JP2022036238A - Decorative material for floor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide decorative material for a floor excellent in adiathermancy, water resistance, moisture proof, and shape stability, as well as excellent in impact resistance, load bearing, and scratch resistance, and also excellent in workability.

SOLUTION: Decorative material for a floor comprises sequentially a foam resin layer, a substrate layer and a decorative layer. An expansion ratio of the foam resin layer is 5 to 20 times and a compression modulus thereof is 20 MPa or more. An elastic modulus of the substrate layer is 180 MPa or more and a thickness of the substrate layer is 1 to 10 mm, and the thickness of the foam resin layer is thicker than the substrate layer.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

The present invention relates to a decorative material for floors.

Conventionally, wood flooring materials have been widely used as flooring materials for residential use, and wood flooring materials are generally made by laminating wood materials such as veneer and applying decorative sheets or paint on them. It is used in. Among residential use, water-related applications such as toilets, washbasins, and kitchens are in a humid environment, so wood flooring is prone to mold and warpage, and is made of resin called a resin floor with excellent moisture resistance. Cushion floors are generally used. However, it is rare that air-conditioning equipment such as an air conditioner is installed in toilets and washbasins, and there is a problem that the cushion floor gets cold in winter. In order to alleviate the bottom cold in this winter, it is conceivable to use a foam flooring material having a foam layer (for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 7-82871

Since the foam flooring material is a non-woody flooring material, it has excellent moisture resistance, water resistance, and heat insulation, so it can be said that the flooring material can solve the above problems. However, since heavy toilet bowls, building materials such as wash basins, and electrical appliances such as washing machines and refrigerators are placed around water, load resistance and scratch resistance against dents on the floor material surface due to long-term loads become problems. The hardness of the floor material surface is important for load resistance and scratch resistance, but if it is too hard, the impact resistance will decrease. It is required to satisfy the performance at the same time. In addition, since the temperature and humidity changes are larger around the water than in other parts of the house, the problem of warpage due to these changes is likely to occur.

Furthermore, while wood flooring is used for living rooms and corridors, resin cushion floors are thinner than flooring materials, and the floor level does not match as it is, so a waste board is installed under the cushion floor. There is also a problem that the construction efficiency deteriorates because the wood flooring material and the craftsman who constructs the cushion floor are different.

Under such circumstances, the present invention has excellent heat insulation, water resistance, moisture resistance, shape stability, impact resistance, load resistance, scratch resistance, and other surface properties, and is easy to install. The purpose is to provide excellent floor decorative materials.

As a result of diligent research to achieve the above object, the present inventors have found that the following invention can solve the problem. That is, the present invention provides the following decorative materials for floors.

[1] It has a foamed resin layer, a support layer and a decorative layer in this order, the foamed resin layer has a foaming magnification of 5 to 20 times, a compressive elastic modulus of 20 MPa or more, and tensile elasticity of the support layer. Floor decorative material with a rate of 180 MPa or more.
[2] The floor decorative material according to the above [1], which has a foamed resin layer, a support layer, a base resin layer, a decorative layer, and a surface protective layer in this order.

According to the present invention, a decorative material for floors is excellent in heat insulation, water resistance, moisture resistance, shape stability, impact resistance, load resistance, scratch resistance and other surface properties, and is also excellent in ease of construction. Can be provided.

It is a schematic diagram which shows the cross section of a preferable example of the decorative material for a floor of this invention. It is a schematic diagram which shows the cross section of a preferable example of the decorative material for a floor of this invention. It is a schematic diagram which shows the cross section of a preferable example of the decorative material for a floor of this invention.

[Floor decorative material]
The floor decorative material of the present invention has a foamed resin layer, a support layer and a decorative layer in this order, and the foamed resin layer has a foaming ratio of 5 to 20 times and a compressive elastic modulus of 20 MPa or more. It is characterized in that the tensile elastic modulus of the support layer is 180 MPa or more. The typical structure of the floor decorative material of the present invention will be described with reference to FIGS. 1 to 3. 1 and 2 are schematic views showing a cross section of a preferable floor decorative material 10 of the present invention. In the embodiment shown in FIG. 1, the floor decorative material 10 of the present invention has a foamed resin layer 1, a support layer 2, and a decorative layer 3 in this order. Further, in the embodiment shown in FIG. 2, a base resin layer 4 is provided between the support layer 2 and the decorative layer 3, and an adhesive layer 7, a transparent resin layer 5, and a transparent resin layer 5 are provided on the decorative layer 3. It has a surface protective layer 6, a foamed resin layer 1, a support layer 2, a base resin layer 4, a decorative layer 3, an adhesive layer 7, a transparent resin layer 5, and a surface protective layer 6 in this order. .. Further, in the embodiment shown in FIG. 3, the support layer 2 has a three-layer structure, and has a structure having a first thermoplastic resin layer 21, a glass component layer 22, and a second thermoplastic resin layer 23 in this order. ing.

