JP2016089379A - Decorative floor sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative floor sheet superior in a decorative sheet rolling-up property, durability to damage, and slipper slidability.SOLUTION: A decorative floor sheet at least comprises, in the following order: a primer layer 3; a thermoplastic resin substrate 1; a picture pattern layer 2; an urethane resin adhesive layer 4; a transparent adhesive resin layer 5; a transparent thermoplastic resin layer 6; a primer layer 7; and a surface protective layer 8. The surface protective layer 8 is a resin layer made from a mixture of: an ionization radiation curable resin, which comprises at least one type selected from polyfunctional (meth)acrylate monomer or oligomer with two polymerizable groups or more, dendritic polymer, photo-radical polymerization initiator; and a thermoplastic resin.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a decorative sheet for floors.

As a conventional decorative material for floors, a veneer is bonded to a plywood, further grooved with a woodworking machine, and the groove is colored, and then coated with an ultraviolet curable paint and cured. Yes. However, because the veneer is a natural wood, there are cases where the color varies and it is difficult to harmonize the color with the walls, ceiling, and furniture.
Then, the flooring decorative material which bonded the decorative sheet which provided the thermoplastic resin base material, the pattern, and the transparent thermoplastic resin in this order on the wooden base material was considered.

However, if the decorative sheet is too thick, it will be in a wave shape (wound state) and difficult to wind, and sheet cutting will be difficult on the production line during continuous lamination with a wooden base material, and productivity will not increase. For this reason, when laminating (bonding) a decorative sheet and a wooden base material, a decorative sheet cut in advance to the same size as that of the wooden base material is prepared, and one sheet is used in a single-wafer method. It was necessary to adopt a manufacturing method such as laminating sheets.
And in order to raise said winding-up suitability, it is necessary to make a decorative sheet as thin as possible, but it exists in the tendency for it to become difficult to take out damage resistance and slipper sliding property, so that it becomes thin.

Here, Patent Document 1 proposes to improve wear resistance and scratch resistance by adding a filler to the surface protective layer. However, when used for the surface protective layer of flooring, the contacted object may be damaged more than necessary. Furthermore, there was a problem that the transparency deteriorated.
Patent Document 2 also proposes improving the scratch resistance and the like by adding spherical glass. However, although transparency is good, there is still a problem that scratch resistance and slipper sliding property are inferior.

JP-A-11-115141 JP 2006-16528 A

  The present invention has been made in consideration of such points, and an object of the present invention is to provide a decorative sheet for a floor that is excellent in winding up of a decorative sheet, and has excellent scratch resistance and slipper sliding properties. .

  In order to solve the problem, a decorative sheet for floor of one embodiment of the present invention includes a primer layer, a thermoplastic resin base material, a pattern layer, a urethane resin adhesive layer, a transparent adhesive resin layer, and a transparent thermoplastic resin layer. A primer layer and a surface protective layer are provided at least in this order, and the surface protective layer is at least one selected from polyfunctional (meth) acrylate monomers or oligomers having two or more polymerizable groups, a dendritic polymer, It is a resin layer comprising a mixture of an ionizing radiation curable resin comprising a photo radical polymerization initiator and a thermosetting resin.

According to the floor decorative sheet of the present invention, by using at least one selected from a polyfunctional (meth) acrylate monomer or oligomer having two or more polymerizable groups in the surface protective layer, and a dendritic polymer, It is possible to provide a floor decorative sheet that can maintain the hardness required for the surface of the material and is excellent in bending workability such as V-cut processing due to the flexibility unique to the dendritic polymer.
Here, by appropriately selecting a thermosetting resin, it is possible to impart excellent weather resistance.

It is explanatory sectional drawing of the decorative sheet for floors concerning embodiment based on this invention. It is a schematic diagram of a dendrimer. It is a schematic diagram of a hyperbranched polymer.

