JP2016169509A - Decorative sheet for floor and decorative material for floor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat-insulating decorative sheet for a floor that prevents warping caused by infrared light.SOLUTION: A decorative sheet 3 is manufactured by forming a thermoplastic resin base layer 11, a printed layer 13, and a surface protection layer 19 in this order. The surface protection layer 19 contains 10 pts.mass or more and 20 pts.mass or less of glass beads 31 having a diameter between 1/3 or more and 2/3 or less of a thickness of the surface protection layer 19, and 3 pts.mass or more and 5 pts.mass or less of a wax component 32. The printed layer 13 includes a solidly printed layer 131 and a pattern layer 132. The solidly printed layer 131 contains a pigment selected from among isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine and titanium oxide, while the pattern layer 132 has a black color reproduced by mixing isoindolinone, diketopyrrolopyrrole, and phthalocyanine pigments.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a floor decorative sheet used as a building material for floors, and a floor decorative material using the same.

A decorative sheet is used for various uses such as indoor and outdoor buildings and furniture and furniture as a building material that is inexpensive and excellent in processability. Among such decorative sheets, the decorative sheet for floors used on the floor surface may be deteriorated by being irradiated with sunlight incident from a window or the like. For this reason, weather resistance is requested | required of the decorative sheet for floors.
As a decorative sheet having weather resistance, a decorative sheet using an olefin-based material is currently in practical use. The weather resistance is evaluated by actual outdoor exposure and accelerated weather resistance test. The weather resistance of a decorative sheet using an olefin-based material satisfies a practical condition. Such a decorative sheet is described in Patent Document 1, for example.

JP 2012-131112 A

However, the existing decorative sheet is evaluated for weather resistance against ultraviolet light of sunlight, and although the prescription is applied, the weather resistance against infrared light has not been considered. In the decorative sheet for floors, heat is stored by absorbing infrared light, and the stored heat is transmitted to the base material of the decorative sheet for floors, so that expansion occurs. When the base material of the floor decorative sheet expands, the floor decorative material to which the floor decorative sheet is bonded is warped, and the beauty of the building material and the function of protecting the building are deteriorated.
This invention is made | formed in view of such a point, It aims at providing the decorative sheet for floors which has heat insulation and can prevent the curvature by infrared light, and a decorative material for floors. .

  In order to solve the above problems, a decorative sheet for floor according to one embodiment of the present invention includes a thermoplastic resin base layer, a printed layer formed on one surface of the thermoplastic resin base layer, and the printed layer. The surface protective layer is formed in this order, and the surface protective layer contains 10 to 20 parts by mass of glass beads having a particle size of 1/3 or more and 2/3 or less of the thickness of the surface protective layer. And the wax component contains 3 parts by mass or more and 5 parts by mass or less, and the printing layer has a solid printing layer and a picture layer in this order from the thermoplastic resin base material layer side, In the printing layer, the pigment is selected from isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine and titanium oxide, and in the pattern layer, black is an isoindolinone pigment, diketopyrrolopyrrole pigment Phthalo Characterized in that it is reproduced by mixing the cyanine pigment

  ADVANTAGE OF THE INVENTION According to this invention, it can provide the decorative sheet for floors and flooring cosmetics which have heat insulation and can prevent the curvature by infrared light.

It is sectional drawing of the decorative material for floors using the decorative sheet for floors of one Embodiment of this invention, and the decorative sheet for floors.

Hereinafter, a floor decorative sheet and a floor decorative material according to an embodiment of the present invention will be described.
(Flooring material)
FIG. 1 is a cross-sectional view for explaining a floor decorative material 1 of the present embodiment. Such a floor decorative material 1 includes a base material 20, a floor decorative sheet 3 bonded to the base material 20, and a first adhesive layer 21 bonded to the base material 20 and the floor decorative sheet 3. doing.
The floor decorative material 1 of the present embodiment is such that the floor decorative material 1 of the present embodiment increases the transmittance of the printing layer 13 for infrared light having a wavelength of 0.7 μm to 1000 μm, and heats the transmitted infrared light. Reflection by the plastic resin base material layer 11 prevents heat storage of the base material 20.

