JP2011220031A - Floor material excellent in flame retardancy - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floor material excellent in flame retardancy that hardly generates harmful gases in combustion, excels in combustion safety, and produces less smoke.SOLUTION: A floor material 10 of the present invention comprises at least substrate layers 1 and 2, and a backing layer 3 stacked on the lower surface side of the substrate layer. The substrate layers 1 and 2 each comprises 5 to 40 pts. mass of red phosphorus, 3 to 20 pts. mass of laminar silicate, and 15 to 50 pts. mass of scale-like filler, and 100 to 230 pts. mass of metal hydroxide relative to 100 pts. mass of a resin with no chlorine atoms in the chemical structure. The backing layer 3 comprises a resin composition containing 1 to 5 pts. mass of laminar silicate relative to 100 pts. mass of the resin with no chlorine atoms in the chemical structure.

Description

  The present invention relates to a flooring material excellent in flame retardancy, for example, used as a flooring material for a ship, a flooring material for a vehicle such as a railway or a bus, or a flooring material for a building such as a building, an apartment, a house, or a commercial facility. .

  Conventionally, as flooring for buildings such as buildings, condominiums, houses, commercial facilities, etc., or flooring for vehicles such as railways and buses, it has excellent flame resistance, wear resistance and heat resistance, and is easy to process and economical. Therefore, many flooring materials made of vinyl chloride resin (PVC) containing a large amount of plasticizer have been employed.

  However, since PVC flooring generates a toxic gas such as hydrogen chloride together with a large amount of smoke during combustion, problems such as disaster prevention such as evacuees inhaling the toxic gas during a fire, There was a problem of causing environmental pollution by incineration disposal. Moreover, since the PVC flooring material contains a large amount of plasticizer, there is a specific odor, and the odor caused by such a plasticizer is said to be one of the causes of sick house syndrome. In addition, the plasticizer bleeds on the surface due to long-term use, and it tends to cause fogging, resulting in poor appearance.

  Therefore, in recent years, it has been proposed to use the following materials as constituent materials for flooring.

  For example, in Patent Document 1, as a flame retardant material, 0.01 to 1 unit of a phosphoric acid compound having a carbon-carbon double bond is graft-reacted to 1 unit of a monomer unit constituting a polyolefin resin. It has been proposed to use a polyolefin-based resin.

  In Patent Document 2, as a flame retardant material, at least one base resin selected from polyester resins, polyacetal resins, styrene resins, polyamide resins, vinyl resins, olefin resins, and acrylic resins is used. A heterocyclic compound having a cyano group, at least one phosphorus-containing compound selected from red phosphorus, phosphate ester, phosphate ester amide, phosphonitrile compound, organic phosphonic acid compound and organic phosphinic acid compound, and polyphenylene From sulfide resin, polyphenylene oxide resin, polycarbonate resin, aromatic nylon, polyarylate resin, aromatic epoxy resin, and resin having an aromatic ring having hydroxyl group and / or amino group in the main chain or side chain At least one selected aromatic tree It has been proposed to use a flame retardant resin composition which is composed of a.

  In these proposed flooring materials, the problem of generation of harmful gases during combustion, the generation of peculiar odors caused by plasticizers and the problem of cloudiness are almost solved.

JP-A-11-171936 JP 2009-132935 A

  However, the flooring materials described in Patent Documents 1 and 2 have problems that the flame retardancy is insufficient and the amount of smoke generated is relatively large during combustion.

  The present invention has been made in view of such a technical background, and provides a flooring material that is less likely to generate harmful gases during combustion, has excellent combustion safety, has low smoke generation, and has excellent flame retardancy. For the purpose.

  In order to achieve the above object, the present invention provides the following means.

[1] A substrate layer and at least a backing layer laminated on the lower surface side of the substrate layer,
The base material layer has 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and 15 to 50 parts of flaky filler with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. It consists of a resin composition containing 100 to 230 parts by mass of a metal hydroxide, 100 parts by mass,
The backing layer is composed of a resin composition containing 1 to 5 parts by mass of a layered silicate with respect to 100 parts by mass of a resin having no chlorine atom in the chemical structure. Wood.

[2] The base layer has a tensile modulus of 100 to 1500 MPa, the backing layer has a tensile modulus of 500 to 1500 MPa,
The tensile modulus of elasticity of the base material layer and the backing layer is 700 MPa or less,
The floor material excellent in flame retardancy according to item 1 above, wherein the ratio of the linear expansion coefficient is in the range of the linear expansion coefficient of the base material layer / the linear expansion coefficient of the backing layer = 1.0 / 1.2 to 4.0. .

[3] At least a first substrate layer, a second substrate layer laminated on the lower surface side of the first substrate layer, and a backing layer laminated on the lower surface side of the second substrate layer,
The first base layer has 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and 15 scaly fillers with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. -50 parts by mass, consisting of a resin composition containing 100-230 parts by mass of metal hydroxide,
The second base layer has 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and 15 scaly fillers with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. -50 parts by mass, consisting of a resin composition containing 100-230 parts by mass of metal hydroxide,
The backing layer is composed of a resin composition containing 1 to 5 parts by mass of a layered silicate with respect to 100 parts by mass of a resin having no chlorine atom in the chemical structure. Wood.

