KR102471547B1 - Decorative material for floor - Google Patents

Abstract

Provided is a floor decorative material that is excellent in heat insulation, water resistance, moisture resistance, shape stability, excellent in surface properties such as impact resistance, load resistance and scratch resistance, and also excellent in ease of installation. A floor decorative material comprising, in this order, a foamed resin layer, a support layer and a decorative layer, the foamed resin layer has an expansion ratio of 5 to 20 times, a compressive modulus of elasticity of 20 MPa or more, and a tensile modulus of elasticity of the support layer of 180 MPa or more.

Description

Floor decorative material {DECORATIVE MATERIAL FOR FLOOR}

The present invention relates to a floor cosmetic material.

[0002] Conventionally, as a flooring material mainly for residential use, wood flooring materials are frequently used, and wood flooring materials obtained by laminating wood materials such as thin wood boards and applying decorative sheets or coating thereon are generally used. In residential use, such as bathrooms, washrooms, and kitchens, where water is often used, since it is in a humid environment, mold and warping are likely to occur in wooden flooring materials, and it is called a resin floor with excellent moisture resistance. Adoption of the floor is common. However, it is rare that air conditioners such as air conditioners are installed in toilets, washrooms, etc., and there have been problems such as cold floors in winter on cushion floors. In order to alleviate the coldness of the floor in this winter, it is considered to use a foam flooring material having a foam layer (for example, Patent Literature 1).

Japanese Unexamined Patent Publication No. 7-82871

Since foam flooring is a non-wooden flooring material, it is excellent in moisture resistance and water resistance, and also has excellent heat insulation properties, so it can be said to be a flooring material that can solve the above problems. However, in places where water is frequently used, heavy building materials such as toilet bowls and washbasins, and electrical appliances such as washing machines and refrigerators are placed, so load resistance and scratch resistance for concave areas on the surface of flooring caused by long-term loads are problematic. do. The hardness of the surface of the flooring material is important for load resistance and scratch resistance, but impact resistance is reduced if it is too hard, so it is required that the flooring material simultaneously satisfy the conflicting performances of load resistance, scratch resistance and impact resistance. In addition, since temperature change and humidity change are greater in a place where water is frequently used than in other places in a dwelling, the problem of warping accompanying these changes is likely to occur.

In addition, while wooden flooring materials are used in living rooms and corridors, cushion floors made of resin are thinner than flooring materials, and the level of the floor does not match as it is, so it is necessary to perform a ground treatment such as constructing a leveling board under the cushion floor. In addition, there is also a problem that construction efficiency deteriorates in that the craftsman who constructs the wooden flooring material and the cushion floor are different.

Under these circumstances, the object of the present invention is to provide a decorative material for floor that is excellent in heat insulation, water resistance, moisture resistance, shape stability, excellent in surface properties such as impact resistance, load resistance and scratch resistance, and also excellent in ease of installation. to be

The inventors of the present invention, as a result of intensive research in order to achieve the above object, found that it can be solved by the following invention. That is, this invention provides the following floor use decorative materials.

[1] A floor covering comprising a foamed resin layer, a support layer and a decorative layer in this order, the foamed resin layer having a foaming ratio of 5 to 20 times, a compressive modulus of elasticity of 20 MPa or more, and a tensile modulus of elasticity of the support layer of 180 MPa or more. re.

[2] The floor decorative material according to [1] above, 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, it is possible to provide a floor decorative material that is excellent in heat insulation, water resistance, moisture resistance, shape stability, excellent in surface properties such as impact resistance, load resistance and scratch resistance, and also excellent in ease of installation.

1 : is a schematic diagram showing the cross section of a preferable example of the floor use decorative material of this invention.
2 : is a schematic diagram which shows the cross section of a preferable example of the floor use decorative material of this invention.
3 : is a schematic diagram which shows the cross section of a preferable example of the floor use decorative material of this invention.