(Effervescent resin layer)
The foamed resin layer is a layer that mainly imparts heat insulating property, load resistance, and impact resistance to the floor decorative material of the present invention, and is formed by foaming a foamed resin composition, and the foaming ratio thereof is 5 to 5. The layer is 20 times larger and has a compressive elastic modulus of 20 MPa or more.

The foaming ratio in the foamed resin layer needs to be 5 to 20 times. If the foaming ratio is out of the above range, excellent heat insulating properties, load bearing resistance, and impact resistance cannot be obtained. From the viewpoint of obtaining excellent heat insulating properties and load bearing capacity, the foaming ratio is preferably 5 to 15 times, more preferably 5 to 12 times.

Further, the compressive elastic modulus of the foamed resin layer needs to be 20 MPa or more. If the compressive elastic modulus is less than 20 MPa, excellent load resistance and impact resistance cannot be obtained. From the viewpoint of obtaining excellent load resistance and impact resistance, the compressive elastic modulus is preferably 20 to 100 MPa, more preferably 20 to 50 MPa. Here, the compressive elastic modulus is a value obtained by preparing a sample of the foam molded product in accordance with the method described in JIS A9511: 1999 "Foam plastic heat insulating material" and measuring it. Specifically, a rectangular parallelepiped test piece having a length of 100 mm, a width of 100 mm, and a thickness of 30 mm is cut out from the foamed resin layer, and the test piece is measured for a compression elastic modulus at a compression rate of 10 mm / min using a Tencilon measuring device. I do. Five test pieces are prepared, the compressive elastic modulus is measured for each test piece in the same manner as described above, and the value obtained by arithmetically averaging them is taken as the compressive elastic modulus.

The method for foaming the foamed resin composition is not particularly limited, and any known method can be adopted, but foaming by the bead method is preferable from the viewpoint of obtaining a homogeneous foamed resin layer. In the bead method, foamed resin particles (pre-foamed particles) are used as a raw material, the foamed resin particles are filled in the cavity of the mold, and the filled pre-foamed particles are secondarily foamed with steam, and the pre-foamed particles are used together. Is a method of obtaining a foamed resin layer by integrating the particles by heat fusion.

The resin used for the foamed resin particles is preferably a thermoplastic resin. Examples of the thermoplastic resin include polyolefin resins such as polyethylene, propylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), ethylene- (meth) acrylic acid-based resin, and acrylonitrile-butadiene-styrene copolymer (ABS resin). , Acrylonitrile-styrene copolymer, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl resin such as polyvinyl alcohol resin, polyester resin such as polyethylene terephthalate resin (PET resin), nylon, polyacetal resin, acrylic resin, polycarbonate resin, polyurethane A simple substance and a copolymer of a thermoplastic resin such as a resin, or a mixed resin thereof is preferable. Among these, polyolefin resin is preferable, and polystyrene resin is particularly preferable, considering the strength of the resin itself.

The styrene monomer forming the polystyrene resin is not particularly limited, and any known styrene monomer can be used. For example, styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, bromostyrene and the like can be mentioned. These styrene-based monomers may be one kind or a mixture of a plurality of kinds. The preferred styrene monomer is styrene.

The foamed resin particles are usually made into resin particles by absorbing a monomer such as a styrene monomer into seed particles made of a resin forming the foamed resin particles together with a plasticizer and polymerizing the particles, and simultaneously or simultaneously with the polymerization. After polymerization, the resin particles are impregnated with a foaming agent and then foamed. Further, the foamed resin particles can also be obtained by a method of impregnating particles obtained by suspension polymerization of a monomer such as a styrene monomer in an aqueous medium with a foaming agent.