[4] The tensile elastic modulus of the first base material layer is 100 to 1500 MPa, the tensile elastic modulus of the second base material layer is 100 to 1500 MPa, and the tensile elastic modulus of the backing layer is 500 to 1500 MPa. ,
The tensile modulus of elasticity of the first base material layer, the second base material layer, and the backing layer is 700 MPa or less,
The ratio of the linear expansion coefficient is the linear expansion coefficient of the first base material layer / the linear expansion coefficient of the second base material layer / the linear expansion coefficient of the backing layer = 1.0 / 1.0 to 3.0 / 1.2 to 4. The flooring material excellent in flame retardancy according to item 3 in the range of 4.0.

[5] As the resin having no chlorine atom in the chemical structure constituting the backing layer, at least a styrene elastomer having a styrene component content of 40 to 80% by mass and a crystalline resin are used,
Any one of the preceding clauses 1-4 which contain 5-40 mass% of said styrene-type elastomer with respect to the whole resin component in said backing layer, and contain 55-80 mass% of said crystalline resin with respect to the whole resin component. The flooring material excellent in flame retardancy described in the item.

  [6] The flooring material excellent in flame retardancy according to any one of items 1 to 5, wherein red phosphorus whose surface is coated with a resin is used as the red phosphorus.

  [7] The flooring material excellent in flame retardancy according to any one of items 1 to 5, wherein red phosphorus whose surface is coated with a phenol resin is used as the red phosphorus.

  [8] The flooring material excellent in flame retardancy according to any one of the above items 1 to 7, wherein flaky glass is used as the flaky filler.

  In the invention of [1], since a resin having no chlorine atom in the chemical structure is used as a constituent material of the base material layer and the backing layer, there is little generation of harmful gas at the time of combustion and excellent combustion safety and disaster prevention. In addition to being convenient, it can contribute to environmental conservation. Moreover, since a base material layer contains 3-20 mass parts of layered silicate with respect to 100 mass parts of resin which does not have a chlorine atom in chemical structure, a flame-retardant effect can be acquired, and also 100 mass of the resin Since 100-230 mass parts of metal hydroxide is contained with respect to a part, the said flame-retardant effect can be improved further. Moreover, since the base material layer contains 15 to 50 parts by mass of the scale-like filler with respect to 100 parts by mass of the resin having no chlorine atom in the chemical structure, the thermal dimensional stability of the flooring can be improved. . Furthermore, since the base material layer contains 5 to 40 parts by mass of red phosphorus with respect to 100 parts by mass of the resin having no chlorine atom in the chemical structure, a higher flame retardancy is achieved while suppressing the amount of smoke generation low. be able to. Moreover, since a backing layer contains 1-5 mass parts of layered silicate with respect to 100 mass parts of resin which does not have a chlorine atom in chemical structure, it can acquire a flame-retardant effect sufficient as a flooring.

  In the invention of [2], the ratio of the linear expansion coefficient is in the range of the linear expansion coefficient of the base material layer / the linear expansion coefficient of the backing layer = 1.0 / 1.2 to 4.0. Can be prevented sufficiently.

  In the invention of [3], since a resin having no chlorine atom in the chemical structure is used as a constituent material of the first base material layer, the second base material layer, and the backing layer, no harmful gas is generated during combustion. Fewer combustion safety, convenient for disaster prevention, and can contribute to environmental conservation. Moreover, in a 1st base material layer and a 2nd base material layer, since 3-20 mass parts of layered silicate is contained with respect to 100 mass parts of resin which does not have a chlorine atom in a chemical structure, a flame-retardant effect is acquired. Furthermore, since the metal hydroxide is contained in an amount of 100 to 230 parts by mass with respect to 100 parts by mass of the resin, the flame retardant effect can be further enhanced. Moreover, in the 1st base material layer and the 2nd base material layer, since 15-50 mass parts of scaly fillers are contained with respect to 100 mass parts of resin which does not have a chlorine atom in chemical structure, the thermal dimension of a flooring material Stability can be improved. Furthermore, in the 1st base material layer and the 2nd base material layer, since red phosphorus is contained 5-40 mass parts with respect to 100 mass parts of resin which does not have a chlorine atom in chemical structure, suppressing the amount of smoke generation low. Further, higher flame retardancy can be achieved. Moreover, since a backing layer contains 1-5 mass parts of layered silicate with respect to 100 mass parts of resin which does not have a chlorine atom in chemical structure, it can acquire a flame-retardant effect sufficient as a flooring.

  In the invention of [4], the ratio of the linear expansion coefficient is: linear expansion coefficient of the first base material layer / linear expansion coefficient of the second base material layer / linear expansion coefficient of the backing layer = 1.0 / 1.0-3. Since it is in the range of 0.0 / 1.2 to 4.0, warping of the flooring can be sufficiently prevented.