(Decorative sheet for floor)
The decorative sheet 3 for floor has a thermoplastic resin base layer 11, a printed layer 13 formed on one surface of the thermoplastic resin base layer 11, and a surface protective layer 19 of the printed layer 13 in this order. It is formed. That is, the decorative sheet 3 for floor is provided with the thermoplastic resin base layer 11, the printing layer 13, the second adhesive layer 15, the overlay film layer 17, and the surface protective layer 19 provided in this order from the thermoplastic resin base material 11 side. Have.
Hereinafter, each layer of the decorative sheet for floor 3 will be described.

<Thermoplastic resin base material layer>
The thermoplastic resin base material layer 11 is a colored base material such as a colored base film layer. The type of the thermoplastic resin used for the thermoplastic resin base material layer 11 is not particularly limited. For example, a known thermoplastic resin used as a material for a base material sheet for a decorative sheet may be arbitrarily used. it can.

  Specifically, as the thermoplastic resin substrate layer 11, for example, polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer or saponified product thereof, ethylene- (meth) acrylic acid Polyolefin copolymers such as (ester) copolymers, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate and polycarbonate, acrylic resins such as polymethyl methacrylate, 6-nylon, 6 Polyamide resins such as 1,6-nylon and 6,10-nylon, polystyrene resins, styrene resins such as acrylonitrile-styrene copolymer resins, acrylonitrile-butadiene-styrene copolymer resins, cellulose acetate, nitrose Fiber derivatives such as loin, chlorinated resins such as polyvinyl chloride and polyvinylidene chloride, fluorinated resins such as polyvinyl fluoride, polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer, or the like Two or three or more types of copolymers or mixtures, composites, laminates, and the like selected from can be used.

As a molding method of the thermoplastic resin base material layer 11, for example, an extrusion molding method, an inflation molding method, a calendar molding method, a cast molding method, or the like can be used. Further, in the present embodiment, the surface of the thermoplastic resin substrate layer 11 may be embossed simultaneously with extrusion, or may be embossed after extrusion.
The thickness of the thermoplastic resin base material layer 11 is preferably in the range of about 20 μm to 200 μm, more preferably in the range of about 50 μm to 150 μm, from the viewpoint of ease of printing and ease of application to the base material 20. It is.

  When the thermoplastic resin base material layer 11 is colored, it is desirable to use an inorganic pigment excellent in high refractive index, weather resistance and hiding properties as a colorant. Inorganic pigments include, for example, yellow lead, yellow iron oxide, titanium yellow, barium yellow, quinacridone, aureolin, molybdate orange, dial, mars violet, manganese violet, cobalt violet, cobalt blue, cerulean blue, ultramarine blue, bitumen, Colored pigments such as emerald green, viridian, iron black, carbon black, 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. In addition, various fillers and weathering prescription additives (benzotriazole-based, benzophenone-based, triazine-based UV absorbers, hindered amine light stabilizers, hindered phenol-based antioxidants, etc.) may be added as appropriate. Is optional. Further, the above resins may be used singly or as a mixture of plural kinds.

  Moreover, in this embodiment, in order to improve the reflectance of the infrared light in the thermoplastic resin base material layer 11, you may add a titanium oxide to the said material and make it contain in a thermoplastic resin base material layer. At this time, in this embodiment, when the thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide, the heat shielding property is improved. When titanium oxide is used for coloring the base material, the total of the content of titanium oxide added for coloring and the titanium oxide added for reflection may be 23 parts by mass or more. Moreover, when the thermoplastic resin base material layer 11 contains 23 mass parts or more of titanium oxide added for coloring, it is not necessary to add titanium oxide any more.

However, when the amount of titanium oxide added to the thermoplastic resin substrate layer 11 increases, the titanium oxide affects the film quality of the thermoplastic resin substrate layer 11. For this reason, suitable content of the titanium oxide of the thermoplastic resin base material layer 11 is 23 mass parts or more and 40 mass parts or less.
In the present embodiment, as shown in FIG. 1, a titanium oxide layer 111 may be provided by applying titanium oxide to the surface of the thermoplastic resin base material layer 11 on the printed layer 13 side. Even when the titanium oxide layer 111 is provided, if the thermoplastic resin base material layer 11 contains 23 parts by mass or more of titanium oxide by the titanium oxide layer 111, the thermoplastic resin base material layer 11 can be applied to the base material 20. Thermal insulation is improved. Under such conditions, the thickness of the titanium oxide layer 111 is preferably 5 μm to 10 μm.

