JP5515938B2 - Floor decorative sheet - Google Patents

Description

  The present invention relates to a decorative sheet for floors used by being bonded to the floor material surface used for floors of apartments, condominiums, ordinary houses and public buildings, and in particular, has excellent sliding resistance before construction and scratch resistance after construction. The present invention relates to a decorative sheet for floors that has excellent adhesion.

When the flooring material used for the above-mentioned use is manufactured and then transported to a place where it is constructed, it is generally packed so that the surface thereof is matched and the surface is not damaged.
Moreover, in order to improve the designability, the flooring material is used in which a decorative sheet is bonded to the surface. As such a decorative sheet, in order to prevent living wounds from being attached to the surface after construction, inorganic fine particles such as glass beads and silica are added to the surface protective layer, or crosslinked and cured using an ionizing radiation curable resin, Or do both.

However, in recent years, since the caster resistance of flooring materials has been regarded as important, the material of the wooden base material has been improved and has become heavy. As the floor material becomes heavier, the problem of slidability has arisen in which the surfaces of the floor material rub against each other and scratch each other.
In order to solve the problem of slidability, the surface of the floor material may be made slippery. However, if the floor surface is too slippery after the construction, it becomes dangerous such as a fall.

JP2008-115657 JP2008-108616

  The present invention has been made in order to solve such problems. That is, the problem is that there is no problem of slidability before construction, and there is no problem of slidability even after construction. An object of the present invention is to provide a decorative sheet for floors having excellent adhesion.

  The present invention solves this problem. That is, the invention according to claim 1 includes at least a colored thermoplastic resin layer, a design pattern layer, a transparent thermoplastic resin layer, and a surface protective layer on a wooden base material. In the decorative sheet for floors in this order, the surface protective layer has at least two layers of a lower surface protective layer on the substrate side and an upper surface protective layer on the surface side, and the lower surface protective layer has a Mohs hardness of 4.0. A floor decorative sheet comprising the above inorganic fine particles, wherein the upper surface protective layer contains inorganic fine particles having a Mohs hardness of less than 4.0 and wax.

  The invention according to claim 2 is the decorative sheet for floor according to claim 1, wherein the resin used for the surface protective layer is made of an ionizing radiation curable resin.

  According to the present invention, the invention according to claim 1 makes it possible to obtain excellent surface hardness due to the hard inorganic fine particles of the lower surface protective layer. With the soft inorganic fine particles and the wax of the upper surface protective layer, moderate slipperiness can be obtained. A decorative sheet for floors having slidability can be obtained. According to the second aspect of the present invention, a decorative sheet for floors having better slidability and surface hardness can be obtained by using an ionizing radiation curable resin as the resin used for the surface protective layer.

It is explanatory drawing which shows the structure of the cross section of one Example of the decorative sheet for floors of this invention.

  Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 shows a cross-sectional structure of an embodiment of the floor decorative sheet of the present invention. A colored thermoplastic resin layer 2, a pattern layer 3, a transparent thermoplastic resin layer 4, a lower surface protective layer 5, and an upper surface protective layer 6 are provided on a wood-based substrate 1. An adhesive layer (not shown) made of an appropriate adhesive may be provided between these layers. The surface of the transparent thermoplastic resin layer 4 may have a satin-like unevenness (not shown).

  The wood-based flooring 1 in the present invention is not particularly limited as long as it can be used for floor surfaces such as wood and plywood, and is obtained by foaming a mixture of wood powder in a synthetic resin. It may be.

  As the colored thermoplastic resin layer 2 in the present invention, any material may be used as long as it has strength as a base material of the decorative sheet and coloring that conceals the surface of the woody base material. For example, any known thermoplastic resin that has been conventionally used as a material for a base sheet for a decorative sheet can be used. Specifically, for example, polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, polyolefin resins such as ethylene-vinyl acetate copolymer or a saponified product thereof, and ethylene- (meth) acrylic acid (ester) copolymer. Copolymer, Polyethylene terephthalate, Polybutylene terephthalate, Polyethylene naphthalate, Polyarylate, Polyester resin such as polycarbonate, Acrylic resin such as polymethyl methacrylate, 6-Nylon, 6,6-Nylon, 6,10-Nylon Polyamide resins such as polystyrene resins, styrene resins such as acrylonitrile-styrene copolymer resins (hereinafter referred to as AS), acrylonitrile-butadiene-styrene copolymer resins (hereinafter referred to as ABS), cellulose acetate, nitrile Fibrin derivatives such as cellulose, chlorine-based resins such as polyvinyl chloride and polyvinylidene chloride, fluorine-based resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer, etc. Two or three or more types of copolymers or mixtures, composites, laminates, and the like selected from can be used. A thickness of about 50 to 150 μm is preferable in terms of ease of printing and ease of pasting when the shape is maintained to some extent when pasting on a substrate.