[Floor toilet material]

The floor decorative material of the present invention has a foamed resin layer, a support layer and a decorative layer in this order, the foamed resin layer has a foaming ratio of 5 to 20 times, a compressive elastic modulus of 20 MPa or more, and a tensile modulus of the support layer of 180 MPa. It is characterized by more than one. The typical structure of the floor use decorative material of this invention is demonstrated using FIGS. 1-3. 1 and 2 are schematic diagrams showing a cross section of a preferred floor use decorative material 10 of the present invention. In the form shown in FIG. 1, the floor decorative material 10 of this invention has the foamed resin layer 1, the support body layer 2, and the decoration layer 3 in order. In addition, in the form shown in FIG. 2, it has the base resin layer 4 between the said support body layer 2 and the decoration layer 3, and also the adhesive material layer 7 on the said decoration layer 3, transparent water It has a paper layer (5) and a surface protective layer (6), and has a foamed resin layer (1), a support layer (2), a base resin layer (4), a decorative layer (3), an adhesive layer (7), and a transparent resin layer. (5) and a surface protective layer (6) in this order. In the form shown in Fig. 3, the support layer 2 has a three-layer structure, and the first thermoplastic resin layer 21, the glass component layer 22, and the second thermoplastic resin layer 23 are sequentially formed. It has a structure with

(foamed resin layer)

The foamed resin layer is a layer that mainly imparts thermal insulation properties, load resistance and impact resistance to the floor decorative material of the present invention, and is formed by foaming a foamed resin composition, has a foaming ratio of 5 to 20 times, and has a compressive modulus of 20 MPa. It is an upper layer.

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

In addition, the compressive elastic modulus of the foamed resin layer is required to be 20 MPa or more. If the compressive 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, and more preferably 20 to 50 MPa. Here, the compressive elastic modulus is a value measured by preparing a sample of a molded-foam article according to the method described in JIS A9511: 1999 "Foamed Plastic Insulator". Specifically, a rectangular parallelepiped test piece having a length of 100 mm × width of 100 mm × thickness of 30 mm is cut out from the foamed resin layer, and the compressive modulus of the test piece is measured using a tensilon measuring instrument at a compression rate of 10 mm/min. Five test pieces are prepared, the compressive elastic modulus is measured in the above manner for each test piece, and the value obtained by arithmetic average of them is taken as the compressive elastic modulus.

The foaming method of the foamed resin composition is not particularly limited, and any known method can be employed, but foaming by a bead method is preferable from the viewpoint of obtaining a homogeneous foamed resin layer. In the bead method, expanded resin particles (pre-expanded particles) are used as a raw material, the expanded resin particles are filled into a cavity of a mold, and the pre-expanded particles are thermally fused together while the filled pre-expanded particles are secondarily expanded with steam. It is a method of obtaining a foamed resin layer by integrating by.

The resin used for the expanded resin particles is preferably a thermoplastic resin. As the thermoplastic resin, polyethylene, propylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), polyolefin resin such as ethylene-(meth)acrylic acid resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile -Styrene copolymers, polyvinyl chloride resins, polyvinyl acetate resins, polyvinyl resins such as polyvinyl alcohol resins, polyester resins such as polyethylene terephthalate resins (PET resins), nylon, polyacetal resins, acrylic resins, polycar Preferable examples thereof include simple substances and copolymers of thermoplastic resins such as bonate resins and polyurethane resins, or mixed resins thereof. Among these, considering the strength of the resin itself, polyolefin resins are preferred, and polystyrene resins are particularly preferred.

The styrene monomer forming the polystyrene resin is not particularly limited, and any known styrene monomer can be used. Examples thereof include styrene, α-methylstyrene, vinyltoluene, chlorostyrene, ethylstyrene, isopropylstyrene, dimethylstyrene, and bromostyrene. These styrenic monomers may be one type or a mixture of multiple types. A preferred styrene monomer is styrene.