Next, embodiments of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiment described below exemplifies 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 component parts are as follows. It is not something specific. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

As shown in FIG. 1, the decorative sheet for floor according to the present embodiment includes a primer layer, a thermoplastic resin base material, a pattern layer, a urethane resin adhesive layer, a transparent adhesive resin layer, a transparent thermoplastic resin layer, and a primer. A layer and a surface protective layer are laminated in this order. Other layers may be added.
The thermoplastic resin substrate 1 is a film made of a thermoplastic resin. The resin constituting the thermoplastic resin substrate 1 is not particularly limited in the material of the resin, and the resin can be selected by selecting from thermoplastic resins. For example, polyolefin resin, vinyl chloride resin, acrylic resin and the like can be used. In particular, polyolefin resin is more preferable in consideration of productivity in a melt extrusion apparatus, environmental compatibility, mechanical strength as a flooring material, durability, price, and the like.
As for the thickness of the thermoplastic resin base material layer 1, 40-150 micrometers is desirable, for example.

The pattern layer 2 imparts design properties as a flooring material. As a design as a design, a desired printed pattern suitable for a flooring material such as cork, stone, tile, pottery, and abstract pattern can be selected in addition to the grain pattern.
The printing ink used for printing is not particularly limited in consideration of printability and weather resistance as a flooring material. As for the printing method, known printing methods such as gravure printing, offset printing, silk screen printing, and ink jet printing can be used. When coloring the entire surface, in addition to the printing method, use a coating method or apparatus. Also good.
The thickness of the pattern layer 2 is, for example, 0.1 to 10 μm.

The primer layer 3 is made of, for example, a two-component urethane primer resin containing silica powder.
The thickness of the primer layer 3 is preferably 0.5 to 1.5 μm, for example.
The urethane resin adhesive layer 4 is made of, for example, a two-component urethane resin adhesive having a polyester polyol as a main component and isophorone diisocyanate as a curing agent.
The thickness of the urethane resin adhesive layer 4 is preferably 0.5 to 2.5 μm, for example.

The transparent adhesive resin layer 5 is made of, for example, maleic acid-modified polypropylene resin.
As for the thickness of the transparent adhesive resin layer 5, 5-15 micrometers is desirable, for example.
For the transparent thermoplastic resin layer 6, for example, a thermoplastic resin film such as polyolefin resin, vinyl chloride resin, or acrylic resin can be used. In particular, polyolefin resin is more preferable in consideration of environmental compatibility, mechanical strength as a flooring material, durability, price, and the like.
As for the thickness of the transparent adhesive resin layer 6, 60-140 micrometers is desirable, for example.

The primer layer 7 is composed of, for example, a two-component urethane resin primer.
As for the thickness of the primer layer 7, 5-10 micrometers is desirable, for example.
The surface protective layer 8 includes at least one selected from polyfunctional (meth) acrylate monomers or oligomers having two or more polymerizable groups, a dendritic polymer, and an ionizing radiation curable resin comprising a radical photopolymerization initiator, It is a resin layer which consists of a mixture with a thermosetting resin.
The thickness of the surface protective layer 8 is preferably 5 to 8 μm, for example.
The dendritic polymer is preferably a hyperbranched polymer.
In the dendritic polymer, it is preferable that at least a part of the branched chain ends have one or more polymerizable groups.

According to the decorative sheet for floor of the present embodiment, at least one selected from a polyfunctional (meth) acrylate monomer or oligomer having two or more polymerizable groups in the surface protective layer, and a dendritic polymer having a high terminal reactive group concentration. And are used. As a result, it is possible to provide a floor decorative sheet that can maintain the required hardness of the surface of the flooring material and is excellent in bending workability such as V-cut processing due to the flexibility unique to the dendritic polymer.
As a result, it is possible to provide a decorative sheet for a floor which is excellent in sheet winding property and transparency, and has excellent scratch resistance and slipper sliding property.
Here, by appropriately selecting a thermosetting resin, it is possible to impart excellent weather resistance.

Moreover, it becomes possible to earn the hardness requested | required of the surface of a flooring material because a surface protective layer contains the ionizing radiation curable resin which consists of radical photopolymerization initiators.
By using a hyperbranched polymer as the dendritic polymer, costs can be reduced.
When at least a part of the branched chain end of the dendritic polymer has one or more polymerizable groups, high hardness and flexibility can be obtained while suppressing shrinkage during curing.

Below, the Example of the decorative sheet for floors based on the said embodiment and the comparative example for a comparison are demonstrated.
<Example 1>
A polyethylene film (“FZ” manufactured by Riken Technos Co., Ltd.) is used as the colored thermoplastic resin substrate 1, and gravure ink (manufactured by Toyo Ink Mfg. Co., Ltd.) is used on one side (surface) of the colored thermoplastic resin substrate 1. The wood grain print was printed with a gravure printing machine with "Lamistor") to provide the pattern layer 2.
Thereafter, the two-component urethane primer resin containing the powder is gravure-coated on the surface (back surface) opposite to the pattern layer of the colored thermoplastic resin so as to have a thickness after drying of 1 μm. Primer layer 3 was provided.