Examples of the foaming agent include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite; N, N'-dimethyl-N, N'-
Nitroso compounds such as dinitrosoterephthalamide, N, N'-dinitrosopentamethylenetetramine; azo compounds such as azodicarboxylicamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene; benzenesulfonyl hydrazide , A sulfonyl hydrazide compounds such as toluene sulfonyl hydrazide; preferably azide compounds such as calcium azide, 4,4'-diphenyldisulfonyl azide, p-toluene sulfonyl azide and the like. As the foaming agent, as a physical foaming agent, in addition to aliphatic hydrocarbons such as propane, normal butane, isopentane, normal pentane and neopentane, fluorinated hydrocarbons such as difluoroethane and tetrafluoroethane having an ozone destruction coefficient of zero. Volatile foaming agents such as the like are also preferably mentioned. These foaming agents can be used alone or in combination of two or more.
The amount of the foaming agent added may be appropriately determined according to the desired expansion ratio and compressive elastic modulus, but is preferably 0.5 to 15 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the resin. ..

Examples of the plasticizer include fatty acid ester compounds such as propylene glycol fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester; phthalic acid esters such as dibutylphthalate (DBP), dioctylphthalate (DOP), and diisononylphthalate (DINP). Compounds; Adipic acid ester compounds such as diisobutyl adipate and dioctyl adipate; Sevacinic acid ester compounds such as dibutyl sebacate and di2-ethylhexyl sebacate; Glycerin fatty acid ester compounds such as glycerin tristearate and glycerin tricaprylate; Natural fats and oils such as coconut oil, palm oil and rapeseed oil are preferably mentioned.
The plasticizer may be added when the monomer is polymerized or may be added when the foaming agent is impregnated. The amount of the plasticizer added may be appropriately determined according to the desired expansion ratio and compressive elastic modulus, but is preferably 0.2 parts by mass or more and less than 3 parts by mass, preferably 0.4 parts by mass with respect to 100 parts by mass of the resin. More preferably less than 1.6 parts by mass. If the amount of the plasticizer added is 0.2 parts by mass or more, the secondary transition temperature becomes low, which is advantageous for pre-foaming and molding at low temperatures. You can get a nice appearance.

Further, the foamed resin particles include flame retardants, flame retardant aids, lubricants, antibonding agents, fusion promoters, antistatic agents, spreading agents, bubble modifiers, cross-linking agents, as long as the physical properties are not impaired. Additives such as fillers and colorants may be included.

In the bead method, for example, the above-mentioned foamed resin particles are filled in the cavity of the mold, and the filled pre-foamed particles are used in a heat medium such as steam at 100 to 150 ° C., preferably 100 to 120 ° C. A foamed resin layer can be obtained by integrating the pre-foamed particles with each other by heat fusion while performing secondary foaming with a heating time of 10 to 40 seconds. In this case, the average particle size of the generally used foamed resin particles is preferably 0.2 to 4 mm, more preferably 0.5 to 2 mm.
Further, in the present invention, the foamed resin layer is not limited to the above-mentioned bead method, and is a resin composition for forming a foamed resin layer containing a resin for a foamed resin layer, a foaming agent, a plasticizer, an inorganic filler, and other necessary additives. It is also possible to obtain a product by forming an unfoamed resin layer by a film-forming method such as an extrusion film-forming method using a T-die or a calendar film-forming method, and then foaming the product at about 220 to 250 ° C. using a heating foaming furnace. can.

Further, as the foamed resin layer, a commercially available heat insulating board such as a bead method polystyrene foam heat insulating plate or an extruded polystyrene foam heat insulating plate can be used as long as it is within a predetermined foaming ratio and tensile elastic modulus.

The thickness of the foamed resin layer varies depending on the expansion ratio and the like, but is preferably 3 to 15 mm, more preferably 5 to 15 mm, and even more preferably 5 to 12 mm. When the thickness of the foamed resin layer is within the above range, excellent heat insulating properties, load bearing resistance, and impact resistance can be obtained.
Further, the thickness of the foamed resin layer is preferably thicker than that of the support layer described later. By being thicker than the support layer, excellent heat insulation, load resistance, and impact resistance can be obtained, and stress warpage due to the difference in elongation due to moisture etc. with other layers such as the support layer is unlikely to occur. Become.

(Support layer)
The support layer is a layer that mainly imparts shape stability, water resistance, moisture resistance, impact resistance, and scratch resistance to the floor decorative material of the present invention, and is a layer having a tensile elastic modulus of 180 MPa or more. ..