The expanded resin particles are usually made into resin particles by allowing a monomer such as a styrene monomer to be absorbed into seed particles containing a resin forming the expanded resin particles together with a plasticizer, if necessary, and polymerizing them, simultaneously with or after polymerization, It is obtained by impregnating the resin particle with a foaming agent and then foaming it. Further, the foamed resin particles can also be obtained by a method in which a foaming agent is impregnated into particles obtained by suspension polymerization of a monomer such as a styrene monomer in an aqueous medium.

As a foaming agent, Inorganic foaming agents, such as sodium hydrogencarbonate, sodium carbonate, ammonium hydrogencarbonate, ammonium carbonate, and ammonium nitrite; nitroso compounds such as N,N'-dimethyl-N,N'-dinitrosoterephthalamide and N,N'-dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, and azodiaminobenzene; sulfonylhydrazide compounds such as benzenesulfonylhydrazide and toluenesulfonylhydrazide; Azide compounds, such as calcium azide, 4,4'-diphenyl disulfonyl azide, and p-toluene sulfonyl azide, etc. are mentioned preferably. In addition, as a foaming agent, as a physical foaming agent, in addition to aliphatic hydrocarbons such as propane, normal butane, isopentane, normal pentane, and neopentane, volatile hydrocarbons such as difluoroethane and tetrafluoroethane having an ozone depletion coefficient of zero such as fluorocarbons A foaming agent is also preferably mentioned. These foaming agents can be used individually or in combination of a plurality.

The addition amount of the foaming agent may be appropriately determined according to the desired expansion ratio or compressive elastic modulus, but is preferably 0.5 to 15 parts by mass and 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 ester compounds such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), and diisononyl phthalate (DINP); adipic acid ester compounds such as diisobutyl adipate and dioctyl adipate; sebacic acid ester compounds such as dibutyl sebacate and diethylhexyl sebacate; glycerin fatty acid ester compounds such as glycerin tristearate and glycerin tricaprylate; Natural oils and fats, such as liquid paraffin, palm oil, palm oil, and rapeseed oil, are mentioned preferably.

A plasticizer may be added when polymerizing a monomer or when impregnating a foaming agent. The addition amount of the plasticizer may be appropriately determined according to the desired expansion ratio or compressive elastic modulus, but is preferably 0.2 parts by mass or more and less than 3 parts by mass, and more preferably 0.4 parts by mass or more and less than 1.6 parts by mass with respect to 100 parts by mass of the resin. If the addition amount of the plasticizer is 0.2 parts by mass or more, the secondary transition temperature is lowered, so pre-foaming and molding at low temperatures are superior, and if it is less than 3 parts by mass, the foam is less likely to shrink and a good appearance is obtained.

In addition, the foamed resin particles may contain additives such as flame retardants, flame retardant aids, lubricants, bonding inhibitors, fusion accelerators, antistatic agents, spreading agents, cell regulators, crosslinking agents, fillers, colorants, etc., within a range that does not impair physical properties. .

In the bead method, for example, the above-mentioned expanded resin particles are filled in a cavity of a mold, and the filled pre-expanded particles are 100 to 150 ° C., preferably 100 to 120 ° C., using a heat medium such as steam, A foamed resin layer can be obtained by integrating the pre-expanded particles with each other by thermal fusion while carrying out secondary foaming at a heating time of 40 seconds. In this case, the average particle diameter of the generally used expanded 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 bead method, and 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 additives as necessary, It can also be obtained by forming an unfoamed resin layer into a film by a film forming method such as an extrusion film forming method using a T die or a calendar film forming method, followed by foaming at about 220 to 250°C using a heating foaming furnace.

Further, as the foamed resin layer, a commercially available heat insulation board such as a bead-processed polystyrene foam insulation board or an extrusion-processed polystyrene foam insulation board may be used as long as the foaming ratio and tensile modulus are within a predetermined range.

The thickness of the foamed resin layer varies somewhat depending on the expansion ratio and the like, but is preferably 3 to 15 mm, more preferably 5 to 15 mm, still more preferably 5 to 12 mm. When the thickness of the foamed resin layer is within the above range, excellent heat insulation properties, load resistance and impact resistance are obtained.