<Print layer>
The printing layer 13 of the present embodiment is provided by gravure printing or the like using an ink using a pigment. The printing layer 13 of this embodiment includes a solid printing layer 131 and a pattern layer 132. The solid print layer 131 is a print layer without a pattern, and the picture layer 132 is a layer for applying an arbitrary pattern to the decorative sheet 3. Examples of the pattern include a wood grain pattern, a stone pattern, a cloth pattern, an abstract pattern, and a geometric pattern. Further, when the design is merely colored or color-adjusted, it may be a solid color. As the pattern of the pattern layer 132, an arbitrary pattern can be adopted according to the use of the decorative sheet 3.

In addition, the solid print layer and the pattern layer 132 may be either a single layer or a laminate of a plurality of layers.
The ink used for the solid print layer 131 and the pattern layer 132 may be any ink that can be printed on the thermoplastic resin base material layer 11. Specifically, the thermoplastic resin base material layer 11 is a random polypropylene resin. If present, a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin is preferably used.

  In the present embodiment, a pigment selected from isoindolinone, disazo, polyazo, diketopyrrolopyrrole, quinacridone, phthalocyanine, and titanium oxide is used as a pigment for the solid print layer 131. In addition, when the solid print layer 131 is provided and the pattern layer 132 represents, for example, a wood conduit, a black pigment is not used, but a black color is obtained by mixing isoindolinone, diketopyrrolopyrrole, and phthalocyanine pigment. To reproduce.

With this configuration, the present embodiment obtains a deep design by combining the pattern layer 132 with the solid print layer 131, suppresses color change over time, and makes the reflectance in the infrared region more than a certain level. It is possible to raise.
The inventors of the present invention printed a wood grain pattern on the solid print layer 131 as described above, and measured the total infrared light transmittance of the print layer 13. According to this measurement, the transmittance of light having a wavelength of 0.781 μm to 2.5 μm was 40% or more.

In addition, for the printing layer 13, for example, extender pigments, plasticizers, dispersants, surfactants, tackifiers, adhesion assistants, drying agents, heat stabilizers, weathering stabilizers, curing agents, curing accelerators. Various additives such as an agent or a curing retarder can be appropriately added.
The method for forming the printing layer 13 is not particularly limited, and various known printing methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method, and an ink jet printing method are used. be able to. In addition, for example, in the case of a solid surface, in addition to the above-described various printing methods, for example, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, kiss coating method, flow coating method Various coating methods such as a dip coating method can also be used. In addition, for example, the hand-drawn method, the ink sink method, the photographic method, the laser beam or electron beam drawing method, the partial vapor deposition method of metal or the like, the etching method, etc., or a combination of these methods can of course be performed.

  Further, prior to the formation of the printing layer 13, if necessary, the surface of the thermoplastic resin substrate layer 11 is subjected to, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment. By performing the surface treatment, the adhesion between the thermoplastic resin base material layer 11 and the printing layer 13 can be improved.

<Second adhesive layer>
The second adhesive layer 15 is provided for the purpose of enabling adhesion by a dry laminating method between the olefin-based thermoplastic resin base material layer 11 and the overlay film layer 17 and expressing adhesive strength between the two layers. It is. The second adhesive layer 15 is made of at least one of acrylic resin, polyester resin, and vinyl chloride = vinyl acetate copolymer resin.

In the present embodiment, in particular, an adhesive made of a urethane resin having a polyester resin as a main chain is employed as the second adhesive layer 15. Examples of the adhesive made of a urethane resin include a polyester polyol type and the like and a two-component urethane resin adhesive of hexamethylene diisocyanate, tolylene diisocyanate, and a mixture thereof as a curing agent. The second adhesive layer 15 is formed by applying such an adhesive so that the thickness after drying becomes 2 μm to 10 μm.
Depending on the intended use of the decorative sheet for flooring, the second adhesive layer 15 may have, for example, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, One or more conventionally known various additives such as a fuel and a filler may be added.