The support layer needs to have a tensile elastic modulus of 180 MPa or more. If the tensile elastic modulus is less than 180 MPa, scratch resistance cannot be obtained. From the viewpoint of obtaining excellent water resistance, moisture resistance, and scratch resistance, the tensile elastic modulus is preferably 180 to 3000 MPa, more preferably 250 to 1000 MPa, and even more preferably 250 to 500 MPa. Further, when the tensile elastic modulus is within the above range, stress warpage due to a difference in elongation due to moisture or the like with another layer such as a foamed resin layer is less likely to occur. Here, for the tensile elastic modulus, a decorative sheet punched out on a dumbbell type test piece conforming to JIS K6732 is prepared, and a tensile compression tester is used under a temperature condition of 20 ° C., a tensile speed of 50 mm / min, between chucks. It was calculated by the following formula from the first straight line part of the tensile stress-strain curve obtained by measuring under the condition of a distance of 80 mm.
E = Δρ / Δε
E: Tension elastic modulus Δρ: Stress difference due to the original average cross-sectional area between two points on a straight line Δε: Strain difference between the same two points

The support layer preferably has a thermoplastic resin layer. Examples of the thermoplastic resin forming the thermoplastic resin layer include polyvinyl chloride resins such as polyvinyl chloride resin, polyvinyl acetate resin and polyvinyl alcohol resin, polyethylene, propylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA) and ethylene. -A single body and copolymer of a polyolefin resin such as (meth) acrylic acid resin, a polyester resin such as polyethylene terephthalate resin (PET resin), an acrylic resin, a polycarbonate resin, and a thermoplastic resin such as polyurethane resin, or a mixture thereof. Resin is preferably mentioned. Of these, polyvinyl resin is preferable.

Further, the support layer may be composed of one layer or a laminated body composed of two or more layers, but is a laminated body composed of two or more layers, and is at least one layer. Preferably contains a glass component. That is, it is preferable that the support layer is a laminate composed of two or more layers, at least one layer is a thermoplastic resin layer, and the other one layer is a glass component layer containing a glass component. With such a configuration, excellent impact resistance can be obtained and shape stability is improved.
As the glass component layer containing a glass component, for example, a layer made of glass fiber or the like is preferably mentioned.

In the present invention, the support layer is preferably a laminate in which a thermoplastic resin layer and a glass component layer are alternately laminated, and in particular, a first thermoplastic resin layer as shown in FIG. A laminate having a glass component layer and a second thermoplastic resin layer in this order is preferable.
When the support layer has a plurality of thermoplastic resin layers, the types of resins forming the thermoplastic resin layer may be the same or different, and the thickness thereof may be the same or different. May be good.

The thickness of the support layer is preferably 1 to 10 mm, more preferably 1 to 5 mm. When the thickness of the support layer is within the above range, excellent water resistance, moisture resistance, impact resistance, and scratch resistance can be obtained. In addition, stress warpage due to a difference in elongation due to temperature or the like with another layer such as a foamed resin layer is less likely to occur.
Further, as described above, the thickness of the support layer is preferably thinner than that of the foamed resin layer. Stress warpage due to the difference in elongation due to moisture or the like with other layers such as the foamed resin layer layer is less likely to occur.

(Decorative layer)
The decorative layer is a layer that imparts decorativeness to the floor decorative material of the present invention, and may be a uniformly colored concealing layer (solid printing layer), or various patterns may be produced using ink and a printing machine. It may be a pattern layer formed by printing, or it may be a combination of a concealing layer and a pattern layer.

By providing a concealing layer, it is possible to conceal the base on which the floor decorative material is to be provided, and when the base material layer is colored or has uneven color, the intended color is given to adjust the surface color. Can be done.
In addition, by providing a pattern layer, a stone pattern that imitates the surface of rock such as wood grain pattern and marble pattern (for example, Travertin marble pattern), a cloth pattern that imitates a cloth grain or a cloth-like pattern, a tiled pattern, and a brick pile. It is possible to give a pattern or the like, or a pattern such as a parquet or a patchwork in which these are combined, to the decorative sheet. These patterns are formed by multi-color printing with ordinary yellow, red, blue, and black process colors, as well as by multi-color printing with special colors, which is performed by preparing plates of the individual colors that make up the pattern. Will be done.

As the ink composition used for the decorative layer, a binder resin mixed with a colorant such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent or the like is used. The binder resin is not particularly limited, and examples thereof include urethane resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, acrylic resin, polyester resin, and nitrocellulose resin. Be done. As the binder resin, any one of these can be used alone or in combination of two or more.
In addition, as colorants, inorganic pigments such as carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal pattern, cadmium red, ultramarine blue, cobalt blue, quinacridone red, and isoindolinone yellow. , Organic pigments such as phthalocyanine blue, metal pigments made of scaly foil pieces such as dyes, aluminum, and brass, titanium dioxide-coated mica, and pearl pigments made of scaly foil pieces such as basic lead carbonate. Preferred.