In addition, it is preferable that the thickness of the foamed resin layer is thicker than the support body layer mentioned later. When it is thicker than the support layer, excellent heat insulation, load resistance and impact resistance are obtained, and stress deflection due to difference in elongation due to moisture or the like with other layers such as the support layer is less likely to occur.

(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 modulus of elasticity of 180 MPa or more.

The support layer requires a tensile modulus of elasticity of 180 MPa or more. When the tensile modulus is less than 180 MPa, scratch resistance is not obtained. From the standpoint of obtaining excellent water resistance, moisture resistance and scratch resistance, the tensile modulus is preferably 180 to 3000 MPa, more preferably 250 to 1000 MPa, still more preferably 250 to 500 MPa. In addition, when the tensile modulus of elasticity is within the above range, stress deflection due to difference in elongation due to moisture or the like with other layers such as the foamed resin layer is less likely to occur. Here, the tensile modulus of elasticity is measured by preparing a decorative sheet punched into a dumbbell-shaped test piece conforming to JIS K6732, using a tensile compression tester under a temperature condition of 20 ° C., under the conditions of a tensile speed of 50 mm / min and a distance between chucks of 80 mm From the first straight line portion of the tensile stress-strain curve obtained by doing, it was calculated by the following equation.

E=Δρ/Δε

E: tensile modulus

Δρ: Stress difference due to the original average cross-sectional area between two points on a straight line

Δε: Distortion difference between two identical points

It is preferable that the support body layer has a thermoplastic resin layer. As the thermoplastic resin forming the thermoplastic resin layer, polyvinyl chloride resin, polyvinyl acetate resin, polyvinyl alcohol resin such as polyvinyl alcohol resin, polyethylene, propylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-(meth) ) Polyolefin resins such as acrylic acid resins, polyester resins such as polyethylene terephthalate resins (PET resins), single and copolymers of thermoplastic resins such as acrylic resins, polycarbonate resins, and polyurethane resins, or mixed resins thereof can be preferably mentioned. Especially, polyvinyl resin is preferable.

Further, the support layer may be composed of one layer or may be a laminate composed of two or more layers, but is a laminate composed of two or more layers, and at least one layer contains a glass component. it is desirable That is, the support layer is a laminate composed of two or more layers, and it is preferable that at least one layer is a thermoplastic resin layer and the other one layer is a glass component layer containing a glass component. By setting it as such a structure, excellent impact resistance is obtained and shape stability improves.

The glass component layer containing a glass component is preferably a layer constituted by, for example, glass fibers.

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. It is preferable that it is a laminated body which has thermoplastic resin layers in order.

When the support layer has a plurality of thermoplastic resin layers, the types of resin forming the thermoplastic resin layers may be the same or different, and the thickness may be the same or different.

It is preferable that it is 1-10 mm, and, as for the thickness of a support body layer, it is more preferable that it is 1-5 mm. When the thickness of the support layer is within the above range, excellent water resistance, moisture resistance, impact resistance and scratch resistance are obtained. In addition, it becomes difficult to generate stress deflection due to a difference in elongation due to temperature or the like with other layers such as the foamed resin layer.

As described above, the thickness of the support layer is preferably thinner than that of the foamed resin layer. Stress deflection due to difference in elongation due to moisture or the like with other layers such as the foamed resin layer is less likely to occur.

(Decoration layer)

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

By providing a concealing layer, the base on which the floor decorative material is installed can be concealed, and in the case where the substrate layer is colored or has uneven color, an intended color can be imparted to adjust the color of the surface.

In addition, by forming a pattern layer, a stone grain pattern imitating the surface of a rock such as a wood grain pattern or a marble pattern (eg travertine marble pattern), a cloth pattern imitating a cloth grain or cloth pattern, a tile attachment pattern, a brick A laminated pattern or the like, or a pattern such as a combination of these, a patchwork pattern, or the like can be imparted to the decorative sheet. These patterns are formed not only by multi-color printing using normal process colors of yellow, red, blue, and black, but also by multi-color printing or the like by preparing individual color plates constituting the pattern.

