JP2017014704A - Floor sheet and railway floor structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a floor sheet excellent in flame resistance and durability of a design layer.SOLUTION: A floor sheet of the present invention comprises a base layer laid on a floor surface and including resin or rubber as a matrix, a design layer laminated on at least a part of one surface side of this base layer, a transparent protective layer laminated on the design layer side of a laminate including the base layer and the design layer and an adhesive layer laminated between the base layer and the design layer, and the protective layer is mainly composed of polyvinyl chloride. The base layer preferably includes the rubber as the matrix. 40 μm-150 μm is desirable as an average thickness of the adhesive layer. The adhesive layer is preferably formed of a hot melt adhesive. The hot melt adhesive is preferably mainly composed of polyester, polyamide, an ethylene acetic acid vinyl copolymer or a combination of these. The floor sheet is preferably laid on the floor surface of a railway vehicle.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a floor sheet and a railroad floor structure.

  A floor structure of a vehicle such as a railway or a bus is formed by laminating a floor sheet on the surface of a floor material. As the floor sheet, a sheet mainly composed of polyvinyl chloride or rubber is often used from the viewpoint of adjusting the hardness to an appropriate level and improving the wear resistance and flame retardancy.

  In recent years, a floor sheet is also required to display a design such as a figure such as a wheelchair space. As a method for imparting a design to a floor sheet, a multilayer structure comprising a base layer mainly composed of polyvinyl chloride or rubber and a design layer laminated on one surface side of the base layer by printing or the like. A method is considered. However, since the above-mentioned design layer has a certain limitation in composition such as containing a colorant, it is difficult to improve the wear resistance and the interlayer adhesion with the base layer, and the durability tends to be insufficient.

  As a method for improving the durability of the design layer, there has been proposed a floor sheet in which a transparent protective layer is further laminated on the design layer side of a laminate including a base layer and a design layer (for example, JP-A No. 2003-161030). reference). However, the above floor sheet is subjected to pressure from the protective layer side by human walking or placing objects after laying, so that components such as additives contained in the protective layer and the design layer, particularly the colorant contained in the design layer And the like components may be transferred to the base layer, and the design layer may be deteriorated due to color loss.

JP 2003-161030 A

  This invention is made | formed in view of these requirements, and makes it a subject to provide the floor sheet which is excellent in a flame retardance and durability of a design layer.

  The invention made in order to solve the above-mentioned problems is a floor sheet laid on the floor surface, and is laminated on at least a part of one side of the base layer containing a resin or rubber as a matrix. A design layer, a transparent protective layer laminated on the design layer side of the laminate including the base layer and the design layer, and an adhesive layer laminated between the base layer and the design layer, The protective layer is mainly composed of polyvinyl chloride.

  The floor sheet is excellent in flame retardancy because the protective layer is mainly composed of polyvinyl chloride. In addition, the floor sheet is coated with a transparent protective layer on the design layer, and an adhesive layer laminated between the design layer and the base layer is added to the base layer of components such as additives contained in the design layer. Inhibiting the migration suppresses the alteration and improves the interlayer adhesion between the base layer and the design layer, so that the design layer is excellent in durability.

  The base layer may contain rubber as a matrix. Thus, when the base layer contains rubber as a matrix, the base layer has a matrix with a resin other than rubber such as polyvinyl chloride. The amount of smoke generated can be reduced.

  The average thickness of the adhesive layer is preferably 40 μm or more and 150 μm or less. As described above, when the average thickness of the adhesive layer is within the above range, inhibition of the migration of components contained in the design layer to the base layer and excellent flame retardancy and buffering properties can be exhibited in a balanced manner.

  The adhesive layer may be formed of a hot melt adhesive. In this way, by forming the adhesive layer with a hot melt adhesive, it becomes easy to adjust the average thickness of the adhesive layer and the position where the adhesive layer is formed.

  The hot melt adhesive is preferably composed mainly of polyester, polyamide, ethylene-vinyl acetate copolymer, or a combination thereof. In this way, the hot melt adhesive is mainly composed of polyester, polyamide, ethylene-vinyl acetate copolymer, or a combination thereof, so that components such as additives contained in the design layer can be transferred to the base layer. It becomes easier to inhibit.

  The said floor sheet is good to further provide the adhesive layer laminated | stacked on the opposite side to the design layer of the said base layer. Thus, the floor sheet can be laid on the floor surface easily and reliably by further including an adhesive layer laminated on the side opposite to the design layer of the base layer.

  The floor sheet may be laid on the floor surface of the railway vehicle. Since the floor sheet is excellent in flame retardancy and durability of the design layer, it can be suitably used for laying on the floor surface of a railway vehicle.

  Another invention made in order to solve the above-mentioned subject is a railroad floor structure provided with the flooring of a railroad car, and the floor sheet laminated on the surface of this flooring.

  The railroad floor structure is excellent in flame retardancy and durability of the design layer because the floorsheet is laminated on the surface of the railcar floor material.

  Here, “resin” is a concept that does not include rubber. “Transparent” may be either colorless and transparent, or translucent (for example, JIS-K7375: 2008 “Plastics—Total light transmittance measured in accordance with total light transmittance and total light reflectance”). This is a concept including a transmittance of more than 0% and 80% or less. The “main component” is a component having the largest content, for example, a component having a content of 50% by mass or more. The “average thickness” means a value measured according to JIS-K7130: 1999 “Plastic-film and sheet-thickness measuring method”. Specifically, it means the average of thicknesses measured at 10 equally spaced locations using a thickness meter.

  The floor sheet and the railroad floor structure are excellent in flame retardancy and durability of the design layer.

It is a typical sectional view showing the floor sheet of one embodiment of the present invention.

  Hereinafter, embodiments of the present invention will be described with appropriate reference to the drawings.