  In the invention of [5], since the resin composition constituting the backing layer contains 5 to 40% by mass of the styrene elastomer with respect to the entire resin component of the backing layer, an adhesive for adhering to the laying base surface; Since the crystalline resin is contained in an amount of 55 to 80% by mass with respect to the entire resin component of the backing layer, warping of the flooring can be more sufficiently prevented.

  In the invention of [6], the red phosphorus whose surface is coated with a resin is used as the red phosphorus, so that the flame retardancy can be further improved.

  In the invention of [7], the red phosphorus whose surface is coated with a phenol resin is used as the red phosphorus, so that the flame retardancy can be further improved.

  In the invention of [8], scale-like glass is used as the scale-like filler, so that the thermal dimensional stability of the flooring can be further improved.

It is sectional drawing which shows one Embodiment of the flooring of this invention. It is sectional drawing which shows other embodiment of the flooring of this invention. It is sectional drawing which shows other embodiment of the flooring of this invention.

  One embodiment of a flooring (10) according to the present invention is shown in FIG. The flooring (10) includes a first base material layer (1), a second base material layer (2) laminated on the lower surface of the first base material layer (1), and the second base material layer ( The backing layer (3) laminated on the lower surface of 2) and the surface layer (4) laminated on the upper surface of the first base material layer (1) are provided. In this invention, as shown in FIG. 2, you may employ | adopt the structure in which the said surface layer (4) is not provided. That is, in the flooring (10), the second substrate layer (2) is laminated on the lower surface of the first substrate layer (1), and the backing layer (3) is formed on the lower surface of the second substrate layer (2). A stacked structure may be used.

  Said 1st base material layer (1) is 5-40 mass parts of red phosphorus, 3-20 mass parts of layered silicate, and scaly filling with respect to 100 mass parts of resin which does not have a chlorine atom in chemical structure. It consists of a resin composition containing 15 to 50 parts by mass of the agent and 100 to 230 parts by mass of the metal hydroxide.

  The second base layer (2) is composed of 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and scale pieces with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. It consists of a resin composition containing 15 to 50 parts by mass of a filler and 100 to 230 parts by mass of a metal hydroxide.

  In addition, in this invention, it is good also as what comprises the laminated part of a said 1st base material layer (1) and a said 2nd base material layer (2) by a single layer. That is, as shown in FIG. 3, a flooring (10) according to another embodiment of the present invention includes a base material layer (6) and a backing layer (3) laminated on the lower surface of the base material layer (6). ) And a surface layer (4) laminated on the upper surface of the base material layer (6). The base material layer (6) contains 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and a scaly filler with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. It consists of a resin composition containing 15 to 50 parts by mass and 100 to 230 parts by mass of a metal hydroxide.

  Next, the configuration of the first base material layer (1), the second base material layer (2), and the base material layer (6) will be described in detail.

  The resin having no chlorine atom in the chemical structure that constitutes the first base material layer (1), the second base material layer (2), and the base material layer (6) is not particularly limited. For example, olefin resin, styrene resin and the like can be mentioned.

  The olefin resin is not particularly limited. For example, ethylene-α olefin copolymer, random polypropylene, polyethylene, polypropylene, polybutene, polypentene, ethylene-propylene copolymer, ethylene-butene copolymer. Polymer, polybutadiene, polyisoprene, hydrogenated polybutadiene, hydrogenated polyisoprene, ethylene-propylene-diene copolymer, ethylene-butene-diene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, And ethylene-methyl methacrylate copolymer.

  The styrene resin is not particularly limited. For example, hydrogenated styrene-butadiene rubber (HSBR), styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS). ), Styrene-butadiene rubber (SBR), styrene-ethylene / propylene-styrene copolymer (SEPS), styrene-ethylene / butylene-styrene copolymer (SEBS), and the like.

  The red phosphorus is not particularly limited, but it is preferable to use red phosphorus whose surface is coated with a resin. By containing red phosphorus, the flooring becomes highly flame retardant. However, the flame retardant performance can be further improved by coating the surface of red phosphorus with a resin. Examples of the coating resin include phenol resin, melamine resin, and epoxy resin. Among these, as the red phosphorus, it is more preferable to use red phosphorus whose surface is coated with a phenol resin.

  The content of the red phosphorus is 5 to 40 parts by mass (including the amount of the coating resin when the resin is coated with a resin) with respect to 100 parts by mass of the resin having no chlorine atom in the chemical structure. To do. If the amount is less than 5 parts by mass, high flame retardancy cannot be obtained. Moreover, when it exceeds 40 mass parts, the problem that the amount of smoke generation increases will be produced. Among them, the content of the red phosphorus is 15 to 30 parts by mass (in the case where the resin is coated with a resin, the amount of the coating resin with respect to 100 parts by mass of the resin having no chlorine atom in the chemical structure). ) Is preferred.

  The layered silicate is not particularly limited, and examples thereof include montmorillonite, mica, saponite, hectorite, beidellite, nontronite, kaolinite, vermiculite, halloysite, and pyrophyllite. Among these, it is preferable to use montmorillonite and / or mica.