As an ink composition used for the decorative layer, a binder resin in which colorants such as pigments and dyes, extender pigments, solvents, stabilizers, plasticizers, catalysts, curing agents, and the like are appropriately mixed is used. The binder resin is not particularly limited, and examples thereof include preferably urethane resins, vinyl chloride/vinyl acetate copolymer resins, vinyl chloride/vinyl acetate/acrylic copolymer resins, acrylic resins, polyester resins, and nitrocellulose resins. can As binder resin, arbitrary things can be used individually by 1 type or in mixture of 2 or more types among these.

In addition, as the colorant, inorganic pigments such as carbon black (ink), iron black, titanium white, antimony white, yellow lead, titanium yellow, bengala, cadmium red, ultramarine blue, cobalt blue, quinacridone red, isoindolinone yellow, phthalocyanine blue Preferable examples include organic pigments such as dyes, metallic pigments including scale-like flakes of aluminum and brass, pearlescent pigments including scale-like flakes such as titanium dioxide-coated mica and basic lead carbonate, and the like. have.

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 installed according to the purpose, and is preferably a layer formed of a thermoplastic resin. As a thermoplastic resin, what was illustrated as a thermoplastic resin provided in the said foamed resin layer is mentioned preferably. Especially, polyolefin resin is preferable, and a polyethylene resin and a propylene resin 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 to be used, those exemplified as the colorant used in the decorative layer are preferably mentioned.

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

In addition, you may add various additives, such as a filler, a flame retardant, a lubricant, antioxidant, a ultraviolet absorber, and a light stabilizer, to the base resin layer as needed.

(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 a thermoplastic resin, what was illustrated as a thermoplastic resin provided in the said foamed resin layer is mentioned preferably. Especially, polyolefin resin is preferable, and a polyethylene resin and a propylene resin are more preferable.

The transparent resin layer is a transparent resin layer, such that the decorative layer is see-through. Here, transparency is a concept including colored transparency and translucency in addition to colorless transparency.

Further, various additives such as fillers, flame retardants, lubricants, antioxidants, ultraviolet absorbers, and light stabilizers may be added to the transparent resin layer as needed within the range of not impairing the transparency.

The thickness of the transparent resin layer is preferably 10 to 150 μm, more preferably 30 to 100 μm, still more preferably 50 to 100 μm. When the thickness of the transparent resin layer is within the above range, the decoration layer can be protected, handling is easy, 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 use decorative material of the present invention.

The surface protective layer is preferably constituted by applying a resin composition containing a curable resin onto a decorative layer or a preferably provided transparent resin layer or adhesive layer and curing it. By containing the crosslinked curable curable resin, the surface properties of the floor use decorative material can be improved.

As the curable resin used for forming the surface protective layer, an ionizing radiation curable resin and a thermosetting resin are preferably used, and a so-called hybrid type may be used in which a plurality of these are used, for example, an ionizing radiation curable resin and a thermosetting resin are used together. .

Among these, from the viewpoint of increasing the crosslinking density of the resin forming the surface protective layer and improving the surface properties, an ionizing radiation curable resin is preferable, and can be applied without a solvent and is easy to handle. Curable resins are more preferred.

An ionizing radiation-curable resin refers to a resin that has energy quanta capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, resins that crosslink and cure by irradiation with ultraviolet rays or electron beams. Specifically, it can be appropriately selected from polymerizable monomers and polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resins.

As the polymerizable monomer, a (meth)acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is suitable, and among these, polyfunctional (meth)acrylates are preferable. As the polyfunctional (meth)acrylate, any (meth)acrylate having two or more ethylenically unsaturated bonds in the molecule is not particularly limited. These polyfunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more type.

Subsequently, as the polymerizable oligomer, an oligomer having a radically polymerizable unsaturated group in the molecule, for example, an epoxy (meth)acrylate type, a urethane (meth)acrylate type, a polyester (meth)acrylate type, or a polyether (meth) An acrylate type|system|group etc. are mentioned.