  As a colorant for coloring, it is desirable to use an inorganic pigment having a high refractive index and excellent weather resistance and hiding properties. Specifically, for example, yellow lead, yellow iron oxide, titanium yellow, barium yellow, quinacridone, aureolin, molybdate orange, petal, mars violet, manganese violet, cobalt violet, cobalt blue, cerulean blue, ultramarine blue, bitumen, emerald Colored pigments such as green, viridian, iron black and carbon black, such as titanium oxide (titanium white, titanium white), zinc oxide (zinc white), basic lead carbonate (lead white), basic lead sulfate, zinc sulfide, White pigments such as lithopone and titanox can be used.

  Further, various additives such as various fillers, ultraviolet absorbers such as benzotriazole-based, benzophenone-based, triazine-based, hindered amine-based light stabilizers, hindered phenol-based antioxidants may be appropriately added. . The above resins can be used alone or in admixture of plural kinds.

  The pattern layer 3 in the present invention is provided by means such as gravure printing on the surface side of the colored thermoplastic resin layer 2 or on the back side of the transparent thermoplastic resin layer 4 described later. Specific examples include two-component curable urethane resin-based ink and vinyl chloride resin-based ink. Examples of pigments include inorganic pigments such as carbon black, titanium white, zinc white, petal, and bitumen, and organic pigments such as azo pigments, lake pigments, anthraquinone pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, and dioxazine pigments. Metal powder pigment such as gold powder, silver powder, copper powder, aluminum powder, bronze powder, pearl luster pigment such as fish scale powder, basic lead carbonate, bismuth oxide oxide, titanium oxide coated mica, fluorescent pigment, nocturnal pigment, etc. A mixture of two or more selected can be used. Further, various additives such as various fillers, ultraviolet absorbers such as benzotriazole-based, benzophenone-based, triazine-based, hindered amine-based light stabilizers, hindered phenol-based antioxidants may be appropriately added. .

  As the transparent thermoplastic resin layer 4 in the present invention, the same resin as the colored thermoplastic resin layer 2 can be used, but a polyolefin resin is preferable from the viewpoint of transparency and processability. Moreover, the transparent thermoplastic resin layer 4 in this invention may provide a conduit | pipe or a satin-like unevenness | corrugation in the surface side. As a method of providing the transparent thermoplastic resin layer 4, a transparent thermoplastic resin layer in which surface irregularities are provided in advance on the surface of the colored thermoplastic resin layer 2 provided with the pattern layer 3 through an adhesive layer as appropriate. 4 and a method of directly providing the transparent thermoplastic resin layer 4 by simultaneous embossing of the molten resin, but are not particularly limited thereto. The thickness is preferably about 50 to 150 μm.

  The lower surface protective layer 5 in the present invention is provided in order to obtain various resistances of the decorative sheet surface, and particularly affects physical properties items of scratch resistance (for example, pencil hardness test and Dupont impact test). In the present invention, in particular, those comprising a resin layer containing inorganic fine particles having a Mohs hardness of 4.0 or more are used. The resin to be used is not particularly limited, and a known thermosetting resin or ionizing radiation resin can be used, and an ultraviolet curable resin is particularly preferable. The layer thickness of the lower surface protective layer 5 is not particularly limited, but is preferably 5 to 10 μm in consideration of balance with other layers and winding with a roll.

The content of inorganic fine particles contained in the lower surface protective layer 5 is preferably 1 to 20% by weight. When the amount is less than 1% by weight, the scratch resistance becomes insufficient. When the amount is more than 20% by weight, the binder effect with the resin is reduced, and the problem that the inorganic fine particles are easily detached from the resin arises.
As the inorganic fine particles contained in the lower surface protective layer 5, those having a Mohs hardness of 4.0 or more are used. If the Mohs hardness is less than 4.0, the scratch resistance becomes insufficient. Examples of inorganic fine particles having a Mohs hardness of 4.0 or more include glass beads, alumina, zirconia, and silicon dioxide. The shape of the inorganic fine particles contained in the lower surface protective layer 5 is not particularly limited. However, if the particle size is too larger than the layer thickness, it tends to come off from the resin and the printed pattern tends to be difficult to see. It is preferable to be slightly less than double.