Further, a two-component urethane resin adhesive having a polyester polyol as a main component and isophorone diisocyanate as a curing agent is applied onto the pattern layer 2 so that the coating amount after drying is 2 g / m ^2. A system adhesive layer 4 was formed.
Thereafter, a transparent adhesive resin layer 5 made of maleic acid-modified polypropylene resin is formed on the urethane resin adhesive layer 4, and a 10 μm and isotactic pentad fraction is 95% on the transparent adhesive resin layer 5. A transparent thermoplastic resin layer 6 mainly composed of polypropylene (manufactured by Prime Polymer Co., Ltd.) was formed by coextrusion lamination so that the thickness was 80 μm and the adhesive layer 5 was on the pattern layer 2 side. .

The urethane resin primer layer 7 is formed by applying a two-component urethane resin primer on the surface of the sheet material formed by coextrusion lamination so that the coating amount after drying is 9 g / m ^2. The surface protective layer 8 was formed thereon.
The surface protective layer 8 of Example 1 is composed of 28 parts by mass of urethane acrylate (“UA-3061” manufactured by Kyoeisha Chemical Co., Ltd.), 22 parts by mass of hyperbranched polymer (“CN-2301” manufactured by Sartomer), and initiation of radical photopolymerization. Agent (BASF "Irgacure 184" 1.5 parts by mass, acrylic polyol resin ("Acrycot QT510-15ED" manufactured by Taisei Fine Chemicals Co., Ltd.) 50 parts by mass, isocyanate curing agent (DIC Graphics Co., Ltd.) “FG700”) 10 parts by mass of a coating solution obtained by stirring and mixing with ethyl acetate to an appropriate viscosity was applied so that the coating amount after drying was 6.5 g / m ^2. (The “Fusion D bulb” manufactured by Heraeus Co., Ltd.) was completely cured at 240 W / cm × 2 to form the surface protective layer 8. Thereafter, 40 Heat-curing for 3 days was performed at 0 ° C. to obtain a floor decorative sheet of this example.

<Comparative example 1>
As the surface protective layer 8 of Comparative Example 1, 50 parts by mass of urethane acrylate (“UA-3061” manufactured by Kyoeisha Chemical Co., Ltd.), a radical photopolymerization initiator (“Irgacure 184” manufactured by BASF) 1.5 parts by mass, acrylic 50 parts by mass of a polyol resin (“Acrycot QT510-15ED” manufactured by Taisei Fine Chemical Co., Ltd.) and 10 parts by mass of an isocyanate curing agent (“FG700” manufactured by DIC Graphics Co., Ltd.) are stirred to an appropriate viscosity with ethyl acetate. The mixed coating liquid was applied so that the coating amount after drying was 6.5 g / m ^2, and 240 W / cm × 2 using an ultraviolet light emitting lamp (“Fusion D bulb” manufactured by Heraeus Co., Ltd.). The surface protective layer 8 was obtained by complete curing with a book.
A decorative sheet was produced using the same materials and production method as in Example 1 except for the surface protective layer 8.

<Comparative example 2>
As the surface protective layer 8 of Comparative Example 2, 100 parts by mass of urethane acrylate (“UA-3061” manufactured by Kyoeisha Chemical Co., Ltd.) and 1.5 parts by mass of a radical photopolymerization initiator (“Irgacure 184” manufactured by BASF) The coating solution stirred and mixed to an appropriate viscosity with ethyl acetate was applied so that the coating amount after drying was 6.5 g / m ² , and an ultraviolet light emitting lamp (“Fusion D” manufactured by Heraeus Co., Ltd.) was applied. The surface protective layer 8 was obtained by complete curing at 240 W / cm × 2 by a valve ”).
A decorative sheet was produced using the same materials and production method as in Example 1 except for the surface protective layer 8.