  As the layered silicate, an organically treated one is preferably used. In the organic treatment, the layer of the layered silicate is expanded using an organic onium salt or the like. When an organic onium ion structure is present between the layered silicate layers, a substance having a small intermolecular force such as a resin can be inserted between the negatively charged silicate layers, and the dispersibility of the layered silicate in the resin Can be improved. The organic onium salt is not particularly limited, but an alkyl onium salt is preferably used. Among them, it is more preferable to use a quaternary ammonium salt having at least one alkyl group having 1 to 32 carbon atoms, and it is particularly preferable to use a quaternary ammonium salt having at least one alkyl group having 1 to 18 carbon atoms. Although it does not specifically limit as said quaternary ammonium salt, For example, tetraethylammonium, tetrabutylammonium, tetraoctylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethylhexadecylammonium , Trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl octadecadienyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, triethyl octadecyl ammonium, tributyl dodecyl ammonium, tributyl tetradecyl Ammo , Tributyl hexadecyl ammonium, tributyl octadecyl ammonium, dimethyl dioctyl ammonium, dimethyl didecyl ammonium, dimethyl ditetradecyl ammonium, dimethyl dihexadecyl ammonium, dimethyl dioctadecyl ammonium, dimethyl dioctadecenyl ammonium, dimethyl dioctadecadi Enylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecylammonium, diethyldioctadecylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium, methylbenzylhexa Decyl ammonium, dibenzyl dihex Examples include decyl ammonium, trioctyl methyl ammonium, tridodecyl methyl ammonium, tritetradecyl methyl ammonium, trioctyl ethyl ammonium, tridodecyl ethyl ammonium, trioctyl butyl ammonium, tridodecyl butyl ammonium, trimethyl benzyl ammonium, and trimethyl phenyl ammonium. .

  As the layered silicate, it is preferable to use one having an interlayer distance of 2.0 nm or more due to the organic treatment. In this case, there is an advantage that the dispersibility of the layered silicate in the resin can be improved. Among them, as the layered silicate, it is more preferable to use one having an interlayer distance of 3.0 nm or more due to the organic treatment.

  The content of the layered silicate is 3 to 20 parts by mass (including the amount of organic matter when organically treated) with respect to 100 parts by mass of the resin having no chlorine atom in the chemical structure. To do. If it is less than 3 parts by mass, sufficient flame retardancy cannot be imparted. If it exceeds 20 parts by mass, the resin composition becomes brittle and mechanical properties such as tensile strength and tensile elongation are lowered. Especially, it is preferable that content of the layered silicate with respect to 100 mass parts of resin which does not have a chlorine atom in the said chemical structure is 5-15 mass parts.

  Although it does not specifically limit as said metal hydroxide, For example, magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide etc. are mentioned. Among these, it is preferable to use magnesium hydroxide because the flame retardant effect can be further enhanced. The average particle diameter of the metal hydroxide is preferably 0.1 to 50 μm.

  As the metal hydroxide, it is preferable to use one that has been treated with a fatty acid or a silane compound. By being treated (contact treatment) with such a substance, there is an advantage that dispersibility with the resin can be improved. The fatty acid is not particularly limited, and examples thereof include stearic acid, aluminum stearate, calcium stearate, magnesium stearate, zinc stearate, sodium stearate, stearic acid amide, erucic acid amide, and oleic acid amide. Of these, stearic acid is preferably used. The silane compound is not particularly limited. For example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxy Propyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- ( Minoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl- N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, N-phenyl- Examples include 3-aminopropyltrimethoxysilane.

  The content of the metal hydroxide is 100 to 230 parts by mass with respect to 100 parts by mass of the resin having no chlorine atom in the chemical structure (in the case where the fatty acid treatment or silane compound treatment is performed, the fatty acid or silane Including the amount of compound). If the amount is less than 100 parts by mass, sufficient flame retardancy cannot be imparted. On the other hand, if it exceeds 230 parts by mass, the resin composition becomes brittle, and mechanical properties such as tensile strength and tensile elongation decrease. Especially, it is preferable that content of the metal hydroxide with respect to 100 mass parts of resin which does not have a chlorine atom in the said chemical structure is 150-200 mass parts.

  The scaly filler is not particularly limited, and examples thereof include scaly glass, scaly graphite, and scaly talc. Among them, it is preferable to use scale-like glass, which can further improve the thermal dimensional stability of the flooring.

  As the glass flakes, those having an average particle diameter of 50 to 1000 μm and an average thickness of 0.1 to 20 μm are preferably used. In this case, the thermal dimensional stability of the flooring can be further improved. .

  As the scale-like glass, it is preferable to use an organically treated glass. By the organic treatment, the adhesiveness at the interface with the resin is improved, and the effect of improving the thermal dimensional stability can be further enhanced. The organic material for the organic treatment is not particularly limited, and examples thereof include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropyl Methyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, 2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3 -Triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate, 3-trimethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine and its partial hydrolyzate , Silane compounds such as N-phenyl-3-aminopropyltrimethoxysilane, and the like.