<Overlay film layer>
As the overlay film layer 17, a single layer or a plurality of layers made of polyvinyl chloride resin, amorphous crystalline polyester resin, amorphous polyester resin, biaxially stretched polyester resin, polypropylene resin, polyethylene resin, or the like is used. The The thickness of the overlay film layer 17 is preferably 70 μm to 200 μm in consideration of weather resistance, heat resistance, ease of winding, scratch resistance, and the like.

The overlay film layer 17 needs to have at least transparency that allows the printed layer 13 as a lower layer to be seen through, and is most preferably colorless and transparent, but may be colored and transparent or translucent. As long as this is the case, the overlay film layer 17 may contain a colorant or a filler.
The surface of the overlay film layer 17 can be appropriately provided with an emboss having a desired pattern as necessary. There is no particular limitation on the type of embossed pattern, and for example, it may be various patterns such as wood grain (particularly conduit pattern), stone texture, fabric texture, Japanese paper texture, geometric pattern, etc. It may be a simple matte shape, grain shape, hairline shape, suede tone or the like. Further, the design can be further improved by synchronizing these embossed patterns with the pattern of the printed layer 13, but if not necessary, the pattern of the printed layer 13 may be out of sync. Embossing of a pattern including both a pattern synchronized with and a pattern not synchronized can be provided.

  The embossing method is not particularly limited, but a mechanical embossing method using a metal embossing plate is the most common. Moreover, there is no restriction | limiting in particular also in the formation time of embossing, Arbitrary time can be selected from before lamination | stacking with the thermoplastic resin base material layer 11 of the transparent acrylic resin film 5, or after lamination | stacking, Moreover, the same or different pattern embossing can be performed a plurality of times at a plurality of times selected from the respective times.

<Surface protective layer>
The surface protective layer 19 in the present invention is provided to obtain various resistances of the surface of the decorative sheet for floors, and a known curable resin can be used, and an ultraviolet curable resin is particularly preferable.
In this embodiment, the surface of the overlay film layer 17 is coated with a material obtained by adding 10 parts of hexamethylene diisocyanate, 5 parts of UV absorber, and 5 parts of hindered amine light stabilizer to 100 parts of acrylic polyol. The surface protective layer 19 was formed so as to have a thickness of 9 μm.

A benzotriazole-based, triazine-based UV absorber, a hindered amine light stabilizer, glass beads 31 and the like are appropriately added to the curable resin. The thickness of the surface protective layer 19, the impact resistance test, considering the recovery of the anti-caster resistance test, ² to 15 g / m ² about 6 g / m of the coating amount after drying is preferred.
The surface protective layer 19 in the present invention contains 10 parts by mass or more and 20 parts by mass or less of glass beads 31 having an average particle diameter of 1/3 or more and 2/3 or less of the layer thickness of the surface protective layer 19. If the average particle size of the glass beads 31 is larger than 2/3 of the layer thickness, the area where the glass beads 31 protrude from the coating surface increases so much that the layers are damaged when the decorative sheets for flooring are laminated. . Further, the separation of the glass beads 31 increases, and the desired physical property values cannot be obtained.

  On the other hand, if the average particle diameter of the glass beads 31 is smaller than 1/3 of the layer thickness, the glass beads 31 will also reach the coating surface, and the effect of improving scratch resistance cannot be obtained. When the glass bead content is less than 10 parts by mass, the effect of improving the scratch resistance cannot be obtained, and when the glass bead 31 content is more than 30 parts by mass, the decorative sheet is easily damaged. turn into.

As the glass beads 31 in the present invention, known glass beads (silica-based, spherical, refractive index of about 1.47) can be used and can be obtained easily and inexpensively. In particular, spherical particles having a refractive index close to that of the surface protective layer 19, a uniform inside, high transparency, close to a true sphere, and a smooth surface are preferable.
The surface protective layer 19 in the present invention contains 3 parts by mass or more and 5 parts by mass or less of the wax component 33. When the content of the wax component 33 is less than 3 parts by mass, the surface protective layer 19 is easily damaged when the decorative sheet for flooring is laminated. On the other hand, when the content of the wax component 33 exceeds 5 parts by mass, the surface of the surface protective layer 19 becomes slippery.

