororesin can be set on the outermost surface as a measure for improving the stain resistance. In particular, fluororesins are widely known to exhibit a minimum level of surface tension and are suitable as stain resistant materials.
Examples of the fluororesin contained in the second surface protective layer 6 include tetrafluoroethylene resin, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, and the like, and many other derivatives are used. be able to.

Manufacturers of these fluororesins include Daikin Industries, Ltd., Mitsui DuPont Fluorochemicals Ltd., and the like.
The amount of the fluororesin contained in the second surface protective layer 6 is preferably 10 parts by mass or more and 100 parts by mass or less. It is more preferably at least 20 parts by mass.
Here, the fluororesin itself may be a curable resin. That is, a part of the fluororesin may also serve as a part of the curable resin which is the main component of the surface protective layer 7. As described above, all the resin components of the second surface protection layer 6 may be fluororesins.

[60 degree specular gloss]
Further, by adding a matting agent such as silica to the second surface protective layer 6 and adjusting the composition of the matting agent to be added and the amount thereof, the second surface protective layer 6 has a temperature of 60 degrees according to 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 this 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 the improvement of the wiping property and the imparting of the design property more than required. At this time, when the designability is relatively important, it is adjusted to 5 to 20, and when the improvement of the wiping property is relatively important, it is preferably adjusted to 20 to 35.

[First surface protection layer 5]
For the first surface protection layer 5, a resin having the same composition as that of the second surface protection layer 6, which is the outermost layer, may be used, or a resin in which the kind, composition, and ratio of the resin are changed may be used. ..
Although the decorative pattern layer 2 side of the decorative sheet 10 is as described above, 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 the front and back surfaces of No. 1 to improve the adhesive strength with the wood base material 11. As the adhesive used for this bonding, for example, an ethylene-vinyl acetate copolymer emulsion type adhesive or the like can be used.
The decorative sheet 10 of the present embodiment having the above-described material configuration has cleaning properties, scratch resistance and bending workability as a floor material, and is particularly suitable as the decorative sheet 10 for floor material. is there. Note that the decorative sheet 10 of the present embodiment is not limited to being applied to floor materials, but can also 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 a fluororesin and an ionizing radiation curable resin, and is a 60-degree mirror surface according 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 and the like accumulated on the floor during indoor construction while providing scratch resistance, and having cleanability as a cosmetic material is provided. It becomes possible to provide. Particularly, by providing the second surface protective layer 6 with a fluororesin, the specular gloss of 60 degrees is specified to be a gloss level of 20 or more and 35 or less to provide a decorative sheet 10 and a decorative sheet with improved cleanability. You can

(2) Of the surface protective layer 7, at least the outermost second surface protective layer 6, which is the outermost layer, contains a fluororesin and an ionizing radiation curable resin, and is a 60-degree mirror surface conforming to 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 and the like accumulated on the floor during indoor construction while providing scratch resistance, and having cleanability as a cosmetic material is provided. It becomes possible to provide. In particular, by including the modified silicone in the second surface protection layer 6 and specifying the 60-degree specular gloss to a gloss of 5 or more and less than 20, the decorative sheet has a low gloss and a high design property while improving the cleaning property. 10 can be provided.

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 base material sheet 1, as the back surface resin coating layer 8, a two-component urethane primer resin containing silica powder was formed 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 with a main component isotactic pentad fraction 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 pattern layer 2 side.

(6) As the first surface protective layer, 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 curing agent (manufactured by DIC Graphics). ) Was mixed to obtain a coating having a thickness of 9 μm after drying.
Further, as the second surface protective layer, a coating liquid obtained by mixing an ultraviolet curable urethane acrylate resin, a fluororesin A and an isocyanate curing agent (manufactured by DIC Graphics) was applied to a thickness of 6 μm after drying. Here, the UV-curable urethane acrylate resin was set to 60 parts by mass and the fluororesin A was set to 30 parts by mass.
At that time, a thermosetting acrylic urethane resin internally added with a matting agent made of silica was added to the first surface protective layer and the second surface protective layer so that the 60-degree specular gloss value according to JIS Z 8741 was 20. did.
Here, the fluororesins A, B and C are as follows.
Fluororesin A: Product name "Defencer FH-700", manufacturer "DIC Corporation"
Fluorine resin B: Product name "Defencer FH-710", manufacturer "DIC Corporation"
Fluororesin C: Product name "Rioduras F-1014", manufacturer "Toyo Ink Co., Ltd."
(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 of Example 1.