  The content of the scaly filler is 15 to 50 parts by mass with respect to 100 parts by mass of the resin having no chlorine atom in the chemical structure. If it is less than 15 parts by mass, the thermal dimensional stability of the flooring cannot be improved. On the other hand, when the amount exceeds 50 parts by mass, sufficient tensile strength and sufficient tensile elongation cannot be provided, so that the heel mark resistance is poor. Especially, it is preferable to contain 20-35 mass parts of scaly fillers with respect to 100 mass parts of resin which does not have a chlorine atom in the said chemical structure.

  Next, the configuration of the backing layer (3) will be described in detail. The said backing layer (3) consists of a resin composition which contains 1-5 mass parts of layered silicate with respect to 100 mass parts of resin which does not have a chlorine atom in chemical structure. If it is less than 1 part by mass, sufficient flame retardancy as a flooring material cannot be ensured. Moreover, when it exceeds 5 mass parts, the curvature of a flooring will become large.

  The layered silicate constituting the backing layer (3) is exemplified as the layered silicate constituting the first substrate layer (1), the second substrate layer (2), and the substrate layer (6). You can use the same as

  Examples of the resin having no chlorine atom in the chemical structure constituting the backing layer (3) include the first base material layer (1), the second base material layer (2), and the base material layer (6). The same thing as illustrated as resin to comprise can be used.

  Among these, as the resin having no chlorine atom in the chemical structure constituting the backing layer (3), it is preferable to use at least a styrene-based elastomer and a crystalline resin. The content of the styrene component in the styrenic elastomer is preferably 40 to 80% by mass from the viewpoint of improving the adhesive strength. Although it does not specifically limit as said styrene-type elastomer, For example, a styrene-ethylene-butylene-styrene (SEBS) copolymer etc. are mentioned. The crystalline resin is not particularly limited, and examples thereof include crystalline polypropylene and crystalline polyethylene.

  In the backing layer (3), the styrene-based elastomer is contained in an amount of 5 to 40% by mass based on the entire resin component of the backing layer (3), and the crystalline resin is contained in the entire resin component of the backing layer (3). It is preferable to adopt a configuration containing 55 to 80% by mass. By containing 5% by mass or more of the styrene-based elastomer, the polarity can be increased and the adhesive force can be improved, and when the content of the styrene-based elastomer is 40% by mass or less, warping of the flooring can be prevented. Moreover, warping of the flooring can be prevented by containing 55% by mass or more of the crystalline resin, and an adhesive for adhering to the laying ground surface by setting the content of the crystalline resin to 80% by mass or less. Adhesion can be improved.

  As resin which comprises the said surface layer (4), resin which does not have a chlorine atom in chemical structure is used. The resin having no chlorine atom in the chemical structure constituting the surface layer (4) is not particularly limited, and examples thereof include polypropylene resins, polyethylene resins, ethylene-vinyl acetate copolymers, ethylene-α olefins. A copolymer, an olefin-type elastomer, etc. are mentioned. The surface layer (4) may be composed of a single layer or a multilayer. By laminating such a surface layer (4), it is possible to provide a flooring (10) with improved wear resistance and stain resistance. The thickness of the surface layer (4) is preferably set to 0.1 to 1.0 mm.

  The surface layer (4) has a structure in which 1 to 10 parts by mass of a layered silicate and 3 to 15 parts by mass of an organic flame retardant are added to 100 parts by mass of a resin having no chlorine atom in the chemical structure. Is preferred.

  1 and 2, the first base material layer (first base material sheet) has a tensile elastic modulus of 100 to 1500 MPa, and the second base material layer (second base material sheet). ) Has a tensile elastic modulus of 100 to 1500 MPa, the backing layer (backing sheet) has a tensile elastic modulus of 500 to 1500 MPa, and the first base layer, the second base layer and the backing layer are integrated. It is preferable to adopt a configuration in which the tensile elastic modulus of the material is 700 MPa or less from the viewpoint that the workability of the flooring can be improved. Moreover, the ratio of the linear expansion coefficient is: linear expansion coefficient of the first base material layer / linear expansion coefficient of the second base material layer / linear expansion coefficient of the backing layer = 1.0 / 1.0 to 3.0 / 1. Adopting a configuration in the range of 2 to 4.0 is preferable in that the warping of the flooring (10) can be sufficiently prevented.

  Further, in the flooring (10) having the structure shown in FIG. 1, the thickness ratio of each layer is as follows: surface layer thickness / first base material layer thickness / second base material layer thickness / backing layer thickness. It is preferable to adopt a configuration in which the thickness is in the range of 1 / 1.0 to 1.3 / 3.0 to 5.0 / 0.8 to 1.2 because the flame retardancy can be further improved.