  As the wax component 33 of the present embodiment, 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. There is. As the synthetic wax, for example, an acrylic or acrylic-styrene emulsion can be used.

(Base material)
The base material 20 is used by sticking (laminating) the floor decorative sheet 3 to the surface. The base material 20 includes various materials such as a metal base material and a wood base material. An example of the metal base material is an Alpolic material. The Alpolic material is an aluminum resin composite plate in which a resin material is sandwiched between metal plates that have been subjected to surface processing such as painting or mirror finishing. As the metal plate, aluminum, galvalume steel plate, stainless steel, titanium or the like is used. As the resin material, polyethylene alone or a material obtained by adding an inorganic material to polyethylene is used.
Moreover, as a wood-type base material, MDF (medium density fiberboard), a plywood, a particle board etc. are used, for example.
For attaching the sheet 3 to the base material 20, for example, an appropriate adhesive such as urethane or vinyl acetate is used.

(First adhesive layer)
As the 1st contact bonding layer 21, if it is a well-known adhesive used for bonding of the decorative sheet for floors and a base material, what kind of thing may be used. In the present embodiment, for example, the first adhesive layer 21 can be formed using a reactive hot-melt adhesive. In particular, the first adhesive layer 21 may be formed using a two-component polyurethane adhesive among reactive hot-melt adhesives. Among such first adhesive layers 21, in the present embodiment, it is particularly preferable to use a member that has been certified non-combustible according to the regulations of the Japan Wallcovering Association.

The first adhesive layer 21 may contain an ultraviolet absorber or a light stabilizer. The thickness of the first adhesive layer 21 is preferably about 5 μm to 50 μm.
According to the present embodiment described above, the color of the isoindolinone pigment, diketopyrrolopyrrole pigment and phthalocyanine pigment is mixed to represent black, so that the light transmittance in the printed layer is higher than that of the existing decorative sheet for floors. Rise. Since the infrared light transmitted through the printing layer 13 is reflected by the thermoplastic resin base material layer, heat is not transmitted to the base material 20, and heat storage of the base material 20 can be prevented. And by preventing the heat storage of the base material 20, it is possible to obtain the flooring decorative material 1 that is less likely to be warped by sunlight even when used outdoors.

  Moreover, according to this embodiment, the filling amount of the glass beads 31 in the surface protective layer 19 is adjusted to 10 to 20 parts by mass, and the filling amount of the wax component is 3 to 5 parts by mass. Furthermore, by adjusting the particle size of the glass beads 31 within the range of 1/3 or more and 2/3 or less of the surface protective layer, which is smaller than the layer thickness, both scratch resistance and resistance to slipping are achieved. Surface characteristics can be obtained.

The embodiment described above exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is based on the material, shape, structure, arrangement, etc. of the component parts. It is not specific to the above. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.
In addition, it should be noted that the drawings in the embodiments 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. Therefore, specific thicknesses and dimensions should be determined in consideration of the above description.

Next, examples of the present invention will be described.
[Example 1]
In Example 1, 3 parts by mass of a hindered phenol antioxidant, 1 part by mass of an ultraviolet absorber, 1 part by mass of a hindered amine light stabilizer, and 23 parts by mass of titanium oxide are added to 100 parts by mass of a polyester resin. Thus, a thermoplastic resin base material layer was produced. The thickness of the thermoplastic resin base material layer was 150 μm.

  Next, in Example 1, a solid printing layer was formed on the surface of the colored thermoplastic resin base material layer. The solid printing layer ink is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin in a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. 3 parts by mass of the product was added, and 5.3 parts by mass of isoindolinone, 2.4 parts by mass of polyazo, and 1.7 parts by mass of phthalocyanine were added as pigments. The solid print layer is formed by printing such an ink on the entire surface of the colored thermoplastic resin base material layer.

  In Example 1, the first layer of the pattern layer was printed on the surface of the solid print layer. The ink of the first layer of the pattern layer is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin at a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. It was manufactured by adding 3 parts by mass of a mixture mixed at a ratio, and adding 6.0 parts by mass of polyazo and 3.1 parts by mass of phthalocyanine as pigments. The first layer of the pattern layer is for printing the bark portion of the wood grain pattern.