<Example 2>
A decorative sheet of Example 2 was produced by the same procedure except that the fluororesin B was used instead of the fluororesin A described in Example 1.
<Example 3>
A decorative sheet of Example 3 was produced in the same procedure except that the fluororesin C was used instead of the fluororesin A described in Example 1.
<Example 4>
A decorative sheet of Example 4 was produced by the same procedure except that the fluororesin A described in Example 1 was replaced with 30 parts by mass and 10 parts by mass of the fluororesin A was used.
<Example 5>
A decorative sheet of Example 5 was produced by the same procedure except that the fluororesin A described in Example 1 was replaced with 30 parts by mass and the fluororesin B was used with 10 parts by mass.
<Example 6>
A decorative sheet of Example 6 was produced in the same procedure except that 10 parts by mass of fluororesin C was used instead of 30 parts by mass of fluororesin A described in Example 1.

<Example 7>
The decorative sheet of Example 7 was prepared by making the following changes in the procedure after (6) described in Example 1.
That is, (6) a coating liquid obtained by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) containing silica internally and an isocyanate curing agent (manufactured by DIC Graphics) for forming the first surface protective layer. Was coated to a thickness of 9 μm after drying.
Further, for forming the second surface protective layer, a UV-curable urethane acrylate resin (manufactured by DIC Graphics) and a thermosetting acrylic urethane resin containing silica internally added (manufactured by DIC Graphics) are mixed in a ratio of 7:3. A coating liquid prepared by mixing 30 parts by mass of the fluororesin A and an isocyanate-based curing agent (manufactured by DIC Graphics Co.) was applied in a thickness of 6 μm after drying.
At that time, a thermosetting acrylic urethane resin internally added with a matting agent made of silica was added to the first surface protective layer and the second surface protective layer so that the 60-degree specular gloss value according to JIS Z 8741 was 20. did.
(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 of Example 7.

<Example 8>
The makeup of Example 8 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer and the second surface protective layer was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 5. Created a sheet.
<Example 9>
The makeup of Example 9 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer and the second surface protective layer was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 8. Created a sheet.

<Example 10>
The makeup of Example 10 was performed in the same manner as in Example 1 except that the composition of the first surface protective layer and the second surface protective layer was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 27. Created a sheet.
<Example 11>
The makeup of Example 11 was performed in the same manner as in Example 1 except that the composition of the first surface protective layer and the second surface protective layer was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 35. Created a sheet.

<Comparative Example 1>
A decorative sheet of Comparative Example 1 was produced by the same procedure except that 1 part by mass of the fluororesin A was used instead of 30 parts by mass of the fluororesin A described in Example 1.
<Comparative example 2>
The decorative sheet of Comparative Example 2 was prepared by changing the procedure as described below in (6) in Example 1 as follows.
That is, (6) a coating liquid prepared by mixing a thermosetting acrylic urethane resin (manufactured by DIC Graphics) containing silica internally and an isocyanate curing agent (manufactured by DIC Graphics) for forming the first surface protective layer. Was coated to a thickness of 9 μm after drying.
Further, as the formation of the second surface protective layer, a 5:5 mixture of a UV-curable urethane acrylate resin (manufactured by DIC Graphics) and a thermosetting acrylic urethane resin containing silica internally (manufactured by DIC Graphics) is used. A coating liquid prepared by mixing 30 parts by mass of the fluororesin A and an isocyanate-based curing agent (manufactured by DIC Graphics Co.) was applied in a thickness of 6 μm after drying.
At that time, a thermosetting acrylic urethane resin internally added with a matting agent made of silica was added to the first surface protective layer and the second surface protective layer so that the 60-degree specular gloss value according to JIS Z 8741 was 20. did.
(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 of Comparative Example 2.

<Comparative example 3>
Makeup of Comparative Example 3 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer and the second surface protective layer was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 3. Created a sheet.
<Comparative example 4>
Makeup of Comparative Example 4 was carried out in the same manner as in Example 1 except that the composition of the first surface protective layer and the second surface protective layer was changed so that the 60-degree specular gloss value according to JIS Z 8741 was 40. Created a sheet.

<Creating a decorative flooring board for evaluation>
The decorative sheets prepared in Examples 1 to 11 and Comparative Examples 1 to 4 were attached to the surface of MDF (hardwood) having a thickness of 3 mm to give a decorative material 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 in a wet state. The coating amount of ² was applied. Then, it was aged for 24 hours to obtain a cosmetic material (cosmetic material for evaluation).