  In the flooring (10) having the configuration shown in FIG. 3, the base layer (base sheet) (6) has a tensile elastic modulus of 100 to 1500 MPa, and the backing layer (backing sheet) (3) has a tensile elastic modulus of 500. It is preferable to adopt a configuration in which the tensile modulus of elasticity of the base material layer (6) and the backing layer (3) is 700 MPa or less because the workability of the flooring material can be improved. . Further, a configuration in which the ratio of the linear expansion coefficient is in the range of the linear expansion coefficient of the base material layer (6) / the linear expansion coefficient of the backing layer (3) = 1.0 / 1.2 to 4.0 is adopted. However, it is preferable at the point which can fully prevent the curvature of a flooring (10).

  In order to improve the design of the flooring (10), for example, a printing layer is formed on the lower surface of the surface layer (4) and / or the upper surface of the base material layers (1), (2) and (6). May be. The printing method for forming the print layer is not particularly limited, and examples thereof include an inkjet method, a gravure printing method, a screen printing method, and a transfer printing method.

  Note that any of the first base material layer (1), the second base material layer (2), the base material layer (6), the backing layer (3), and the surface layer (4) is stearic acid. , Aluminum stearate, calcium stearate, magnesium stearate, zinc stearate, sodium stearate, stearamide, erucamide, oleic acid amide, polyethylene wax, antioxidant, UV absorber, lubricant, heat stabilizer, light Various additives such as a stabilizer, a weather resistance stabilizer, a flame retardant, a colorant, an antistatic agent, an antibacterial and antifungal agent, and a patterning agent (for the purpose of improving design properties) may be appropriately contained.

  Moreover, you may form a membrane | film | coat by applying a processing agent to the flooring (10) surface as needed. Taking the configuration of FIGS. 1 and 3 as an example, a film may be formed by applying a treatment agent on the upper surface of the surface layer (4). For example, from the viewpoint of improving wear resistance, a film mainly composed of a urethane resin or an acrylic resin may be formed on the upper surface of the surface layer (4). Such a film is generally formed to a thickness of 50 μm or less.

  Further, a configuration may be adopted in which a cloth made of a resin having no chlorine atom in its chemical structure is laminated and integrated on the lower surface of the backing layer (3) by heating and melting, and a fiber layer is further laminated. Although it does not specifically limit as said cloth, For example, a knitted fabric, a woven fabric, a nonwoven fabric etc. are mentioned. Since the fiber layer is provided, the adhesive is sufficiently impregnated into the fiber layer when the flooring is applied, and the flooring is sufficiently fixed to the laying surface by the anchor effect. Examples of the knitted fabric include a cold koji, and examples of the nonwoven fabric include a polypropylene nonwoven fabric, a polyester nonwoven fabric, and a nylon nonwoven fabric. Among them, a spunbond type nonwoven fabric that can be thinned is preferable, and a polypropylene spunbond nonwoven fabric is particularly suitable.

  The thickness of the flooring (10) of the present invention is preferably set to 1.0 to 4.0 mm as the total thickness (T) (see FIGS. 1 to 3). Especially, it is especially preferable that the total thickness (T) of the flooring (10) is set to 1.5 to 3.0 mm.

  The flooring (10) of the present invention may be configured as a tiled flooring (for example, a 500 mm square tile) or a sheeted flooring (for example, a long sheet having a width of about 600 to 2500 mm). There is no particular limitation. Moreover, you may provide an anti-slip | skid function by forming an uneven | corrugated pattern in the surface of a flooring (10).

  In addition, as a manufacturing method of each component layer (sheet | seat), such as a 1st base material layer (1), a 2nd base material layer (2), a base material layer (6), a backing layer (3), and a surface layer (4). Is not particularly limited, and can be produced by a known apparatus such as a calendaring machine or an extruder.

  Next, specific examples of the present invention will be described, but the present invention is not particularly limited to these examples.

<Example 1>
100 parts by mass of an olefin resin, 8 parts by mass of red phosphorus (red phosphorus whose surface is coated with a phenol resin), 5 parts by mass of montmorillonite (organized montmorillonite, “Esven WX” manufactured by Hojun Co., Ltd.), scaly glass (Nippon Sheet Glass Co., Ltd. “Glass flake REF-160A”, average thickness 5 μm, average particle size 160 μm) 20 parts by mass, average particle size 5 μm magnesium hydroxide (treated with stearic acid) 180 parts by mass The resin composition was kneaded with a Banbury mixer, and a first base sheet having a thickness of 0.30 mm was prepared using a two-roll tester having a set temperature of 160 ° C. and a diameter of 25 cm. The tensile modulus of the first substrate sheet (first substrate layer) was 190 MPa.

  Moreover, the 2nd base material sheet of thickness 1.2mm was created like the above using the resin composition of the same composition as the said resin composition. The tensile modulus of the second base sheet (second base layer) was 190 MPa.

  Further, 5 parts by mass of an ethylene elastomer, 25 parts by mass of a styrene elastomer (the content of styrene component is 67% by mass), 70 parts by mass of a crystalline polypropylene resin, montmorillonite (organized montmorillonite, “Esben” manufactured by Hojun Co., Ltd. WX ") 3 parts by mass of a resin composition was kneaded with a Banbury mixer, and a backing sheet having a thickness of 0.27 mm was prepared using a two-roll tester having a set temperature of 160 ° C and a diameter of 25 cm. The tensile modulus of the backing sheet (backing layer) was 650 MPa.