  The floor sheet shown in FIG. 1 is used by being laid on the floor surface, and includes a base layer 1, a design layer 2 laminated on one surface side of the base layer 1, and a base layer 1 and a design layer 2. The transparent protective layer 3 laminated on the body design layer 2 side, the adhesive layer 4 laminated between the base layer 1 and the design layer 2, and the base layer 1 on the opposite side of the design layer 2. The pressure-sensitive adhesive layer 5 is provided. Hereinafter, among the thickness direction of the floor sheet and each layer, the side on which the adhesive layer 4, the design layer 2 and / or the protective layer 3 are laminated on the base layer 1 is referred to as “surface side (upper side in FIG. 1)”, The opposite side may be referred to as “back side (lower side in FIG. 1)”. In addition, unless otherwise indicated, the material illustrated below can be used individually by 1 type or in combination of 2 or more types.

  In the floor sheet, each layer may have appropriate flexibility and elasticity from the viewpoint of improving handling properties and buffering properties.

  It does not specifically limit as a planar shape and size of the said floor sheet, It can change suitably according to a use etc. When the floor sheet is laid on the floor surface of a railway vehicle, the shape of the floor sheet is preferably a long sheet. In this case, the floor sheet may be stored and transported in a wound state wound around a core material or the like along the longitudinal direction.

  When the floor sheet is in the form of a long sheet, the average length of the floor sheet is not particularly limited, but one floor sheet can be laid from one end to the other end of the railcar floor. It is preferable that The lower limit of the specific average length of the floor sheet is preferably 10 m, more preferably 12 m, still more preferably 14 m, and particularly preferably 16 m. On the other hand, the upper limit of the average length of the floor sheet is preferably 28 m, more preferably 26 m, still more preferably 24 m, and particularly preferably 22 m.

  When the floor sheet is in the form of a long sheet, the average width (average length in the short direction) of the floor sheet is not particularly limited, but a plurality of (for example, two) floor sheets may be used as a railcar floor. It is preferable that the surface can be covered from one end to the other end in the short direction. The lower limit of the specific average width of the floor sheet is preferably 0.8 m, more preferably 1 m, further preferably 1.2 m, and particularly preferably 1.4 m. On the other hand, the upper limit of the average width of the floor sheet is preferably 2.2 m, more preferably 2 m, still more preferably 1.8 m, and particularly preferably 1.6 m.

  The lower limit of the average thickness of the floor sheet is preferably 1.6 mm, and more preferably 2 mm. On the other hand, the upper limit of the average thickness of the floor sheet is preferably 10.5 mm, more preferably 5.0 mm, and even more preferably 3.0 mm. When the average thickness of the floor sheet is smaller than the lower limit, there is a risk that buffering properties, durability, and the like are insufficient. Conversely, when the average thickness of the floor sheet exceeds the above upper limit, the handleability may be reduced.

(Base layer)
The base layer 1 contains a resin or rubber as a matrix and has characteristics required for a floor sheet such as flame retardancy and buffering properties. The base layer 1 preferably contains rubber as a matrix. When the base layer 1 contains rubber as a matrix, the amount of smoke generated when the floor sheet is burned can be reduced as compared with the case where the matrix is a resin other than rubber such as polyvinyl chloride. The base layer 1 is formed of, for example, a base layer forming composition described later.

  As a minimum of average thickness of base layer 1, 0.5 mm is preferred, 1.5 mm is preferred, and 2.0 mm is more preferred. On the other hand, the upper limit of the average thickness of the base layer 1 is preferably 10.0 mm, more preferably 4.5 mm, and even more preferably 3.0 mm. When the average thickness of the base layer 1 is smaller than the above lower limit, the durability, buffering property and the like of the floor sheet may be reduced. On the contrary, when the average thickness of the base layer 1 exceeds the upper limit, there is a fear that the manufacturing cost of the floor sheet may increase or the handling property may be lowered.

  As the lower limit of the type A durometer hardness measured in accordance with JIS-K6253-3: 2012 “vulcanized rubber and thermoplastic rubber—how to obtain hardness—part 3: durometer hardness” of the base layer 1 50 is preferable, 70 is more preferable, and 85 is more preferable. On the other hand, the upper limit of the hardness of the base layer 1 is preferably 95, more preferably 90. When the hardness of the base layer 1 is smaller than the lower limit, the durability of the floor sheet may be reduced or the ease of walking may be reduced. On the contrary, when the hardness of the base layer 1 exceeds the upper limit, the cushioning property of the floor sheet may be insufficient.

[Base layer forming composition]
The composition for forming a base layer contains a resin or rubber as a matrix. The composition for forming a base layer usually contains an inorganic flame retardant, an organic flame retardant and / or a filler.

  Examples of the resin contained in the base layer forming resin composition include olefin resins such as polyethylene and polypropylene, vinyl resins such as polyvinyl acetate and polyvinyl chloride, and urethane resins. Vinyl chloride is preferred. The resin may have a crosslinked structure.

  Polyvinyl chloride is a polymer having vinyl chloride as a monomer. However, the polyvinyl chloride may be a copolymer of vinyl chloride with other monomers such as ethylene and vinyl acetate. The lower limit of the proportion of structural units derived from vinyl chloride relative to the total structural units of polyvinyl chloride is preferably 60 mol%, more preferably 80 mol%, and even more preferably 95 mol%. Further, the ratio of the structural unit derived from vinyl chloride to the total structural unit of polyvinyl chloride is particularly preferably 100 mol%.

  Examples of the rubber contained in the base layer forming composition as a matrix include general-purpose rubbers such as natural rubber, styrene-butadiene rubber, and butadiene rubber. Among these, from the viewpoint of processability and production cost, styrene- Butadiene rubber is preferred. The rubber may be vulcanized or not vulcanized.

  The mass ratio of styrene to butadiene (styrene / butadiene) in the styrene-butadiene rubber is not particularly limited, but is, for example, 23.5 or more and 46 or less. By setting the mass ratio within the above range, the base layer 1 can be easily and reliably formed even with ordinary rubber processing equipment.