<Evaluation items and evaluation methods>
The decorative sheets using the decorative sheets prepared by the material configurations and procedures of Examples 1 to 11 and Comparative Examples 1 to 4 were tested and evaluated by the following evaluation items and evaluation methods.
(1) Measurement of 60-degree specular gloss value The test method was based on JIS Z 8741.
(2) Wipeability test "Tiger putty 120" (also used as a base and finish) made by Yoshino Gypsum was hand-painted on each decorative material, and after curing for 1 hour, wiped with a mop that was squeezed hard and then wiped with a dry wipe.
Confirmation of wiping unevenness A sensory test was performed on 10 testers.
The evaluation indicators are as follows.
◯: Good people 7 to 10 people △: Good people 1 to 6 people
×: 0 good people

(3) Designability test A luster designability as a cosmetic material was subjected to a sensory test with 10 testers.
The evaluation indicators are as follows.
◯: Good people 7 to 10 people △: Good people 1 to 6 people
X: 0 people considered good (4) Slipper sliding test The slipper made of vinyl chloride 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.
◎: Three evaluations ○: Two evaluations and one evaluation △: One evaluation and two evaluations ×: One or more × evaluation

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

In Examples 1 to 11, (5) the overall evaluation was “Δ” or higher, and good results were shown in the range of the 60-degree specular gloss value of 5 to 35.
In Comparative Example 1 in which the addition amount of the fluororesin A is 1% by mass, the evaluation in the slipper test is low. It can be seen that the effect on cleanability does not appear unless the fluorine resin is added to a certain extent or more.
In Comparative Example 2 in which the ratio of the ultraviolet curable urethane acrylate resin and the thermosetting acrylic urethane resin was 5:5, the evaluation in the slipper test was low. It can be seen that the effect of cleaning property is not exhibited unless the ionizing radiation curable resin is added to a certain extent or more.

In Comparative Example 3 in which the 60-degree specular gloss value was 3 relatively, it was confirmed that unevenness after wiping was easily noticeable. This indicates that the gloss value has an effect on the noticeability of uneven wiping.
In Comparative Example 4 in which the 60-degree specular gloss value of the second surface protective layer is 40, the pattern has an excellent wiping resistance, but the pattern tends to be difficult to see due to reflection of light, and the design is unacceptable. It can be seen that the 60° gloss value of 35 or less is effective for satisfying the design property.
When these results are summed up, it can be seen that the outermost surface having a 60-degree gloss value of 5 or more and 35 or less makes it possible to provide a decorative sheet having cleanability and designability as a decorative material.
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.

In addition, in Examples 1 to 7 and 9 to 11 in which the 60-degree gloss value of the outermost surface was 8 or more and less than 35, 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.
Further, in Examples 1-2, 10 and 11 in which the amount of the fluororesin to be added is 30 parts by mass or more, the thermosetting acrylic urethane resin is not included, and the gloss value is 20 to 35, other implementations are performed. The evaluation in terms of wiping-off property or slippery sliding property was better than that of the example. This indicates that the proportion of the ionizing radiation-curable resin as the main component, the amount of fluororesin, and the gloss value determine the degree of effect on the cleanability.
From the above results, it was verified that according to the present invention, it is possible to provide a decorative sheet having cleanability and designability as a decorative material.

1 Base Material Sheet 2 Pattern Layer 3 Transparent Adhesive Layer 4 Transparent Thermoplastic Resin Layer 5 First Surface Protective Layer 6 Second Surface Protective Layer 7 Surface Protective Layer 8 Backside Resin Coat Layer 10 Decorative Sheet 11 Base Material 20 Decorative Plate

Claims (6)

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,
An outermost layer located on at least the outermost surface of the surface protective layer is an ionizing radiation-curable fluororesin only consists of, and Ri 20 below der 60 degree specular gloss is 5 or more conforming to JIS Z 8741,
The decorative sheet is characterized in that the transparent adhesive layer is composed only of a maleic acid-modified polypropylene resin. 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,
An outermost layer located on at least the outermost surface of the surface protective layer consists only of the hardening type fluororesin, and 60-degree specular gloss conforming to JIS Z 8741 is 5 to 20,
The curable fluororesin contains an ionizing radiation curable resin and a thermosetting resin,
Weight of the mixture between the upper SL-Ionizing radiation curable resin and the thermosetting resin is at least 70% of the total mass of the resin constituting the outermost layer,
The mixing ratio of the upper SL-Ionizing radiation curable resin and the thermosetting resin, the mass ratio of 7: 3 to 9: Ri der 1 range,
The decorative sheet is characterized in that the transparent adhesive layer is composed only of a maleic acid-modified polypropylene resin. The decorative sheet according to claim 1 or 2 , wherein the transparent thermoplastic resin layer contains polypropylene having an isotactic pentad fraction of 95%. The layer located on the transparent thermoplastic resin layer side of the surface protective layer contains silica and a thermosetting acrylic urethane resin, and any one of claims 1 to 3 is described. Makeup sheet. The decorative sheet according to any one of claims 1 to 4 , wherein at least the outermost layer located on the outermost surface of the surface protective layer contains silica. A decorative board produced using the decorative sheet according to any one of claims 1 to 5 .

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