The thickness of the decorative layer is usually 0.5 to 10 μm, preferably 1 to 5 μm. When the thickness of the decorative layer is within the above range, an excellent design can be imparted to the floor decorative material, and concealment can be imparted.

(Base resin layer)
The base resin layer is a layer provided as desired, preferably a layer formed of a thermoplastic resin. As the thermoplastic resin, those exemplified as the thermoplastic resin provided in the foamed resin layer can be preferably mentioned. Of these, polyolefin resins are preferable, and polyethylene resins and propylene resins are more preferable.

The base resin layer may be transparent or colored, and is preferably colored from the viewpoint of concealing the base on which the floor decorative material is provided. As the colorant used, those exemplified as the colorant used in the decorative layer can be preferably mentioned.

The thickness of the base resin layer is preferably 10 to 150 μm, more preferably 30 to 100 μm, and even more preferably 40 to 80 μm. When the thickness of the base resin layer is within the above range, it is easy to handle and the floor decorative material does not become thicker than necessary.

Further, various additives such as a filler, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer may be added to the base resin layer, if necessary.

(Transparent resin layer)
The transparent resin layer is an arbitrary layer provided to protect the decorative layer, and is preferably a layer formed of a thermoplastic resin. As the thermoplastic resin, those exemplified as the thermoplastic resin provided in the foamed resin layer can be preferably mentioned. Of these, polyolefin resins are preferable, and polyethylene resins and propylene resins are more preferable.

The transparent resin layer is a transparent resin layer so that the decorative layer can be seen through. Here, transparency is a concept that includes not only colorless transparency but also colored transparency and translucency.
Further, various additives such as fillers, flame retardants, lubricants, antioxidants, ultraviolet absorbers, and light stabilizers may be added to the transparent resin layer as necessary without impairing its transparency. good.

The thickness of the transparent resin layer is preferably 10 to 150 μm, more preferably 30 to 100 μm, and even more preferably 50 to 100 μm. When the thickness of the transparent resin layer is within the above range, the decorative layer can be protected, it is easy to handle, and the floor decorative material does not become thicker than necessary.

(Surface protective layer)
The surface protective layer is a layer provided as desired, which imparts surface characteristics such as impact resistance, load resistance, and scratch resistance to the floor decorative material of the present invention. The surface protective layer is provided on the outermost surface of the floor decorative material of the present invention.
The surface protective layer is preferably composed of a decorative layer, a preferably provided transparent resin layer, or an adhesive layer on which a resin composition containing a curable resin is applied and cured. By containing the cross-linked and cured curable resin, the surface characteristics of the floor decorative material can be improved.

Preferred examples of the curable resin used for forming the surface protective layer include an ionizing radiation curable resin and a thermosetting resin, and a plurality of these are used, for example, an ionizing radiation curable resin and a thermosetting resin are used in combination. , So-called hybrid type may be used.
Of these, an ionizing radiation curable resin is preferable from the viewpoint of increasing the crosslink density of the resin forming the surface protective layer and improving the surface characteristics, and it can be applied without a solvent and is easy to handle. Therefore, an electron beam curable resin is more preferable.

The ionizing radiation curable resin refers to a resin having an energy quantum capable of cross-linking and polymerizing molecules in an electromagnetic wave or a charged particle beam, that is, a resin that is cross-linked and cured by irradiating with ultraviolet rays or an electron beam. Specifically, it can be appropriately selected and used from a polymerizable monomer, a polymerizable oligomer or a prepolymer conventionally used as an ionizing radiation curable resin.
As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate is particularly preferable. The polyfunctional (meth) acrylate may be any (meth) acrylate having two or more ethylenically unsaturated bonds in the molecule, and is not particularly limited. One of these polyfunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

Next, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, epoxy (meth) acrylate-based, urethane (meth) acrylate-based, polyester (meth) acrylate-based, or polyether (meth) acrylate. The system etc. can be mentioned.
Further, as the polymerizable oligomer, a highly hydrophobic polybutadiene (meth) acrylate-based oligomer having a (meth) acrylate group in the side chain of the polybutadiene oligomer, and a silicone (meth) acrylate-based oligomer having a polysiloxane bond in the main chain. , Aminoplast resin (meth) acrylate-based oligomers modified from aminoplast resin having many reactive groups in small molecules, or in molecules such as novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationically polymerizable functional group.