  As a minimum of content of the above-mentioned resin or rubber in a composition for base layer formation, 15 mass% is preferred and 20 mass% is more preferred. On the other hand, the upper limit of the content of the resin or rubber is preferably 70% by mass, more preferably 50% by mass, and still more preferably 30% by mass. When the content of the resin or rubber is smaller than the lower limit, the base layer 1 may be difficult to mold. Conversely, when the content of the resin or rubber exceeds the upper limit, the content of additives such as flame retardants and fillers may be insufficient, and the flame retardancy of the floor sheet may be insufficient. .

  The inorganic flame retardant contained in the base layer forming composition is not particularly limited, but aluminum hydroxide and antimony trioxide are preferable from the viewpoint of reducing the amount of smoke generated from the floor sheet and improving the flame retardancy.

  When the base layer-forming composition contains aluminum hydroxide, the lower limit of the aluminum hydroxide content in the base layer-forming composition is preferably 70 parts by weight with respect to 100 parts by weight of the resin or rubber. Mass parts are more preferred, and 78 parts by mass are even more preferred. On the other hand, as an upper limit of content of aluminum hydroxide, 88 mass parts is preferable with respect to 100 mass parts of resin or rubber, 85 mass parts is more preferable, 82 mass parts is further more preferable. When content of aluminum hydroxide is smaller than the said minimum, there exists a possibility that the amount of fumes of the said floor sheet may increase, or a flame retardance may fall. On the contrary, when the content of aluminum hydroxide exceeds the above upper limit, the base layer 1 becomes rigid and the buffering property of the floor sheet may be lowered.

  When the composition for forming a base layer contains antimony trioxide, the lower limit of the content of antimony trioxide in the composition for forming a base layer is preferably 2 parts by mass with respect to 100 parts by mass of the resin or rubber. Mass parts are more preferred, and 4 parts by mass are even more preferred. On the other hand, as an upper limit of content of antimony trioxide, 8 mass parts is preferable with respect to 100 mass parts of resin or rubber, 7 mass parts is more preferable, and 6 mass parts is still more preferable. When content of antimony trioxide is less than the said minimum, there exists a possibility that the flame retardance of the said floor sheet may fall. On the contrary, when the content of antimony trioxide exceeds the above upper limit, the base layer 1 becomes rigid and the buffering property of the floor sheet may be lowered.

  Although it does not specifically limit as an organic flame retardant which the composition for base layer formation contains, A chlorinated paraffin is preferable. When the base layer forming composition contains chlorinated paraffin, the lower limit of the content of chlorinated paraffin in the base layer forming composition is preferably 0.5 parts by mass with respect to 100 parts by mass of the resin or rubber. 1 part by mass is more preferable, and 1.5 parts by mass is more preferable. On the other hand, as an upper limit of content of chlorinated paraffin, 15 mass parts is preferable with respect to 100 mass parts of resin or rubber, 10 mass parts is more preferable, and 9 mass parts is further more preferable. When content of chlorinated paraffin is smaller than the said minimum, there exists a possibility of the flame retardance fall of the said floor sheet. On the other hand, when the content of chlorinated paraffin exceeds the above upper limit, harmful gas may be easily generated during combustion of the floor sheet.

  Although it does not specifically limit as carbon number of a chlorinated paraffin, For example, they are 12 or more and 26 or less. The ratio of the total atomic weight of chlorine atoms in the molecular weight of the chlorinated paraffin (chlorination rate) is not particularly limited, but is preferably 40% or more and 70% or less from the viewpoint of improving flame retardancy.

  Examples of the filler contained in the base layer forming composition include clay and calcium carbonate. As content of the clay in the composition for base layer formation, it is 80 to 150 mass parts with respect to 100 mass parts of resin or rubber | gum, for example. Moreover, as content of the calcium carbonate in the composition for base layer formation, it is 25 mass parts or more and 60 mass parts or less with respect to 100 mass parts of resin or rubber | gum, for example.

  When the base layer forming composition contains an unvulcanized rubber, the base layer forming composition preferably further contains sulfur and a vulcanization accelerator for vulcanization of the rubber. In this case, the sulfur content in the base layer forming composition is, for example, 2 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the rubber. Moreover, as content of the vulcanization accelerator in the composition for base layer formation, it is 0.5 mass part or more and 5 mass parts or less with respect to 100 mass parts of rubber | gum, for example.

  In addition to the above components, the base layer forming composition may further contain other optional components such as an anti-aging agent, a tackifier, a silane coupling agent, diethylene glycol, zinc oxide, stearic acid, and titanium oxide. . Although it does not specifically limit as content of the said other arbitrary component in the composition for base layer formation, For example, it is 0.5 mass part or more and 10 mass parts or less with respect to 100 mass parts of resin or rubber | gum.

[Design layer]
The design layer 2 is a layer provided with a design. The design layer 2 may be a layer laminated by printing on the front surface side of the adhesive layer 4 or the back surface side of the protective layer 3, and a resin film to which a design visible from the front surface side is given (hereinafter “resin film with design”). "). The design imparted to the design layer 2 is not particularly limited and can be appropriately changed according to the use. For example, a figure such as a wheelchair space, a pictogram indicating the position of an emergency exit, various guidance characters, patterns, photographs, etc. Etc. The design applied to the design layer 2 may be single color or multicolor. Although it does not specifically limit as average thickness of the design layer 2, For example, they are 1 micrometer or more and 500 micrometers or less.

  The design layer 2 usually contains a colorant for imparting the design. The colorant contained in the design layer 2 is not particularly limited, and examples thereof include titanium oxide, zinc oxide, lead white, carbon black, iron black, petal, cadmium red, chrome lead, titanium yellow, cobalt blue, and ultramarine blue. Inorganic colorants, aniline black, quinacridone red, polyazo red, isoindolinone yellow, benzidine yellow, phthalocyanine blue, indanthrene blue, and other organic colorants, aluminum, brass, titanium dioxide-coated mica, basic lead carbonate and other scaly foils Examples include glittering colorants formed from pieces.