  Next, in Example 1, the second layer of the pattern layer was printed. The ink of the second layer of the pattern layer is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin in a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. It was manufactured by adding 3 parts by mass of the mixture in a proportion and adding 2.4 parts by mass of isoindolinone, 5.2 parts by mass of polyazo, and 2.7 parts by mass of phthalocyanine as pigments. The second layer of the pattern layer is for printing the bark portion of the wood grain pattern.

  Next, in Example 1, the third layer of the pattern layer was printed. The ink of the third layer of the pattern layer is a mixture of urethane resin and vinyl chloride = vinyl acetate copolymer resin in a ratio of 7: 3, and hexamethylene diisocyanate and isophorone diisocyanate as a curing agent in a ratio of 2: 8. It was manufactured by adding 3 parts by weight of the mixture in a proportion and adding 3.2 parts by weight of isoindolinone, 4.9 parts by weight of polyazo, and 3.0 parts by weight of phthalocyanine as pigments. The third layer of the pattern layer is to print a wood-patterned conduit portion.

Next, in Example 1, a two-component urethane resin adhesive having isophorone diisocyanate as a main component and having a polyester polyol as a main agent is applied onto the printing layer so that the coating amount after drying is 2 g / m ^2. Thus, an adhesive layer was produced. Next, in Example 1, an overlay film layer was provided on the adhesive layer. The overlay film layer is made of a transparent polypropylene resin and an adhesive resin (maleic acid-modified polypropylene resin) so that 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 printed layer side. Made by coextrusion lamination.

Furthermore, in Example 1, the surface of the overlay film layer, thickness after drying was provided recoat layer comprising a 2-component urethane resin so that 1 g / m ^2. And the surface protective layer 19 was provided in the surface of the recoat layer.
The surface protective layer 19 was produced by adding 100 parts by mass of urethane acrylate (“Ebecryl 4858: product name” manufactured by Daicel Usubi Co., Ltd.) and pentaerythritol tetraacrylate (“PETA-K: product name produced by Daicel Usubi Co., Ltd.). ] 20 parts by mass, 0.5 parts by mass of benzophenone photoinitiator (“Ebecryl BZO: product name” manufactured by Daicel-Usibi Co., Ltd.), 0.5 parts by mass of benzotriazole UV absorber, hindered amine light stabilizer An ultraviolet curable resin added with 0.5 parts by mass, 15 parts by mass of spherical glass beads having an average particle diameter of 6 μm and 4 parts by mass of a polyethylene wax component having an average particle diameter of 6 μm was applied to a thickness of 15 μm, and a metal halide lamp was used. This was done by curing by UV irradiation.
The floor decorative sheet of Example 1 was obtained through the above steps.

[Example 2]
In Example 2, the production of the thermoplastic resin base material layer was carried out only in that diketopyrrolopyrrole 2 parts, quinacridone 2 parts, phthalocyanine 1 part, and titanium oxide were added as pigments to 23 parts. And production conditions are different. Other manufacturing conditions are the same as those in Example 1.

[Example 3]
Example 3 is different from Example 1 in the production conditions only in that an antioxidant, an ultraviolet absorber and a hindered amine light stabilizer are not added in the production of the thermoplastic resin base material layer. Other manufacturing conditions are the same as those in Example 1.
Moreover, in order to compare with the decorative sheet for floors of Example 1 and Example 2, the inventors of this invention produced the decorative sheet for floors used as a comparative example.

[Comparative Example 1]
In the decorative sheet for floor of Comparative Example 1, carbon black was used as a black pigment in the printed layer of Example 1. Other manufacturing conditions for the decorative sheet for flooring are the same as in Example 1.
[Comparative Example 2]
The decorative sheet for floor of Comparative Example 2 is produced by changing the filling amount of the glass beads of the surface protective layer of Example 1 from 15 parts by mass to 0. Other manufacturing conditions for the decorative sheet for flooring are the same as in Example 1.

[Comparative Example 3]
The decorative sheet for floor of Comparative Example 3 is manufactured by changing the filling amount of the glass beads of the surface protective layer of Example 1 from 15 parts by mass to 30 parts by mass. Other manufacturing conditions for the decorative sheet for flooring are the same as in Example 1.
[Comparative Example 4]
The decorative sheet for floor of Comparative Example 4 is produced by changing the filling amount of the polyethylene wax in the surface protective layer of Example 1 from 4 parts by mass to 0. Other manufacturing conditions for the decorative sheet for flooring are the same as in Example 1.