<Comparative Example 3>
As the surface protective layer 8 of Comparative Example 3, an isocyanate-based curing agent (“FG700” manufactured by DIC Graphics Co., Ltd.) is used with respect to 100 parts by mass of an acrylic polyol resin (“Acrycot QT510-15ED” manufactured by Taisei Fine Chemical Co., Ltd.). A coating solution obtained by stirring and mixing 10 parts by mass with ethyl acetate to an appropriate viscosity was applied so that the coating amount after drying was 6.5 g / m ² , followed by warm drying at 40 ° C. for 3 days. To make a decorative sheet.
A decorative sheet was produced using the same materials and production method as in Example 1 except for the surface protective layer 8.

Each evaluation result of the above Example 1 and Comparative Examples 1-3 is put together in Table 1, and is shown.

"Evaluation method"
The floor decorative sheets of Example 1 and Comparative Examples 1 to 3 were bonded to the surface of the wooden base material to make a floor decorative material, and these floor decorative materials were evaluated by the following methods.
Here, MDF (hardwood) having a thickness of 3 mm was used as the woody base material. In addition, a two-component aqueous emulsion adhesive (“Rikabond” manufactured by Chuo Rika Kogyo Co., Ltd. (mass ratio BA-10L / BA-11B = 100: 2.5)) is wet on the surface of the wood-based substrate. After coating at 100 g / m ² , the floor decorative sheet was bonded and cured for 24 hours to obtain the above-mentioned floor decorative material.

<Slipper sliding test>
In order to evaluate surface durability aptitude, the bottom surface was rubbed 35,000 times with a load of 80 g / cm ² using a slipper made of vinyl chloride, and the degree of increase in gloss value was confirmed. In the 60-degree gloss value measurement, a gloss value change within ± 2 was regarded as acceptable “◯”, and other than ± 2 was regarded as unacceptable “x”.
<V-cut processing test>
In order to evaluate the suitability of bending, from the MDF surface of the flooring decorative material, leave only the flooring decorative sheet, and insert a V-shaped groove at an angle of 90 degrees. Appearance was evaluated. The case where a crack could not be confirmed was evaluated as “good”, and the case where a crack was confirmed was determined as “failed”.

<Metal weather test>
In order to evaluate the weather resistance, the weather resistance evaluation was performed using a metal weather manufactured by Daipura Wintes Co., Ltd. As irradiation mode, irradiation energy 650W / m2 (using Ushio Denki's UVD-365PD irradiator), black panel temperature 53 ° C, humidity 70%, irradiation time 20 hours, condensation mode as black panel temperature 30 ° C, humidity 98%, condensation time 4 hours. As the rain conditions, 10 cycles were tested with 1 cycle of 2 hours of rainfall every 1 hour in the irradiation mode, irradiation mode + dew condensation mode. The case where there was no significant change in the appearance state was judged as “good”, and the case where the surface had a gloss change due to cracks and cracks, and the case was cracked was judged as “failed”.

<Evaluation results>
As can be seen from Table 1, in Example 1, which is the scope of the present invention, it was confirmed that the slipper sliding test, the V-cut processing test, and the metal weather test were good. That is, it was confirmed that the decorative sheet for floors was excellent in winding property, scratch resistance, and slipper slidability.
On the other hand, in Comparative Examples 1 and 3, slipper slidability was rejected, and there was a problem in surface durability. Further, in Comparative Example 2, the V-cut processing test and the metal weather test were rejected, and there was a problem in winding property and weather resistance.

DESCRIPTION OF SYMBOLS 1 Thermoplastic resin base material 2 Picture pattern layer 3 Primer layer 4 Urethane resin adhesive layer 5 Transparent adhesive resin layer 6 Transparent thermoplastic resin layer 7 Primer layer 8 Surface protective layer

Claims (3)

A primer layer, a thermoplastic resin base material, a pattern layer, a urethane resin adhesive layer, a transparent adhesive resin layer, a transparent thermoplastic resin layer, a primer layer, and a surface protective layer are provided at least in this order.
The surface protective layer is an ionizing radiation curable resin comprising at least one selected from polyfunctional (meth) acrylate monomers or oligomers having two or more polymerizable groups, a dendritic polymer, and a radical photopolymerization initiator; A decorative sheet for floors, which is a resin layer made of a mixture with a thermosetting resin.   The decorative sheet for floor according to claim 1, wherein the dendritic polymer is a hyperbranched polymer.   3. The decorative sheet for floor according to claim 1, wherein at least a part of the end of the branched chain of the dendritic polymer has one or more polymerizable groups.

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