  When the design layer 2 is a layer laminated by printing on the front surface side of the adhesive layer 4 or the back surface side of the protective layer 3, the ink used for the printing is improved in affinity with the adhesive layer 4 and the protective layer 3 In view of the above, a resin-based ink containing a resin, a solvent, and a colorant is preferable. That is, the design layer 2 is preferably formed of a resin-based ink. The resin contained in the resin-based ink is preferably an acrylic resin from the viewpoint of affinity with the adhesive layer 4 and the protective layer 3.

  The acrylic resin is a homopolymer of (meth) acrylic acid alkyl ester or a copolymer thereof.

  The design layer 2 may contain other components in addition to the components described above. As said other component, additives, such as a plasticizer, antioxidant, a flame retardant, etc. are mentioned, for example. Examples of the flame retardant include inorganic flame retardants and organic flame retardants exemplified in the base layer 1. When the design layer 2 contains the other component, the content of the other component in the design layer 2 is, for example, 0.1% by mass or more and 20% by mass or less.

  In the floor sheet, the adhesive layer 4 is laminated between the base layer 1 and the design layer 2, so that even if the content of components such as colorants and additives in the design layer 2 is increased, the adhesive is used. Since the layer 4 inhibits the migration of the above components to the base layer 1, decolorization of the design layer 2 and curing of the adhesive layer 4 and the base layer 1 can be suppressed. Therefore, the characteristics required for the design layer 2 such as the plasticity of the design layer 2 and the sharpness of the applied design can be easily improved.

  A sealing layer (not shown) formed by silver coating or the like may be laminated on the back surface of the design layer 2. Thus, even if it increases content of components, such as a coloring agent and an additive, in the design layer 2 because the sealing layer is laminated | stacked on the back surface of the design layer 2, the sealing layer adheres the said component. Since the transfer to the agent layer 4 and the base layer 1 is inhibited, the characteristics required for the design layer 2 described above can be improved more easily.

[Protective layer]
The protective layer 3 is a transparent layer mainly composed of polyvinyl chloride and excellent in wear resistance and flame retardancy, and improves the flame retardance of the floor sheet and the durability of the design layer 2. As the polyvinyl chloride, the same ones as exemplified in the base layer 1 can be used, and the description thereof is omitted.

  As a minimum of average thickness of protective layer 3, 0.08 mm is preferred, 0.15 mm is more preferred, and 0.18 mm is still more preferred. On the other hand, the upper limit of the average thickness of the protective layer 3 is preferably 0.60 mm, more preferably 0.50 mm, still more preferably 0.40 mm, and particularly preferably 0.25 mm. Moreover, as average thickness of the protective layer 3, 0.18 mm or more and 0.25 mm or less are especially preferable. When the average thickness of the protective layer 3 is smaller than the said minimum, there exists a possibility that the durability of the design layer 2 may fall or the flame retardance of the said floor sheet may fall. Conversely, if the average thickness of the protective layer 3 exceeds the above upper limit, the amount of smoke generated may increase during combustion of the floor sheet.

  As a minimum of content of polyvinyl chloride in protective layer 3, 70 mass% is preferred, 80 mass% is more preferred, and 85 mass% is still more preferred. On the other hand, the upper limit of the content of polyvinyl chloride in the protective layer 3 is preferably 99% by mass, and more preferably 95 parts by mass. When the content of polyvinyl chloride in the protective layer 3 is smaller than the above lower limit, the flame retardancy of the floor sheet and the durability of the design layer 2 may be reduced. On the contrary, when the content of polyvinyl chloride in the protective layer 3 exceeds the above upper limit, the content of other components described later becomes small, and thus there is a possibility that desired properties cannot be imparted to the protective layer 3. However, the content of polyvinyl chloride in the protective layer 3 may be 100% by mass.

  The protective layer 3 may contain other components as long as the transparency, abrasion resistance, flame retardancy and the like are not impaired. Examples of the other components include additives such as plasticizers, antioxidants, flame retardants, and colorants, and other resins. Examples of the flame retardant include inorganic flame retardants and organic flame retardants exemplified in the base layer 1. When the protective layer 3 contains the other component, the content of the other component in the protective layer 3 is, for example, 1 part by mass or more and 20 parts by mass or less with respect to 100 parts by mass of polyvinyl chloride.

[Adhesive layer]
The adhesive layer 4 is a layer formed of an adhesive, and is laminated between the base layer 1 and the design layer 2, and inhibits migration of components contained in the design layer 2 to the base layer 1. The adhesive layer 4 also improves the interlayer adhesion between the base layer 1 and the design layer 2. Although it does not specifically limit as an adhesive agent which forms the adhesive bond layer 4, For example, reaction type | system | group adhesives, such as a photocurable adhesive agent, a thermosetting adhesive agent, a moisture curable adhesive agent, a two-component mixed adhesive agent, hot Examples include melt adhesives, solvent-based adhesives, water-dispersed adhesives, etc. From the viewpoint of making it easy to adjust the average thickness of the adhesive layer 4 and the position at which the adhesive layer 4 is formed. An adhesive is preferred, and a sheet-like hot melt adhesive is more preferred.

  As a minimum of average thickness of adhesive bond layer 4, 40 micrometers is preferred, 50 micrometers is more preferred, and 60 micrometers is still more preferred. On the other hand, the upper limit of the average thickness of the adhesive layer 4 is preferably 150 μm, more preferably 120 μm, and still more preferably 80 μm. When the average thickness of the adhesive layer 4 is smaller than the above lower limit, the inhibition of the migration of the components contained in the design layer 2 to the base layer 1 may be insufficient. On the other hand, when the average thickness of the adhesive layer 4 exceeds the above upper limit, the flame retardancy and buffering properties of the floor sheet may be reduced.