[Comparative Example 5]
The decorative sheet for floor of Comparative Example 5 is produced by changing the filling amount of the polyethylene wax in the surface protective layer of Example 1 from 4 parts by mass to 8 parts by mass. Other manufacturing conditions for the decorative sheet for flooring are the same as in Example 1.
[Evaluation]
The inventors of the present invention evaluated the slipperiness, slidability, heat insulation performance, and heat storage performance of Example 1, Example 2, Example 3, and Comparative Examples 1 to 5, respectively.

In the evaluation, the above-described decorative sheet for floor was attached to the surface of a 12 mm thick plywood. The lamination of the floor decorative sheet and the plywood is a two-part aqueous emulsion adhesive (100 parts by mass of “Rikabond: product name” (“BA-20” and “BA-11B” manufactured by Chuo Rika Kogyo Co., Ltd.): 5 The inventors of the present invention applied the adhesive to the surface of the plywood so as to be 100 g / m ² in a wet state, and used a laminator in Example 1. The floor decorative sheets of Example 2, Example 3 and Comparative Examples 1 to 5 were bonded to the thermoplastic resin substrate layer and cured for 12 hours to prepare a floor decorative material.

<Slidability evaluation>
Evaluation of slipperiness was performed using a dry bore amuse (“TYPE: 94iII: product name” manufactured by HEIDON). The inventors of the present invention put a stocking on the floor decorative material, and measured the coefficient of static friction between the floor decorative material and the sliding piece of the measuring device.
<Scratch resistance evaluation>
The scratch resistance was evaluated by a test in which a 10-yen coin inclined at 45 degrees was contacted with a load of 1 kg to 4 kg and scratched with respect to the decorative base material for floor. In this test, the inventors of the present invention visually determined the load at which scratches began to occur.

<Slidability evaluation>
The evaluation of slidability is made by combining the surfaces of two flooring decorative materials, applying a load of 1 kg / cm ² from the back side of one flooring decorative material, and reciprocating 2000 times to obtain the surface of the flooring decorative material. It was done by rubbing each other. The inventors of the present invention visually observed the surface of the floor decorative material after rubbing.

<Heat insulation performance>
The evaluation of the heat shielding property was performed using a method for measuring the solar reflectance of the coating film defined in JIS standard, K5602. The measurement was performed with a spectrophotometer UV3600 (product name) manufactured by Shimadzu Corporation. The inventors of the present invention evaluated “◯” if the solar reflectance of the coating film was 40% or more, and evaluated “X” if it was 40% or less, according to the provisions of JIS standard, K5602. .

<Heat storage performance>
Evaluation of heat storage performance was performed using a test piece in which a decorative sheet for flooring was bonded to one surface of an uncoated steel sheet having a length of 21 cm, a width of 29.7 cm, and a thickness of 0.5 mm using an adhesive. The inventors of the present invention installed a halogen bulb at a position 15 cm above the surface of the test piece and separated from the surface, and set the temperature of the front and back surfaces of the test piece to 1 minute while irradiating halogen light for 120 minutes. Measured every time and recorded the maximum temperature.

  Table 1 summarizes the evaluation of the slipperiness, scratch resistance, slidability, heat shielding performance and heat storage performance. According to Table 1, regarding the slipperiness, the floor protection materials of Examples 1, 2 and 3 in which the surface protective layer contains 15 parts by weight of glass beads and 4 parts by weight of polyethylene wax are all “slip. It was difficult. " However, the floor decorative material of Comparative Example 2 in which the surface protective layer did not contain glass beads and Comparative Example 3 in which the surface protective layer contained 30 parts by mass of glass beads was evaluated as “slightly slip”. Furthermore, the floor decorative material of Comparative Example 5 containing 8 parts by mass of polyethylene wax was evaluated as “slid”.