In the present invention, a monofunctional (meth) acrylate may be appropriately used in combination with the polyfunctional (meth) acrylate or the like for the purpose of lowering the viscosity thereof, as long as the object of the present invention is not impaired. .. One of these monofunctional (meth) acrylates may be used alone, or two or more thereof may be used in combination.

Examples of the thermosetting resin include epoxy resin, phenol resin, urea resin, unsaturated polyester resin, melamine resin, alkyd resin, polyimide resin, silicone resin, hydroxyl group functional acrylic resin, carboxyl functional acrylic resin, and amide functional co-weight. Combined, urethane resin and the like are preferable.

Further, as the thermosetting resin, a two-component curable resin is also preferable, and a two-component curable resin of a polyol and an isocyanate is preferable.
Here, examples of the polyol are preferably acrylic polyol, polyester polyol, epoxy polyol and the like.
The isocyanate may be a polyvalent isocyanate having two or more isocyanate groups in the molecule, for example, 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, 4,4. Aromatic isocyanates such as'-diphenylmethane diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate and other aliphatic (or Polyisocyanate such as alicyclic) isocyanate is used. Alternatively, adducts or multimers of these various isocyanates, such as adducts of tolylene diisocyanate and trimers of tolylene diisocyanate, are also used.

Further, various additives can be contained in the resin composition constituting the surface protective layer as long as the performance is not impaired. Examples of various additives include ultraviolet absorbers (UVA), light stabilizers (HALS, etc.), polymerization inhibitors, cross-linking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, and thixophilic imparting agents. , Coupling agents, plasticizers, antifoaming agents, fillers, solvents and the like.

The thickness of the surface protective layer is preferably 3 to 20 μm, more preferably 5 to 20 μm. When the thickness of the surface protective layer is within the above range, excellent surface characteristics can be obtained.

(Adhesive layer)
The adhesive layer is a layer provided as necessary when laminating the resin layer when the base resin layer and the transparent resin layer are provided. Preferred examples of the adhesive used for the adhesive layer include urethane adhesives, acrylic adhesives, acrylic / urethane adhesives, polyester adhesives, polyester urethane adhesives, polyamide adhesives, polystyrene adhesives, cellulose adhesives and the like. .. These adhesives can be used alone or as a mixture of two or more.

The thickness of the adhesive layer is preferably 3 to 30 μm, more preferably 3 to 15 μm. When the thickness of the adhesive layer is within the above range, good adhesiveness can be obtained, and the floor decorative material does not become thicker than necessary.

The floor decorative material of the present invention having each of the above layers has excellent impact resistance, heat insulation, water resistance, moisture resistance, load resistance, and scratch resistance, and is also excellent in ease of construction. It is suitable for residential flooring, especially for water-related applications such as toilets, washbasins, and kitchens.
The thickness of the floor decorative material of the present invention is preferably 5 to 25 mm, more preferably 7 to 20 mm, from the viewpoint of obtaining excellent impact resistance, heat insulating property, water resistance, moisture resistance, load resistance, and scratch resistance. It is preferable, and 8 to 15 mm is more preferable. Further, in consideration of ease of construction, it is preferable that the thickness is the same as that of the wood flooring material provided in a place other than the water area such as a living room or a corridor. The thickness of the wood flooring material is usually 8 mm, 12 mm, 15 mm or the like, and 12 mm is the standard thickness.

[Manufacturing method of decorative materials for floors]
The floor decorative material of the present invention can be produced, for example, through the following steps.

(Preparation process of foamed resin layer)
First, the foamed resin layer is prepared. As described above, the foamed resin layer is produced by the bead method or by foaming the resin composition for the foamed resin layer so that the foaming ratio is 5 to 20 times and the compressive elastic modulus is 20 MPa or more. The foaming ratio and compressive elastic modulus of the foamed resin layer can be appropriately adjusted depending on the foaming temperature at the time of foaming, the type of resin, the amount of the foaming agent and the plasticizer used, and the like.

(Formation process of decorative layer)
An ink composition is used to form a decorative layer on a support layer or, if necessary, a base resin layer. The ink composition may be applied by, for example, gravure printing, offset printing, screen printing, flexographic printing, inkjet printing, or the like. Further, when the concealing layer (solid printing layer) is formed, it may be formed by, for example, various coating methods such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, and a comma coat.