  The hot melt adhesive is mainly composed of a thermoplastic resin. Examples of the thermoplastic resin include olefinic resins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polyamides, thermoplastic polyurethanes, thermoplastic polyamides, and ethylene-vinyl acetate copolymers. Of these, polyester, polyamide, ethylene-vinyl acetate copolymer, and combinations thereof are preferable as the thermoplastic resin. In addition, as a vinyl acetate content rate of the said ethylene-vinyl acetate copolymer, it is 20 to 40 mass%, for example. The ethylene-vinyl acetate copolymer may be a modified ethylene-vinyl acetate copolymer. Examples of the modified ethylene-vinyl acetate copolymer include saponified ethylene-vinyl acetate copolymer, ethylene-vinyl acetate copolymer modified by grafting carboxylic acid such as maleic anhydride, vinyl chloride, styrene, and the like. Among them, an ethylene-vinyl acetate copolymer saponified product is preferable.

  The lower limit of the molecular weight of the thermoplastic resin is preferably 5,000, more preferably 10,000, and even more preferably 20,000. On the other hand, the upper limit of the molecular weight of the thermoplastic resin is preferably 100,000, more preferably 50,000, and still more preferably 40,000. When the molecular weight of the thermoplastic resin is smaller than the lower limit, the strength of the adhesive layer 4 may be reduced, or the migration of components contained in the design layer 2 to the base layer 1 may be insufficient. On the contrary, when the molecular weight of the thermoplastic resin exceeds the upper limit, the melting point and MFR of the thermoplastic resin are excessively increased, which may reduce the adhesiveness of the adhesive layer 4 and the like. Here, “molecular weight” refers to gel permeation chromatography in accordance with JIS-K7252-1: 2008 “Plastics—Method for obtaining average molecular weight and molecular weight distribution of polymer by size exclusion chromatography—Part 1: General rules”. Refers to the number average molecular weight measured using chromatography (GPC).

  As a glass transition point of the said thermoplastic resin, it is -10 degreeC or more and 20 degrees C or less, for example. Here, the “glass transition point” refers to a midpoint glass transition temperature measured using a differential scanning calorimetry (DSC) in accordance with JIS-K7121: 1987 “Method for measuring plastic transition temperature”.

The lower limit of the density of the thermoplastic resin is preferably 0.9 g / cm ^3, more preferably ^{1.1g / cm 3, 1.25g / cm} 3 is more preferred. On the other hand, the upper limit of the density of the thermoplastic resin is preferably ^{1.4g / cm 3, 1.3g / cm} 3 is more preferable. When the density of the thermoplastic resin is smaller than the above lower limit, the strength of the adhesive layer 4 may be lowered, or the migration of components contained in the design layer 2 to the base layer 1 may be insufficient. Conversely, when the density of the thermoplastic resin exceeds the upper limit, the flexibility of the adhesive layer 4 may be reduced. Here, “density” refers to a value measured in accordance with JIS-K7112: 1999 “Plastics—Method for measuring density and specific gravity of non-foamed plastic”.

  As a minimum of melting point of the above-mentioned thermoplastic resin, 80 ° C is preferred and 100 ° C is more preferred. On the other hand, the upper limit of the melting point of the thermoplastic resin is preferably 150 ° C., more preferably 120 ° C. When the melting point of the thermoplastic resin is smaller than the lower limit, the strength of the adhesive layer 4 may be reduced. On the other hand, when the melting point of the thermoplastic resin exceeds the upper limit, the other layers may be deteriorated during bonding. Here, the “melting point” refers to a melting point peak temperature measured by a differential scanning calorimeter (DSC) in accordance with JIS-K7121: 2012 “Method for measuring plastic transition temperature”.

  The lower limit of the melt flow rate (MFR) at 190 ° C. of the thermoplastic resin is more preferably 5 g / 10 minutes, further preferably 10 g / 10 minutes, and further preferably 15 g / 10 minutes. On the other hand, the upper limit of the MFR is preferably 25 g / 10 minutes, and more preferably 18 g / 10 minutes. When the MFR is smaller than the lower limit, the strength of the adhesive layer 4 may be reduced. Conversely, when the MFR exceeds the upper limit, the interlayer adhesion between the base layer 1 and the design layer 2 may be reduced. Here, "MFR" means JIS-K7210-1: 2014 "Plastics-Determination of melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastics-Part 1: Standard test method". The value measured in compliance.

  As a minimum of content of the above-mentioned thermoplastic resin in the above-mentioned hot melt adhesive, 60 mass% is preferred, 80 mass% is more preferred, and 95 mass% is still more preferred. When the content of the thermoplastic resin is smaller than the above lower limit, there is a risk that the interlayer adhesion between the base layer 1 and the design layer 2 may be insufficient, or the migration of components contained in the design layer 2 to the base layer 1 may be hindered. May be insufficient.

  The hot melt adhesive may further contain other optional components such as a flame retardant, a curing agent, a plasticizer, an antioxidant, a reinforcing agent, a filler, an antifoaming agent, and a surfactant. Examples of the flame retardant include inorganic flame retardants and organic flame retardants exemplified in the base layer 1. As content of the said other component in the said hot-melt-adhesive, it is 1 mass part or more and 10 mass parts or less with respect to 100 mass parts of thermoplastic resins, for example.

[Adhesive layer]
The pressure-sensitive adhesive layer 5 is laminated on the back side of the base layer 1. As an adhesive which forms this adhesive layer 5, an acrylic adhesive is mentioned, for example.

  An acrylic pressure-sensitive adhesive is a pressure-sensitive adhesive mainly composed of an acrylic resin. The acrylic resin can be obtained, for example, by vinyl polymerization of (meth) acrylic acid alkyl ester by a conventional method. The acrylic resin may be a copolymer with a modifying monomer from the viewpoint of improving optical properties, heat resistance, and the like.

  The (meth) acrylic acid alkyl ester has a linear or branched alkyl group. The lower limit of the carbon number of the alkyl group is usually 1 and 4 is preferable. On the other hand, the upper limit of the carbon number of the alkyl group is, for example, 18 and 12 is preferable. Specific alkyl (meth) acrylates include, for example, butyl (meth) acrylate, isobutyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and isooctyl (meth) acrylate. , Isononyl (meth) acrylate, allyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and the like.