In addition, 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, a silicone (meth)acrylate-based oligomer having a polysiloxane bond in the main chain, and a small Aminoplast resin modified from aminoplast resin having many reactive groups in the molecule Cationic polymerization in molecules of (meth)acrylate-based oligomers, novolak-type epoxy resins, bisphenol-type epoxy resins, aliphatic vinyl ethers, aromatic vinyl ethers, etc. There are oligomers having sexual functional groups, and the like.

In the present invention, a monofunctional (meth)acrylate can be appropriately used in combination with the polyfunctional (meth)acrylate and the like for the purpose of reducing the viscosity thereof within a range not impairing the object of the present invention. . These monofunctional (meth)acrylates may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the thermosetting resin include epoxy resins, phenol resins, urea resins, unsaturated polyester resins, melamine resins, alkyd resins, polyimide resins, silicone resins, hydroxyl functional acrylic resins, carboxyl functional acrylic resins, amide functional copolymers, and urethanes. Resin etc. are mentioned preferably.

Moreover, as a thermosetting resin, a 2-component curable resin is also mentioned preferably, and a 2-component curable resin of a polyol and an isocyanate is preferable.

Here, as a polyol, acrylic polyol, polyester polyol, epoxy polyol, etc. are mentioned preferably.

In addition, as an isocyanate, any polyhydric isocyanate having two or more isocyanate groups in a molecule is sufficient, and examples thereof include 2,4-tolylene diisocyanate (TDI), xylene diisocyanate (XDI), naphthalene diisocyanate, and 4,4'-diphenyl. Aromatic isocyanates such as methane diisocyanate, 1,6-hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), methylene diisocyanate (MDI), hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. Polyisocyanates such as aliphatic (or alicyclic) isocyanates are used. Alternatively, adducts or multimers of these various isocyanates, such as tolylene diisocyanate adducts and tolylene diisocyanate trimers, are also used.

In addition, various additives can be contained in the resin composition constituting the surface protective layer within a range that does not impair its performance. Examples of various additives include ultraviolet absorbers (UVA), light stabilizers (HALS, etc.), polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropy imparting agents, coupling agents, plasticizers, and 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 properties are obtained.

(adhesive layer)

The adhesive layer is a layer provided as necessary when laminating the resin layer when providing the base resin layer and the transparent resin layer. As the adhesive used in the adhesive layer, urethane adhesives, acrylic adhesives, acrylic/urethane adhesives, polyester adhesives, polyesterurethane adhesives, polyamide adhesives, polystyrene adhesives, cellulosic adhesives and the like are preferably used. These adhesives can be used individually by 1 type or as a mixture of 2 or more types.

The adhesive layer thickness 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 is obtained and the floor use 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 installation, and is a residential flooring material, especially for toilets, washrooms, It is suitable for use in places where water is frequently used, such as kitchens.

The thickness of the floor decorative material of the present invention is preferably 5 to 25 mm, more preferably 7 to 20 mm, and still more preferably 8 to 15 mm, from the viewpoint of obtaining excellent impact resistance, heat insulation, water resistance, moisture resistance, load resistance and scratch resistance. desirable. In addition, considering the ease of installation, it is preferable to set it as the same thickness as that of a wooden flooring installed in a place other than a place where water is frequently used, such as a living room or a corridor. The thickness of the wood flooring material is usually 8 mm, 12 mm, 15 mm, etc., and 12 mm is the standard thickness.

[Method of manufacturing floor decorative materials]

The floor use decorative material of this invention can be manufactured through the following process, for example.

(Preparation process of foamed resin layer)

First, a foamed resin layer is prepared. As described above, the foamed resin layer is prepared 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, and the amount of foaming agent and plasticizer used.