(Attachment process between the foamed resin layer and the support layer)
The foamed resin layer obtained in the preparation step of the foamed resin layer and the support layer forming the decorative layer are attached to each other by using, for example, a heat-sensitive adhesive, a pressure-sensitive adhesive, or a hot melt adhesive. It can be carried out. As the hot melt adhesive, for example, a reactive hot melt adhesive such as a urethane-based reactive hot melt (hereinafter referred to as "PUR") is preferably mentioned. This PUR contains a functional group (isocyanate group) that reacts with water in the component, and after cooling and curing, reacts with the water adhering to the substrate or the decorative sheet and the water given through them. After the reaction, it does not melt even when heated and has a characteristic of having high adhesive strength.

(Laminating process of transparent resin layer)
After forming the decorative layer, the transparent resin layer is preferably provided by a dry lamination method via an adhesive layer. For example, a decorative layer is formed on the base base material layer by the above method, and then dry lamination such as a two-component curable urethane resin, an acrylic resin, and a vinyl chloride-vinyl acetate copolymer using blocked isocyanate as a curing agent. An adhesive layer can be applied to form an adhesive layer, and a transparent resin layer can be provided by a dry lamination method.

(Step of forming the surface protective layer)
The surface protective layer has a curable resin composition on the decorative layer or on the transparent resin layer after the above-mentioned step of forming the decorative layer, or after the step of laminating the resin layer when laminating the transparent resin layer. An uncured resin layer is formed by applying an object and applying it by a known method such as gravure coat, bar coat, roll coat, reverse roll coat, comma coat, etc. so that the thickness after curing is about 3 to 20 μm. Then, the uncured resin layer can be formed by applying heat or irradiating the uncured resin layer with ionizing radiation such as an electron beam or ultraviolet rays to cure the uncured resin layer.

The heating temperature in the case of thermosetting is appropriately determined depending on the resin used.
When an electron beam is used as ionizing radiation, the acceleration voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but it is usually preferable to cure the uncured resin layer at an acceleration voltage of about 70 to 300 kV. .. The irradiation dose is preferably an amount at which the crosslink density of the resin layer is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).
The electron beam source is not particularly limited, and for example, a cockloft Walton type, a van de Graaff type, a resonance transformer type, an insulated core transformer type, or various electron beam accelerators such as a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. The ultraviolet source is not particularly limited, and for example, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a carbon arc lamp, or the like is used.

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited to this example.

(Evaluation and measurement method)
The floor decorative materials obtained in each Example and Comparative Example were evaluated and measured by the following methods.
1. 1. Evaluation of scratch resistance (pencil hardness test)
The "scratch hardness (pencil method) test" based on JIS K5600-5-4 was conducted 5 times to scratch the surface of the floor decorative material with a load of 500 g, and the hardness of the pencil that did not cause scars 3 times or more was determined. It was evaluated as pencil hardness according to the following criteria.
It was B or higher and had extremely excellent scratch resistance.
It was Δ2B or more and had excellent scratch resistance.
× 3B or less, and inferior in scratch resistance.

2. 2. Evaluation of load bearing capacity Four 2 cm square metal jigs were placed at the four corners of the floor decorative material (15 cm square), and a weight of 80 kg was placed so that the load was evenly applied to the four jigs. After being left in this state for one week, the weight was removed and the appearance of the floor decorative material was evaluated according to the following criteria.
〇 No change in the surface of the floor decorative material could be confirmed.
△ A slight dent was confirmed on the surface of the floor decorative material, but there was no problem in practical use.
× A dent was confirmed on the surface of the floor decorative material.

3. 3. Evaluation of shape stability (evaluation of warpage)
When leaving a scale-sized (30.3 cm square) floor decorative material at 5 ° C x 30% RH for one week and then at 40 ° C x 90% RH for one week, before leaving, when changing temperature conditions, And the degree of warpage after leaving was measured and evaluated according to the following criteria.
〇 The warp was less than ± 0.6 mm.
Δ The warp was ± 0.6 mm or more and ± 0.8 mm or less.
× The warp was greater than 0.8 mm or less than -0.8 mm.
Here, + indicates that the decorative layer side of the floor decorative material has a convex shape and warps, and − indicates that the decorative layer side has a concave shape and warps.