  A curing agent such as an isocyanate curing agent, a plasticizer, an antioxidant, a reinforcing agent, a filler, an antifoaming agent, a surfactant, and the like may be added to the acrylic pressure-sensitive adhesive.

  When a curing agent is added to the acrylic pressure-sensitive adhesive, the lower limit of the amount of the curing agent is preferably 0.1 parts by weight, more preferably 1 part by weight, with respect to 100 parts by weight of the acrylic pressure-sensitive adhesive. More preferably, 3 parts by mass. On the other hand, as an upper limit of the addition amount of the said hardening | curing agent, 5 mass parts is preferable with respect to 100 mass parts of acrylic adhesives, 3 mass parts is more preferable, and 2 mass parts is more preferable. When the addition amount of the curing agent is smaller than the lower limit, it may be difficult to give the adhesive layer 5 appropriate elasticity. On the contrary, when the addition amount of the curing agent exceeds the above upper limit, the adhesive force of the adhesive layer 5 may be insufficient.

  The lower limit of the average thickness of the pressure-sensitive adhesive layer 5 is preferably 50 μm, more preferably 60 μm, further preferably 70 μm, particularly preferably 80 μm, and particularly preferably 90 μm. On the other hand, the upper limit of the average thickness of the pressure-sensitive adhesive layer 5 is preferably 500 μm, more preferably 400 μm, further preferably 300 μm, particularly preferably 200 μm, and particularly preferably 160 μm. When the average thickness of the pressure-sensitive adhesive layer 5 is smaller than the above lower limit, there is a possibility that the adhesive force when the floor sheet is laid on the floor surface is insufficient. On the other hand, when the average thickness of the pressure-sensitive adhesive layer 5 exceeds the above upper limit, there is a fear that the manufacturing cost of the floor sheet may increase or the handleability may deteriorate.

(Use)
The floor sheet is used by being laid on a floor surface of a building such as a station, a residence, an office, or a vehicle such as a bus or a railroad. As a use of the floor sheet, it can be suitably used for laying on the floor surface of a railway vehicle from the viewpoint of exhibiting excellent flame retardancy and design.

<Fabric sheet manufacturing method>
As a method for producing the floor sheet, for example, a step of preparing a base layer (base layer preparation step), a step of preparing a transparent protective layer (protective layer preparation step), a base layer, an adhesive layer, a design layer, and A step of forming a laminate in which protective layers are laminated in this order (laminate formation step), a step of heating and pressurizing the laminate (heat pressurization step), and a back side of the laminate after the heating and pressurizing step And a method of laminating the pressure-sensitive adhesive layer (pressure-sensitive adhesive layer laminating step).

(Base layer preparation process)
In this step, a base layer is prepared. As a method for preparing the base layer, for example, the above-described composition for forming a base layer is kneaded using an open roll, a Banbury mixer, a pressure kneader or the like, and formed into a sheet by rolling using a calendar roll or the like. Is mentioned. In addition, when the composition for base layer formation contains the rubber | gum which is not vulcanized, after processing it into a sheet form, it is good to vulcanize | cure using a continuous vulcanizer (load press) etc. As conditions for the vulcanization process, for example, the temperature may be 140 ° C. or more and 200 ° C. or less, and the time may be 5 minutes or more and 30 minutes or less.

(Protective layer preparation process)
In this step, a protective layer is prepared. The method for preparing the protective layer is not particularly limited, and examples thereof include a method of forming a composition containing polyvinyl chloride and an optional component into a sheet by the method exemplified for the base layer. Moreover, you may use a commercially available polyvinyl chloride sheet.

(Laminate formation process)
In this step, a laminate in which a base layer, an adhesive layer, a design layer, and a protective layer are laminated in this order (hereinafter also referred to as “first laminate”) is formed. Although it does not specifically limit as a method of forming a 1st laminated body, For example, the 1st method, the 2nd method, the 3rd method, the 4th method etc. which are mentioned later are mentioned. Hereinafter, each method will be described.

  In the first method, a base layer, a sheet-like hot melt adhesive as an adhesive layer, a resin film with a design as a design layer, and a protective layer are superposed in this order to form a first laminate. To do. In the first method, as a method of superimposing the adhesive layer and the design layer on the base layer, the design layer is laminated by printing on a sheet-like hot melt adhesive, and the obtained adhesive layer and the design layer are included. You may use the method of superimposing the adhesive bond layer side of a laminated body on the surface side of a base layer. Furthermore, in the first method, as a method of superimposing the design layer and the protective layer on the adhesive layer, the design layer is laminated on the back side of the protective layer by printing, and the laminate including the obtained design layer and the protective layer is obtained. You may use the method of superimposing the design layer side on the surface side of an adhesive bond layer (sheet-like hot-melt-adhesive).

  In the second method, an adhesive layer is laminated on the surface side of the base layer by applying a liquid adhesive, and the design as a design layer is formed on the adhesive layer side of the obtained laminate including the base layer and the adhesive layer. A 1st laminated body is formed by superimposing a resin film with a cover and a protective layer in this order. In the second method, as a method of superimposing the design layer and the protective layer on the laminate including the base layer and the adhesive layer, the design layer is obtained by laminating the design layer on the back side of the protective layer by printing. Alternatively, a method of superimposing the design layer side of the laminate including the protective layer on the adhesive layer side of the laminate including the base layer and the adhesive layer may be used.

  In the third method, an adhesive layer is first formed by applying a liquid adhesive on the back side of a resin film with a design as a design layer. Next, the design layer of the laminate including the base layer, the adhesive layer, and the design layer obtained by superimposing the adhesive layer side of the laminate including the obtained adhesive layer and the design layer on the surface side of the base layer A 1st laminated body is formed by superimposing the back surface side of a protective layer on the side.