(Formation process of decorative layer)

A decorative layer is formed on the support layer or on the base resin layer provided as needed, using the ink composition. The ink composition may be applied by a method such as gravure printing, offset printing, screen printing, flexographic printing, or inkjet printing, for example. In addition, what is necessary is just to form by various coating methods, such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc., when forming a concealing layer (less printed layer), for example.

(Adhesion process between foamed resin layer and support layer)

Bonding between the foamed resin layer obtained in the step of preparing the foamed resin layer and the support layer on which the decorative layer is formed can be performed using, for example, a hot melt adhesive other than a heat-sensitive adhesive or a pressure-sensitive adhesive. 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 preferable. This PUR contains a functional group (isocyanate group) that reacts with moisture in its components, and after cooling and curing, reacts with moisture adhering to the substrate or decorative sheet or moisture imparted through them. After the reaction, it has the characteristics of not melting even when heated and having high adhesive strength.

(Laminating process of transparent resin layer)

It is preferable to provide the transparent resin layer by dry lamination through an adhesive layer after forming the decorative layer. For example, a decorative layer is formed on the base substrate layer by the above method, and then, for example, a two-component curing type urethane resin, acrylic resin, vinyl chloride-vinyl acetate copolymer and the like using a block isocyanate as a curing agent are dried. An adhesive layer may be formed by applying an adhesive for lamination, and a transparent resin layer may be provided by a dry lamination method.

(Process of forming surface protective layer)

The thickness of the surface protective layer is obtained by applying a curable resin composition on the decorative layer or on the transparent resin layer after the decorative layer formation step or, in the case of laminating the transparent resin layer, after the resin layer lamination step, and curing. Apply by a known method such as gravure coating, bar coating, roll coating, reverse roll coating, comma coating, etc. to form an uncured resin layer so that is about 3 to 20 μm, and then to the uncured resin layer, It can be formed by applying heat or irradiating ionizing radiation such as electron beams or ultraviolet rays to cure the uncured resin layer.

The heating temperature in the case of thermal curing is appropriately determined according to the resin to be used.

In the case of using an electron beam as the ionizing radiation, the accelerating voltage can be appropriately selected depending on the resin used and the thickness of the layer, but it is usually preferable to cure the uncured resin layer at an accelerating voltage of about 70 to 300 kV. . The irradiation dose is preferably an amount that saturates the crosslinking density of the resin layer, 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, various types of electron beam accelerators such as Cockcroft Walton type, van der Graf type, resonance transformer type, insulating core transformer type, linear type, dynamite type, and high frequency type can be used.

When using ultraviolet rays as ionizing radiation, those containing ultraviolet rays with a wavelength of 190 to 380 nm are radiated. The ultraviolet light source is not particularly limited, and for example, a high-pressure mercury-vapor lamp, a low-pressure mercury-vapor lamp, a metal halide lamp, a carbon arc lamp, or the like is used.

Example

Next, the present invention will be described in more detail by examples, but the present invention is not limited at all by these examples.

(Evaluation and measurement methods)

About the decorative materials for floors obtained in each Example and Comparative Example, it was evaluated and measured by the following method.

1. Evaluation of scratch resistance (pencil hardness test)

In the "scratch hardness (pencil method) test" in accordance with JIS K5600-5-4, a test of scratching the surface of a floor decorative material with a load of 500 g was performed 5 times, and the hardness of a pencil that did not generate scratches 3 times or more was measured. It was referred to as hardness and evaluated according to the following criteria.

○ B or higher, and had very excellent scratch resistance.

It was 2B or more and had excellent scratch resistance.

x 3B or less, and scratch resistance was inferior.

2. Evaluation of load capacity

Four metal jigs of 2 cm square were placed at the four corners of the floor decorative material (15 cm square), and weights of 80 kg were placed so that the load was applied evenly to the four jigs. After leaving it to stand for one week in this state, the weight was removed and the external appearance of the floor use decorative material was evaluated according to the following criteria.

○ Surface change of the floor decorative material could not be confirmed.

(triangle|delta) Although a slight recess was confirmed on the surface of the floor use decorative material, there was no problem in practical use.