  The upper surface protective layer 6 in the present invention is provided in order to obtain various resistances on the surface of the decorative sheet, and particularly affects physical properties such as slipperiness, slidability, and scratch resistance. In the present invention, those comprising a resin layer containing inorganic fine particles having a wax and Mohs hardness of 2.0 to 4.0 are particularly used. The resin to be used is not particularly limited, and a known thermosetting resin or ionizing radiation resin can be used, and an ultraviolet curable resin is particularly preferable. The layer thickness of the upper surface protective layer 6 is not particularly limited, but is preferably 5 to 10 μm in consideration of balance with other layers and winding with a roll.

  As the wax, it can be appropriately selected from known natural waxes or synthetic waxes. Examples of natural waxes that can be used in the present invention include animal waxes such as beeswax, wool fat and whale wax, vegetable waxes such as carnauba wax and tree wax, or mineral waxes such as montan wax and paraffin wax. Is mentioned. Examples of synthetic waxes include acrylic or acrylic-styrene emulsions.

  The content of the wax contained in the upper surface protective layer 6 is preferably 1 to 5% by weight although there is a balance with the inorganic fine particles contained at the same time. If it is less than 1% by weight, the slidability problem occurs that the surfaces are scraped off and damaged. If it exceeds 5% by weight, the surface layer becomes slippery, so it is inappropriate for a floor sheet.

The content of inorganic fine particles contained in the upper surface protective layer 6 is preferably 1 to 20% by weight. If the amount is less than 1% by weight, the above-mentioned wax effect is stronger and the surface of the flooring tends to slip. When it exceeds 20% by weight, the binder effect with the resin is reduced, and the problem that the inorganic fine particles are easily detached from the resin arises.
As the inorganic fine particles contained in the upper surface protective layer 6, those having a Mohs hardness of 2.0 to 4.0 are used. If the Mohs hardness is less than 2.0, the effect is not obtained because it is too soft. If the Mohs hardness is 4.0 or more, the resin in the surface layer is too hard and a sliding problem occurs. Examples of inorganic fine particles having a Mohs hardness of 2.0 to 4.0 include silica, selenite, alabaster, fluorite, malachite, and mica.
The particle size of the inorganic fine particles contained in the upper surface protective layer 6 is preferably less than twice the layer thickness because it tends to be detached from the resin if it is much larger than the layer thickness and the printed pattern tends to be difficult to see. .
The form of the inorganic fine particles contained in the upper surface protective layer 6 is not particularly limited, but the effect of the indefinite form can be expected because the function of preventing the wax from slipping is excessive.

  A 70 μm thick polyester film (made by Riken Technos Co., Ltd.) is used as the colored thermoplastic resin layer 2, and a gravure ink (“Lamister” made by Toyo Ink Co., Ltd.) is used to print a wood grain print on a single side with a gravure printing machine. Thus, the pattern layer 3 was obtained. Thereafter, a two-component urethane primer resin containing silica powder on the surface opposite to the printed surface was applied with a gravure so that the thickness after drying was 1 μm.

  Thereafter, a two-component urethane resin adhesive having a polyester polyol as a main component and isophorone diisocyanate as a curing agent is applied on the pattern layer 3 so that the coating amount after drying is 2 g / m 2. As the plastic resin layer 4, a transparent polypropylene resin and an adhesive resin (maleic acid-modified polypropylene resin) are used. The thickness of the transparent polypropylene resin is 80 μm, the thickness of the adhesive resin is 20 μm, and the adhesive resin is on the pattern layer 3 side. Co-extrusion lamination was performed.

  A two-part curable acrylic urethane resin containing 100 parts by weight of acrylic polyol and 10 parts by weight of polyisocyanate (hexamethylene diisocyanate) on the surface of the transparent thermoplastic resin layer 4 has an average particle size of 6 μm and a Mohs hardness of 6 7 parts by weight of spherical glass beads of .5 were added, applied to a thickness of 8 μm, and cured by hot air drying to provide the lower surface protective layer 5.

  On the surface of the lower surface protective layer 5, a benzotriazole-based ultraviolet absorbent 0.5 is added to a two-part curable acrylic urethane resin containing 100 parts by weight of acrylic polyol and 10 parts by weight of polyisocyanate (hexamethylene diisocyanate). Part, 0.2 part of a hindered amine light stabilizer, 1 part of spherical polyethylene wax having an average particle diameter of 6 μm and 4 parts of amorphous silica having an average particle diameter of 5 μm and a Mohs hardness of 3.0 are added so that the thickness becomes 8 μm. It was applied and cured by hot air drying to provide an upper surface protective layer 6 to obtain a floor decorative sheet of the present invention.