  In the fourth method, the design layer is first laminated by printing on the back side of the protective layer, and the adhesive layer is laminated by applying a liquid adhesive to the design layer side of the laminate including the protective layer and the design layer. To do. Next, a 1st laminated body is formed by superimposing the adhesive layer side of the laminated body containing a protective layer, a design layer, and an adhesive bond layer on the surface side of a base layer.

  In addition, when using a resin film with a design as a design layer in the first to third methods, from the viewpoint of improving the interlayer adhesion between the design layer and the protective layer, a sheet-like hot melt between the resin film with the design and the protective layer An adhesive may be further laminated, and an adhesive may be applied in advance to the front surface side of the resin film with design and / or the back surface side of the protective layer.

  In addition, from the viewpoint of improving the interlayer adhesive strength of each layer, before this step, the protective layer, the sheet-like hot melt adhesive, the resin film with a design, and / or the protective layer are formed using an organic solvent, an aqueous emulsion, or the like. It is preferable to degrease and wash.

  When laminating the design layer by printing, examples of the printing method include gravure printing, screen printing, offset printing, ink jet printing, and the like. Among these, gravure printing and screen printing are preferable. In this step, a plurality of printing methods may be used in combination.

(Heating and pressing process)
In this step, the laminate is heated and pressurized. As conditions for the heating and pressing, for example, the temperature is 100 ° C. or more and 170 ° C. or less, the time is 30 seconds or more and 500 seconds or less, and the pressure is 0.5 N / cm ² or more and 20 N / cm ² or less.

(Adhesive layer lamination process)
In this step, an adhesive layer is laminated on the back side of the laminate. It does not specifically limit as a method of laminating an adhesive layer on the back side of the above-mentioned layered product, and a conventionally well-known method can be used.

<Railway floor structure>
The railway floor structure includes a floor material of a railway vehicle and the floor sheet laminated on the surface of the floor material.

  The railcar floor material is not particularly limited, and a conventionally known material can be used, and examples thereof include a stainless steel material, a urethane base material, and an epoxy base material.

<Method for manufacturing railway floor structure>
Examples of the method for manufacturing the railway floor structure include a method including a step of laminating the floor sheet so that the back side faces the surface of the floor material of the railway vehicle. When the floor sheet does not include the pressure-sensitive adhesive layer, a step of applying an adhesive or a pressure-sensitive adhesive to the back surface side of the floor sheet and / or the surface side of the floor material of the railway vehicle is further performed before the step of laminating. It is good to have.

<Other embodiments>
The present invention is not limited to the above-described embodiment, and can be implemented in a mode in which various changes and improvements are made in addition to the above-described mode.

  In the floor sheet, the pressure-sensitive adhesive layer has an arbitrary configuration. Therefore, in the manufacturing process of the said floor sheet, an adhesive layer formation process is an arbitrary process.

  Moreover, the design layer may be laminated | stacked on the whole surface side of the base layer, and may be laminated | stacked only on a part of surface side of a base layer. When the design layer is laminated only on a part of the surface side of the base layer, the protective layer is laminated only on the region where the design layer is laminated on the surface side of the laminate including the base layer and the design layer. It may be further laminated on a part or the entire surface of the region where the design layer is not laminated. The adhesive layer may be laminated only in a region where the design layer is laminated on the surface side of the base layer, or may be further laminated on a part or the whole surface of the region where the design layer is not laminated. Good. However, the adhesive layer is not usually laminated in a region where the protective layer is not laminated on the surface side of the base layer. When the adhesive layer is further laminated in a region where the design layer is not laminated on the surface side of the base layer, the adhesive layer also contributes to improving the adhesion between the base layer and the protective layer.

  The floor sheet may further include other layers. Examples of the other layers include a topcoat layer laminated on the surface side of the protective layer, a primer layer laminated on the surface side and / or the back side of the adhesive layer, and a release layer laminated on the back side of the pressure-sensitive adhesive layer. A mold sheet etc. are mentioned. The floor sheet may further include an adhesive layer laminated between the design layer and the protective layer. In this case, the design layer may be a layer laminated by printing on the back side of the adhesive layer. Further, the adhesive layer may be laminated only between the design layer and the protective layer, and further laminated on a part of or the entire surface of the back surface side of the protective layer where the design layer is not laminated. May be.

  Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.

[Manufacture of base layer]
First, a composition having a predetermined composition is kneaded using a Banbury mixer and an open roll, then rolled with a calendar roll to obtain a sheet-like long product, and then a continuous vulcanizer (roof press). The base layer (average thickness 2.3 mm) used for a floor sheet was manufactured by vulcanization (160 ° C., 10 minutes).

The predetermined composition is as follows.
Unvulcanized rubber: 90 parts by mass of styrene-butadiene rubber (SBR) (“JSR1502” from JSR) 10 parts by mass of unvulcanized rubber: high styrene rubber (“JSR0061” from JSR) Filler: clay (RT 125 parts by weight of Vanderbilt's “Dixie Clay” Filler: 50 parts by weight of calcium carbonate (“heavy coal” by Maruo Calcium Co., Ltd.) Inorganic flame retardant: aluminum hydroxide (“Hijilite H-42M” by Showa Denko KK ) 80 parts by weight Inorganic flame retardant: antimony trioxide (Suzuhiro Chemical's “Fire Cut AT3”) 5 parts by weight Organic flame retardant: chlorinated paraffin (Ajinomoto Fine Techno Co., Ltd. “Empara 70F”) 8 parts by weight Aging 4 parts by weight of inhibitor ("Nocrack 224" from Ouchi Shinsei Chemical Co., Ltd.) Tackifier (aliphatic hydrocarbon resin, Nippon Zeon " Inton A-100 ") 5 parts by weight Diethylene glycol (" Diethylene glycol "from Mitsubishi Chemical Corporation) 3 parts by weight Silane coupling agent (" Si-69 "from Degussa Japan) 1 part by weight Zinc oxide (" Zinc Oxide 3 "by Hux Itec Corp.) Species G ") 5 parts by weight Stearic acid (" Beadstearate "from Nippon Oil & Fats Co., Ltd.) 2 parts by weight Sulfur (" Oil Sulfur "from Hosokawa Chemical Co., Ltd.) 6 parts by weight Vulcanization accelerator "Noxeller NS-P") 1.5 parts by mass

[Manufacture of floor sheet of Test Example 1]
A film of polyvinyl chloride (PVC) having an average thickness of 0.2 mm as a protective layer (“CL54620” manufactured by Bando Chemical Co., Ltd.) was placed on the base layer, and heated and pressurized (120 ° C., 300 seconds, 10 N / cm ² ) The floor sheet of Test Example 1 was manufactured.