X Concave part was confirmed on the surface of the floor use decorative material.

3. Evaluation of shape stability (evaluation of warpage)

Warpage when a floor decorative material of chuck angle size (30.3 cm square) is left at 5°C × 30% RH for one week and then 40°C × 90% RH for one week before leaving, when the temperature condition is changed, and after leaving The degree of was measured and evaluated according to the following criteria.

○ Warpage was less than ±0.6mm.

△ Warpage was ±0.6 mm or more and ±0.8 mm or less.

× Warpage was greater than 0.8 mm or less than -0.8 mm.

Here, + represents that the decoration layer side of the floor decorative material becomes convex and bends, - represents that it becomes concave and bends.

Example 1

On a colored polypropylene resin film (thickness: 60 μm, color: white), a 2 μm-thick stone-grain decorative layer was formed using an ink composition (acrylic urethane-based) by gravure printing. Subsequently, a transparent polypropylene resin film (thickness: 80 µm) was dry laminated on the decorative layer using a urethane-based dry lamination adhesive, and installed. On the transparent polypropylene resin film, an electron beam curable resin composition (acrylate-based) was applied by gravure printing at a coating amount of 15 g/m 2 to form a coating film, and electron beams were irradiated under conditions of 175 keV and 5 Mrad (50 kGy) to The coating film was crosslinked and cured to form a surface protective layer (thickness: 15 μm), and a decorative sheet (thickness: 160 μm) was produced.

Subsequently, a medium-density polyethylene resin sheet (tensile modulus: 200 MPa, thickness: 3 mm) was prepared as a support layer, and the support layer and the decorative sheet were placed so as to face the colored polypropylene resin film (base resin layer) of the decorative sheet. , and bonded by dry lamination through an adhesive for urethane-based dry lamination.

Subsequently, as a foamed resin layer, a 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)) is used, and produced by the beads method. One foamed resin layer (foaming ratio: 10 times, compressive elastic modulus: 43 MPa, thickness: 9 mm) was prepared, and the support layer and the foamed resin layer to which the cosmetic sheet was adhered were bonded using a urethane-based reactive hot melt adhesive, A cosmetic material for the floor was produced. The result of evaluating the obtained floor use decorative material is shown in Table 1.

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 for changing to the foamed resin layer and the support layer shown in Table 1. The result of evaluating the obtained floor use decorative material is shown in Table 1.

*1, PE1; Medium Density Polyethylene Resin Sheet

PE2; Low Density Polyethylene Resin Sheet

PVC; Glass fiber-reinforced vinyl chloride board (three-layer structure of polyvinyl chloride resin layer / glass fiber layer / polyvinyl chloride resin layer, total thickness is 3 mm)

PP; polypropylene resin sheet

ADVANTAGE OF THE INVENTION According to this invention, it is possible to obtain a floor decorative material that is excellent in heat insulation, water resistance, moisture resistance, shape stability, excellent in surface properties such as impact resistance, load resistance and scratch resistance, and also excellent in ease of installation. The floor decorative material of the present invention is suitably used as a residential flooring material, particularly a flooring material for places where water is frequently used, such as toilets, washrooms, and kitchens.

10: floor cosmetic 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, the foamed resin layer has a foaming ratio of 5 to 20 times, a compressive modulus of elasticity of 20 MPa or more, and a tensile modulus of elasticity of the support layer of 180 MPa or more and 300 MPa or less.
The thickness of the support layer is 1 to 10 mm,
The floor cosmetic material in which the foamed resin layer is thicker than the support layer. The floor decorative material according to claim 1, comprising a foamed resin layer, a support layer, a base resin layer, a decorative layer and a surface protection 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 claim 1 or 2, wherein the foamed resin layer is formed by a bead method. The floor decorative material according to claim 1 or 2, 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 comprising a first thermoplastic resin layer, a glass component layer, and a second thermoplastic resin layer in this order. The floor decorative material according to claim 1 or 2, wherein the foamed resin layer has a thickness of 5 to 15 mm.

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