  The upper surface protective layer 6 of Example 1 is made of 100 parts of urethane acrylate ("Ebecryl 4858" manufactured by Daicel Usubi Co., Ltd.) and 20 parts of pentaerythritol tetraacrylate ("PETA-K" produced by Daicel Usubi Co., Ltd.), benzophenone -Based photoinitiator ("Ebecryl BZO" manufactured by Daicel-Usibi Co., Ltd.) 0.5 part, benzotriazole-based UV absorber 0.5 part, hindered amine-based light stabilizer 0.5 part, spherical polyethylene having an average particle size of 6 μm An upper surface protective layer is formed by applying an ultraviolet curable resin to which 1 part of wax and 4 parts of amorphous silica having an average particle size of 5 μm and Mohs hardness 3.0 are added to a thickness of 8 μm and cured by ultraviolet irradiation with a metal halide lamp. A decorative sheet for flooring was obtained in the same manner as in Example 1 except for using 6.

<Comparative Example 1>
A decorative sheet for flooring was obtained in the same manner as in Example 1 except that the wax contained in the upper surface protective layer 6 was removed.

<Comparative example 2>
Example 1 except that an amorphous glass bead with an average particle size of 5 μm and a Mohs hardness of 6.0 was used instead of the amorphous silica with an average particle size of 5 μm and a Mohs hardness of 3.0 contained in the upper surface protective layer 6. Similarly, a flooring decorative sheet was obtained.

<Comparative Example 3>
Similar to Example 1 except that in place of spherical glass beads having an average particle size of 6 μm and a Mohs hardness of 6.5 contained in the lower surface protective layer 5, amorphous silica having an average particle size of 6 μm and a Mohs hardness of 3.0 was used. A flooring decorative sheet was obtained.

<Comparative Example 4>
A flooring decorative sheet was obtained in the same manner as in Example 1 except that the upper surface protective layer was formed by removing amorphous silica having an average particle diameter of 5 μm and a Mohs hardness of 3.0 contained in the upper surface protective layer 6.

<Comparative Example 5>
A flooring decorative sheet was obtained in the same manner as in Example 1 except that the upper surface protective layer was formed by removing spherical glass beads having an average particle size of 6 μm and a Mohs hardness of 6.5 contained in the lower surface protective layer 5.

<Performance evaluation method>
Using a 12 mm thick plywood, a two-part aqueous emulsion adhesive ("Rikabond" manufactured by Chuo Rika Kogyo Co., Ltd. ("BA-20" and "BA-11B" mixed in 100 parts: 5 parts) was used on this surface. And after applying this to 100 g / m <2> in a wet state, the said Example 1-Example 2 and the coloring thermoplastic resin layer side of the decorative sheet of Comparative Example 1-Comparative Example 5 were bonded together with the laminator, 12 Time-cured and used as flooring.

<Slidability evaluation>
The flooring was made to face to face, a load of 500 g / cm 2 was applied from above the face to face, and the flooring was rubbed back and forth 2000 times, and then the surface of the flooring was observed. The evaluation method was as follows: the surface state did not change at all, ◎, slightly scratched (no problem in practical use), ◯, scratched, and the surface coating could be scraped.

<Slippery evaluation>
Using a dry bore amuse (“TYPE: 94iII” manufactured by HEIDON), the sliding piece was covered with stockings, and the coefficient of static friction between the flooring and the sliding piece was measured. 0.4..., Less than 0.3.

<Scratch resistance evaluation>
As an evaluation of scratch resistance, a pencil hardness test was performed. The test method conforms to JIS K 5600-5-4 paint general test method scratch hardness (pencil method). The evaluation method visually confirmed the hardness of the pencil that began to scratch.
The results are shown in Table 1.

  The decorative sheet for floor of the present invention can be used by being bonded to the floor material surface used for the floor surface of apartments, condominiums, ordinary houses and public buildings.

DESCRIPTION OF SYMBOLS 1 ... Wood type base material 2 ... Colored thermoplastic resin layer 3 ... Picture pattern layer 4 ... Transparent thermoplastic resin layer 5 ... Lower surface protective layer 6 ... Upper surface protective layer

Claims (2)

  In a decorative floor sheet having a colored thermoplastic resin layer, a pattern layer, a transparent thermoplastic resin layer, and a surface protective layer in this order on a wooden substrate, the surface protective layer is a lower surface protective layer on the substrate side. And the upper surface protective layer on the surface side, the lower surface protective layer contains inorganic fine particles having a Mohs hardness of 4.0 or more, and the Mohs hardness is 4.0 in the upper surface protective layer. A decorative sheet for floors comprising less inorganic fine particles and wax.   The decorative sheet for floor according to claim 1, wherein the resin used for the surface protective layer is made of an ionizing radiation curable resin.

Images