[Manufacture of floor sheet of Test Example 2]
Test example, except that a protective layer was formed using an ethylene-vinyl acetate copolymer (EVA) film ("Ultrasen" manufactured by Tosoh Nikkemi Co., Ltd.) having an average thickness of 0.2 mm instead of the polyvinyl chloride film The floor sheet of Test Example 2 was manufactured in the same manner as in Example 1.

[Manufacture of floor sheet of Test Example 3]
A test example was prepared in the same manner as in Test Example 1 except that a protective layer was formed using an acetate film (Aki Sangyo "TAC film") having an average thickness of 0.2 mm instead of the polyvinyl chloride film. Three floor sheets were produced.

[Manufacture of Floor Sheet of Test Example 4]
Test Example 1 except that a protective layer was formed using a thermoplastic elastomer film (“SR sheet” from JSR) having an average thickness of 0.10 mm instead of the polyvinyl chloride film. Four floor sheets were produced.

[Manufacture of floor sheet of Test Example 5]
The same operation as in Test Example 1 was performed except that a protective layer was formed by applying a wax (“Raster” from Suisho Yuka Kogyo Co., Ltd.) to an average thickness of 0.03 mm instead of the polyvinyl chloride film. A floor sheet of Test Example 5 was produced.

<Evaluation of wear resistance>
JIS-K6264-2: 2005 "Vulcanized rubber and thermoplastic rubber-Determination of wear resistance-Part 2: Test method" The Taber abrasion test in accordance with Taber abrasion test was used to determine the abrasion resistance of the floor sheets of Test Examples 1-5. evaluated. The test conditions were a load of 9.8 N, a rotational speed of 60 times / minute, a wear wheel CS-H22, and a rotational speed of 1,000 times. Abrasion resistance is "good (A)" when the protective layer remains after the test and the base layer is not exposed, and "good (B) when the protective layer is worn and the base layer is exposed." ) ”. The evaluation results are shown in Table 1.

<Evaluation of flame retardancy>
The flame retardancy of the floor sheets of Test Examples 1 to 3 was evaluated in accordance with a combustion test (non-metallic material for railway vehicles) carried out by the “Japan Railway Vehicle Machinery Technology Association”. Specifically, first, each floor sheet is cut into a B5 size (182 mm × 257 mm) as a test piece, and the longitudinal direction of the test piece is inclined by 45 ° with respect to the horizontal plane, and the surface side is downward. Retained. Next, 0.5 cc of pure ethyl alcohol was placed in a cylindrical iron fuel container having a diameter of 17.5 mm, a depth of 7.1 mm, and a thickness of 0.8 mm. The fuel container was placed on a cork base, and the center of the bottom surface of the fuel container was disposed so as to be located 25.4 mm vertically below the center of the surface side (combustion surface) of the test piece. After that, ignite the pure ethyl alcohol in the fuel container and let it stand until it burns out, observe during and after combustion, and in accordance with the standards of flammability standards of this combustion test, incombustibility, extreme flame resistance, difficulty Classified as flammable, slow flammable or flammable. Note that the test chamber was maintained at a temperature of 15 ° C. to 30 ° C. and a humidity of 60% to 75% and no air flow. The flame retardancy of each test specimen is classified as “good (A)” when classified as non-flammable, extremely flame retardant, or flame retardant according to the above flammability standards, and when classified as slow flammable or flammable Was evaluated as “not good (B)”. The evaluation results are shown in Table 2.

  As is clear from Tables 1 and 2, the floor sheet of Test Example 1 was good in both wear resistance and flame retardancy. From this, the said floor sheet is judged to be excellent in a flame retardance and the durability of a design layer because the main component of a protective layer is polyvinyl chloride. On the other hand, the floor sheets of Test Examples 2 to 5 were not good in at least one of wear resistance and flame retardancy.

  The floor sheet and the railroad floor structure are excellent in flame retardancy and durability of the design layer.

1 Base layer 2 Design layer 3 Protective layer 4 Adhesive layer 5 Adhesive layer

Claims (8)

A floor sheet laid on the floor surface,
A base layer containing a resin or rubber as a matrix, a design layer laminated on at least part of one side of the base layer, and a design layer side of a laminate including the base layer and the design layer. A transparent protective layer, and an adhesive layer laminated between the base layer and the design layer,
A floor sheet, wherein the protective layer is mainly composed of polyvinyl chloride.   The floor sheet according to claim 1, wherein the base layer contains rubber as a matrix.   The floor sheet according to claim 1 or 2, wherein an average thickness of the adhesive layer is 40 µm or more and 150 µm or less.   The floor sheet according to claim 1, wherein the adhesive layer is formed of a hot melt adhesive.   The floor sheet according to claim 4, wherein the hot melt adhesive is mainly composed of polyester, polyamide, ethylene-vinyl acetate copolymer, or a combination thereof.   The floor sheet according to any one of claims 1 to 5, further comprising a pressure-sensitive adhesive layer laminated on the side opposite to the design layer of the base layer.   The floor sheet according to any one of claims 1 to 6, wherein the floor sheet is laid on a floor surface of a railway vehicle. Railway vehicle flooring,
A railroad floor structure comprising: the floor sheet according to any one of claims 1 to 7 laminated on a surface of the flooring.

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