  The first base sheet, the second base sheet and the backing sheet were superposed in this order, and the tensile elastic modulus of the three layers was measured, and it was 430 MPa.

  Next, a 300 μm-thick polypropylene sheet (the tensile modulus of elasticity of this sheet is 300 MPa) having a pattern printed on the lower surface (overlapping surface) is prepared, and the backing sheet, the second base sheet, 1 The base material sheet and the polypropylene sheet (surface layer) are stacked in this order, and the thickness (T) is 2 by performing compression molding for 5 minutes under the conditions of 160 ° C. and 1.0 MPa using a press machine in this stacked state. A flooring of 0.02 mm was obtained (see FIG. 1).

<Examples 2 to 11 and Comparative Examples 1 to 10>
A flooring was obtained in the same manner as in Example 1 except that the composition of the resin composition of each sheet (each layer) was configured as shown in Tables 1 to 4. In Examples 2 to 10 and Comparative Examples 1 to 10, the surface layer has the same configuration as that of Example 1. Note that only the surface layer was not provided in Example 11.

  The tensile elastic modulus of each constituent layer of the flooring materials described in Tables 1 to 4 is a value measured by the following measurement method. In Tables 1 to 4, “the tensile modulus of elasticity with three layers” is the tensile modulus of elasticity with three layers of the first base material layer, the second base material layer, and the backing layer.

  Moreover, the ratio of the linear expansion coefficient described in Tables 1 to 4 (first base material layer / second base material layer / backing layer) is based on the value of the linear expansion coefficient of each layer (each sheet) measured by the following measurement method. It is calculated.

<Measurement method of tensile modulus>
Based on JIS K6251-2004, the tensile modulus (MPa) of each layer of the flooring material (that is, each sheet before being laminated and integrated by compression molding) was measured.

<Measuring method of linear expansion coefficient>
The linear expansion coefficient (unit: 1 / K) was measured according to JIS A1325-1995. That is, the linear expansion coefficient of each layer of the flooring material (that is, each sheet before being laminated and integrated by compression molding) was measured using a thermomechanical measuring device (TMA) manufactured by Seiko Instruments Inc.

  Next, performance evaluation was performed on each flooring obtained as described above based on the following evaluation method. These results are shown in Tables 1-4.

<Flame retardancy evaluation method>
IMO as defined by the International Maritime Organization Based on the surface flammability test of 653 (16), a floor material combustion test was conducted and evaluated based on the following criteria.
(Criteria)
“◯”: passing the above surface flammability test standard value “x”: not passing the above surface flammability test standard value.

<Smokeability evaluation method>
IMO as defined by the International Maritime Organization Based on the smoke and toxicity test of 653 (16), the smoke generation test of the flooring material was conducted and evaluated based on the following criteria.
(Criteria)
“○”: Passes the above smoke emission test standard value (low smoke emission)
“X”: The smoke quality test standard value is not passed.

<Evaluation method for workability (warpage)>
The amount of warp (mm) of the flooring was measured based on the warp test of 6.10 of JIS A 1454-2005 and evaluated based on the following criteria.
(Criteria)
“◯”: The amount of warpage is −1.0 mm to 0.0 mm (including 0.0 mm).
“Δ”: The amount of warpage exceeds 0.0 mm and 0.5 mm or less. “X”: The amount of warpage exceeds 0.5 mm.

<Evaluation method for workability (hardness)>
Based on JIS K6251-2004, the hardness (MPa) of the flooring was measured and evaluated based on the following criteria.
(Criteria)
“◯”: Hardness of 500 MPa or less “Δ”: Hardness of over 500 MPa to 600 MPa or less “x”: Hardness of over 600 MPa

<Measurement of residual dent rate>
Residual dent rate (%) was measured based on JIS A1454-2005 6.6 residual dent test A method, and evaluated based on the following criteria.
(Criteria)
“◯”: Residual dent rate is 6.0% or less “Δ”: Residual dent rate exceeds 6.0% to 8.0% or less “×”: Residual dent rate exceeds 8.0%.

  As is clear from Tables 1 and 2, the flooring materials of Examples 1 to 11 of the present invention are excellent in flame retardancy, low smoke generation, small warpage, excellent workability, and residual dent rate. Small and excellent in heel mark resistance.