  Regarding the scratch resistance, each of the floor decorative materials of Examples 1, 2 and 3 in which the surface protective layer contains 15 parts by mass of glass beads and 4 parts by mass of polyethylene wax is subjected to a load of 4 kg. The wound started to scratch. On the other hand, the floor decorative material of Comparative Example 2 in which the surface protective layer did not contain glass beads began to be damaged when a load of 1 kg was applied. In addition, in the floor decorative material of Comparative Example 3 in which the surface protective layer did not contain polyethylene wax, scratching began when a load of 3 kg was applied.

  Regarding the slidability, all of the floor covering materials of Example 1, Example 2 and Example 3 in which the surface protective layer contains 15 parts by mass of glass beads and 4 parts by mass of polyethylene wax are after the above slidability test. No surface change was seen. However, in the floor decorative material of Comparative Example 3 in which 30 parts by mass of the glass beads are filled in the surface protective layer and in the floor decorative material of Comparative Example 4 in which the polyethylene wax is not filled, the surface is tested by sliding test. Abrasion occurred.

From the above results, it was confirmed that the floor decorative material obtains good slipperiness, scratch resistance and slidability by filling the surface protective layer with appropriate amounts of glass beads and polyethylene wax.
In addition, the floor decorative materials of Example 1, Example 2, Example 3, and Comparative Examples 2 to 5 representing black by mixing color of isoindolinone, polyazo and phthalocyanine are all about the heat shielding performance. A rating of “O” was obtained. On the other hand, the floor decorative material of Comparative Example 1 using carbon black as the black pigment was evaluated as “x” for the heat shielding performance.

  Moreover, about the thermal storage performance, the test piece of Example 1, Example 2, Example 3, and the comparative example 2 to the comparative example 5 became 61 degreeC or 62 degreeC, whereas the test piece of the comparative example 1 was 71. The temperature rose to ° C. This difference is due to the fact that Example 1, Example 2, Example 3 and Comparative Example 2 to Comparative Example 5 are mixed with isoindolinone pigments, diketopyrrolopyrrole pigments and phthalocyanine pigments to represent black. On the other hand, it is considered that Comparative Example 1 occurred because carbon black was used as the black pigment.

  In addition, the inventors of the present invention indicate that the surface protective layer includes 10 parts by mass of glass beads, the surface protective layer includes 20 parts by mass of glass beads, the surface protective layer includes 3 parts by mass of a wax component, and the surface protective layer includes A floor decorative sheet was prepared in the same manner as in Example 1, Example 2 and Example 3 except that 5 parts by mass of the wax component were combined. And the slipperiness | lubricity, sliding property, heat insulation performance, and heat storage performance of the produced floor decorative sheet were evaluated. As a result, the floor decorative sheet prepared under such conditions obtained good results in any evaluation as in Examples 1 to 3.

  The above-described decorative base for floors and decorative sheets for floors according to the present invention are suitable for indoor flooring that is exposed to sunlight because they do not easily warp even when exposed to sunlight.

DESCRIPTION OF SYMBOLS 1 Decorative material for floors 3 Decorative sheet for floors 11 Thermoplastic resin base material layer 13 Print layer 15 Second adhesive layer 17 Overlay film layer 19 Surface protective layer 20 Base material 21 First adhesive layer 31 Glass beads 33 Wax component 111 Titanium oxide layer

Claims (3)

A thermoplastic resin substrate layer, a printed layer formed on one surface of the thermoplastic resin substrate layer, and a surface protective layer of the printed layer are formed in this order, and the surface protective layer has a particle size Contains 10 to 20 parts by weight of glass beads that are 1/3 or more and 2/3 or less of the thickness of the surface protective layer, and contains 3 to 5 parts by weight of a wax component,
The printing layer has a solid printing layer and a pattern layer in this order from the thermoplastic resin base material layer side, and the solid printing layer has pigments such as isoindolinone, disazo, polyazo, and diketopyrrolo. A decorative sheet for floors, which is selected from pyrrole, quinacridone, phthalocyanine and titanium oxide, and black is reproduced in the pattern layer by mixing isoindolinone pigment, diketopyrrolopyrrole pigment and phthalocyanine pigment. .   2. The floor according to claim 1, wherein the thermoplastic resin base material layer has a film made of a paint containing titanium oxide as a pigment on a surface on the side of the printing layer, or contains titanium oxide as a pigment. 3. Cosmetic sheet.   A floor decorative material comprising the floor decorative sheet according to claim 1 bonded to a base material.

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