Example 1
A stone-grained decorative layer having a thickness of 2 μm was formed on a colored polypropylene resin film (thickness: 60 μm, color: white) using an ink composition (acrylic urethane) by gravure printing. Next, a transparent polypropylene resin film (thickness; 80 μm) was dry-laminated on the decorative layer using a urethane-based dry-laminating adhesive. An electron beam curable resin composition (acrylate-based) is applied onto the transparent polypropylene resin film at a coating amount of 15 g / m ² by gravure printing to form a coating film, and electrons are formed under the conditions of 175 keV and 5 Mrad (50 kGy). The coating film was crosslinked and cured by irradiating with a line to form a surface protective layer (thickness: 15 μm) to prepare a decorative sheet (thickness: 160 μm).
Next, a medium-density polyethylene resin sheet (tensile elasticity; 200 MPa, thickness; 3 mm) is prepared as a support layer, and the support is provided so as to face the colored polypropylene resin film (base resin layer) of the decorative sheet. The body layer and the decorative sheet were attached by dry laminating via a urethane-based dry laminating adhesive.
Next, polystyrene resin (foaming agent; butane (7 parts by mass with respect to 100 parts by mass of polystyrene resin), plasticizer; liquid paraffin (0.15 parts by mass with respect to 100 parts by mass of polystyrene resin)) was used as the foamed resin layer. A foamed resin layer (foaming ratio; 10 times, polystyrene elastic rate; 43 MPa, thickness; 9 mm) prepared by the bead method was prepared, and the support layer and the foamed resin layer to which the above-mentioned decorative sheet was attached were formed. A urethane-based reactive hot melt adhesive was used for pasting to prepare a decorative material for floors. Table 1 shows the results of evaluating the obtained floor decorative materials.

Examples 2 to 5 and Comparative Examples 1 to 2
In Example 1, a floor decorative material was produced in the same manner as in Example 1 except that the foamed resin layer and the support layer shown in Table 1 were replaced. Table 1 shows the results of evaluating the obtained floor decorative materials.

＊１，ＰＥ１；中密度ポリエチレン樹脂シート
ＰＥ２；低密度ポリエチレン樹脂シート
ＰＶＣ；ガラス繊維強化塩化ビニル板（塩化ビニル樹脂層／ガラス繊維層／塩化ビニル樹脂層の三層構成で、合計厚さは３ｍｍ）
ＰＰ；ポリプロピレン樹脂シート

* 1, PE1; Medium density polyethylene resin sheet PE2; Low density polyethylene resin sheet PVC; Glass fiber reinforced vinyl chloride plate (three-layer structure of vinyl chloride resin layer / glass fiber layer / vinyl chloride resin layer, total thickness 3 mm )
PP; polypropylene resin sheet

According to the present invention, a decorative material for floors is excellent in heat insulation, water resistance, moisture resistance, shape stability, impact resistance, load resistance, scratch resistance and other surface properties, and is also excellent in ease of construction. Can be obtained. The flooring decorative material of the present invention is suitably used as a flooring material for a house, particularly as a flooring material for water-related applications such as toilets, washbasins, and kitchens.

10. Floor decorative material 1. Foamed resin layer 2. Support layer 21. First thermoplastic resin layer 22. Glass component layer 23. Second thermoplastic resin layer 3. Decorative layer 4. Base resin layer 5. Transparent resin layer 6. Surface protective layer 7. Adhesive layer

Claims (9)

It has a foamed resin layer, a support layer, and a decorative layer in this order, and the foaming ratio of the foamed resin layer is 5 to 20 times.
Moreover, the compressive elastic modulus is 20 MPa or more, and the tensile elastic modulus of the support layer is 180 MPa or more.
A floor decorative material in which the thickness of the support layer is 1 to 10 mm and the foamed resin layer is thicker than the support layer. The floor decorative material according to claim 1, which has a foamed resin layer, a support layer, a base resin layer, a decorative layer, and a surface protective layer in this order. The floor decorative material according to claim 1 or 2, wherein the foamed resin layer is made of a thermoplastic resin. The floor decorative material according to claim 3, wherein the thermoplastic resin is a polystyrene resin. The floor decorative material according to any one of claims 1 to 4, wherein the foamed resin layer is formed by the bead method. The floor decorative material according to any one of claims 1 to 5, wherein the support layer has a thermoplastic resin layer. The floor decorative material according to claim 6, wherein the support layer is a laminate composed of two or more layers, and at least one layer is a glass component layer containing a glass component. The floor decorative material according to claim 7, wherein the support layer is a laminate having a first thermoplastic resin layer, a glass component layer, and a second thermoplastic resin layer in this order. The floor decorative material according to any one of claims 1 to 8, wherein the foamed resin layer has a thickness of 5 to 15 mm.

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