  On the other hand, in the flooring of Comparative Example 1, the content of red phosphorus in the base material layer is less than the specified range of the present invention, so that the flame retardancy is insufficient. Further, the flooring material of Comparative Example 2 was highly smokeable because the content of red phosphorus in the base material layer was larger than the specified range of the present invention. In the flooring of Comparative Example 3, the flame retardant property was insufficient because the content of the layered silicate in the base material layer was less than the specified range of the present invention. In the flooring material of Comparative Example 4, the flame retardant property was insufficient because the content of the scaly filler in the base material layer was less than the specified range of the present invention. In the flooring of Comparative Example 5, the content of the metal hydroxide in the base material layer was less than the specified range of the present invention, so the flame retardancy was insufficient. In the flooring of Comparative Example 6, since the content of the metal hydroxide in the base material layer is larger than the specified range of the present invention, the workability evaluation from the viewpoint of hardness is poor, the residual dent rate is large, and the heel resistance is high. Poor mark quality. In the flooring material of Comparative Example 7, the content of the layered silicate in the base material layer is larger than the specified range of the present invention, so the residual dent ratio is large and the heel mark resistance is poor. In the flooring material of Comparative Example 8, since the content of the scaly filler in the base material layer is larger than the specified range of the present invention, the residual dent ratio is large and the heel mark resistance is poor. In the flooring material of Comparative Example 9, since the content of the metal hydroxide in the second base material layer is larger than the specified range of the present invention, the workability evaluation in terms of warpage is poor, the residual dent rate is large, and the resistance is high. Inferior to the heel mark. In the flooring of Comparative Example 10, since the content of the layered silicate in the backing layer is larger than the specified range of the present invention, the workability evaluation in terms of warpage is poor.

  The flooring according to the present invention is less likely to generate harmful gases during combustion, is excellent in combustion safety, has low smoke generation, and further has flame retardancy, workability, thermal dimensional stability, and heel mark resistance. Since it is excellent, for example, it is suitably used as a flooring material for ships, flooring materials for vehicles such as railways and buses, and flooring materials for buildings such as buildings, condominiums, houses, and commercial facilities.

DESCRIPTION OF SYMBOLS 1 ... 1st base material layer 2 ... 2nd base material layer 3 ... Backing layer 4 ... Surface layer 6 ... Base material layer 10 ... Flooring material

Claims (8)

Comprising at least a base material layer and a backing layer laminated on the lower surface side of the base material layer,
The base material layer has 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and 15 to 50 parts of flaky filler with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. It consists of a resin composition containing 100 to 230 parts by mass of a metal hydroxide, 100 parts by mass,
The backing layer is composed of a resin composition containing 1 to 5 parts by mass of a layered silicate with respect to 100 parts by mass of a resin having no chlorine atom in the chemical structure. Wood. The tensile elastic modulus of the base material layer is 100 to 1500 MPa, the tensile elastic modulus of the backing layer is 500 to 1500 MPa,
The tensile modulus of elasticity of the base material layer and the backing layer is 700 MPa or less,
The floor having excellent flame retardancy according to claim 1, wherein the ratio of the linear expansion coefficient is in the range of the linear expansion coefficient of the base material layer / the linear expansion coefficient of the backing layer = 1.0 / 1.2 to 4.0. Wood. At least a first substrate layer, a second substrate layer laminated on the lower surface side of the first substrate layer, and a backing layer laminated on the lower surface side of the second substrate layer,
The first base layer has 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and 15 scaly fillers with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. -50 parts by mass, consisting of a resin composition containing 100-230 parts by mass of metal hydroxide,
The second base layer has 5 to 40 parts by weight of red phosphorus, 3 to 20 parts by weight of layered silicate, and 15 scaly fillers with respect to 100 parts by weight of a resin having no chlorine atom in the chemical structure. -50 parts by mass, consisting of a resin composition containing 100-230 parts by mass of metal hydroxide,
The backing layer is composed of a resin composition containing 1 to 5 parts by mass of a layered silicate with respect to 100 parts by mass of a resin having no chlorine atom in the chemical structure. Wood. The tensile elastic modulus of the first base material layer is 100 to 1500 MPa, the tensile elastic modulus of the second base material layer is 100 to 1500 MPa, and the tensile elastic modulus of the backing layer is 500 to 1500 MPa,
The tensile modulus of elasticity of the first base material layer, the second base material layer, and the backing layer is 700 MPa or less,
The ratio of the linear expansion coefficient is the linear expansion coefficient of the first base material layer / the linear expansion coefficient of the second base material layer / the linear expansion coefficient of the backing layer = 1.0 / 1.0 to 3.0 / 1.2 to The flooring material excellent in flame retardancy according to claim 3, which is in a range of 4.0. As a resin having no chlorine atom in the chemical structure constituting the backing layer, at least a styrene elastomer having a styrene component content of 40 to 80% by mass and a crystalline resin are used,
5. The backing layer contains 5 to 40% by mass of the styrenic elastomer with respect to the entire resin component, and 55 to 80% by mass of the crystalline resin with respect to the entire resin component. Item 1. A flooring material excellent in flame retardancy according to item 1.   The flooring material excellent in flame retardancy according to any one of claims 1 to 5, wherein red phosphorus whose surface is coated with a resin is used.   The flooring material excellent in flame retardancy according to any one of claims 1 to 5, wherein red phosphorus whose surface is coated with a phenol resin is used.   The floor material excellent in flame retardancy according to any one of claims 1 to 7, wherein scaly glass is used as the scaly filler.

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