Resin composition for anti-slip mat and method for producing same, and anti-slip mat and method for producing same

Abstract

This resin composition for anti-slip mats comprises synthetic barium sulfate and a thermoplastic elastomer composition as essential components, wherein the synthetic barium sulfate is contained in an amount of 20-70 mass%, the resin composition having a durometer type-A hardness of 20-80. With this resin composition, anti-slip mats for use in wet areas can be easily produced, the mats being flexible, able to sink under water by itself, lightweight and easy to handle even for elderly and other persons, and excellent in terms of mechanical strength and wear resistance.

Description

[Technical Field]

[0001] The present invention relates to a resin composition for an anti-slip mat, and a method for producing the resin composition for an anti-slip mat.Furthermore, the present invention relates to an anti-slip mat, and a method for producing the anti-slip mat. [Background technology]

[0002] Anti-slip mats are used in a wide range of locations around water to prevent falls on wet floors, such as poolsides, pool bottoms, bathroom floors, bathtubs, toilet floors, etc. In particular, there have been many cases of elderly people falling and getting injured in bathtubs, so it is known to use anti-slip mats sunk into the bathtub bottom to prevent falls. Resin compositions for such non-slip mats must have a specific gravity heavier than water, be resistant to slippage, and be non-slip even when stepped on or sat on. Furthermore, they must have sufficient strength and abrasion resistance for practical use, and flexibility to provide a comfortable feel. In addition, they may also be required to be resistant to chlorine water, which is resistant to the chlorine contained in tap water. From an economic perspective, high productivity is required to reduce costs, and from an environmental perspective, recyclable materials are required to reduce environmental impact.

[0003] The anti-slip mat is made of a flexible material such as rubber, and exhibits its anti-slip function through the frictional effect of the flexible material. Therefore, by increasing the specific gravity of the flexible material, the mat can be prevented from slipping on the floor even in wet environments. Furthermore, the mat is required to have mechanical strength to withstand the actions of people stepping on or sitting on it, and abrasion resistance to prevent wear from repeated use. Furthermore, a moderate degree of flexibility is required to ensure comfort when sitting on it.

[0004] Conventionally, flexible materials used in anti-slip mats have had to be cross-linked to address issues of strength and abrasion resistance, necessitating a vulcanization process. Furthermore, they have been produced using batch manufacturing techniques such as compression molding, resulting in low productivity.

[0005] Patent Document 1 proposes a composition for anti-slip mats that comprises a styrene-based elastomer, a polypropylene resin, a rubber softener, and calcium carbonate. This method is not intended for use in wet areas, particularly in underwater environments, and has the drawback of insufficient anti-slip effect in wet environments due to the low specific gravity of the composition itself. Furthermore, the composition alone does not have sufficient strength when in use, so it is necessary to fuse the resin with a base resin, which makes the manufacturing process complicated.

[0006] Patent Document 2 proposes a manufacturing method in which a large amount of high-specific-gravity barium sulfate is added to synthetic rubber or natural rubber, and then the rubber is embossed to provide anti-slip properties, followed by vulcanization. In this method, since the melt viscosity of the composition is high when the composition is mixed, it is necessary to use a batch-type roll mixer, and further, the manufacturing process is complicated, resulting in low productivity.

[0007] Patent Document 3 proposes a composition that is highly filled with a styrene elastomer, a thermoplastic resin, a rubber softener, and further heavy calcium carbonate or barium sulfate in order to increase the specific gravity of the styrene elastomer and thereby improve sound insulation. This method had a high breaking strength but a low breaking elongation, and the mechanical strength required for an anti-slip mat was insufficient. Furthermore, because the melt viscosity was high, a complicated manufacturing process was required, such as preparing the composition using a batch mixer, forming a sheet using a roll molding machine, and then obtaining the product using a compression molding machine, resulting in low productivity.

[0008] Furthermore, Patent Document 4 proposes an anti-slip sheet made of a thermoplastic elastomer or rubber and an inorganic filler. This method, which aims to make the mat sink in water, results in a sheet with a high specific gravity of over 2.2, making it difficult for the elderly, whose numbers have been increasing in recent years with the aging of society, and for infants and children who help with housework (hereinafter, elderly and infants and children are collectively referred to as "elderly, etc.") to handle. Furthermore, although the mat is flexible, has a non-slip effect, and has a specific gravity sufficient for use in water as a bathtub mat, the product has a three-layer structure of a surface layer, a high-specific-gravity middle layer, and a back layer, each of which complements the other's functions, which results in a complicated manufacturing process and low productivity. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] Japanese Patent Application Publication No. 10-279747 [Patent Document 2] Japanese Patent Application Publication No. 10-215911 [Patent Document 3] Japanese Patent Publication No. 62-256845 [Patent Document 4] Japanese Patent Application Laid-Open No. 2001-181408 Summary of the Invention [Problem to be solved by the invention]

[0010] As described above, conventionally known anti-slip mats have had manufacturing problems, namely, the need for a vulcanization process of the raw material composition, the inability to recycle materials from molded products, and low productivity due to batch production. The object of the present invention is to provide a resin composition which provides an anti-slip mat that has excellent moldability, a specific gravity that is easy to handle, excellent abrasion resistance, can be self-sinked in water, and exhibits an anti-slip effect when stepped on, a method for producing the same, and an anti-slip mat and a method for producing the same. [Means for solving the problem]

[0011] The present inventors conducted extensive research to solve the above problems and found that, among barium sulfates, the use of synthetic barium sulfate significantly improves strength and abrasion resistance compared to the use of natural barium sulfate (elutriated barium sulfate). They then discovered that the use of a resin composition containing a specific thermoplastic elastomer and synthetic barium sulfate and having a Type A durometer hardness within a certain range results in an optimal specific gravity, a good balance between tensile strength and elongation, a high anti-slip effect, and excellent abrasion resistance, leading to the completion of the present invention. Furthermore, it has been found that by adding a specific amount of antifungal agent to the resin composition, the resulting mat can be prevented from developing mold even when used in wet areas, particularly bathrooms and bathtubs. The present invention provides the following means.

[0012] [1] A resin composition for anti-slip mats, characterized in that synthetic barium sulfate and a thermoplastic elastomer composition are essential components, the resin composition contains 20 to 70 mass% of the synthetic barium sulfate, and has a Type A durometer hardness of 20 to 80. [2] The thermoplastic elastomer composition comprises a thermoplastic elastomer component (A), an olefin-based resin component (B), and a softener component (C), The resin composition for anti-slip mats according to [1] above, containing 10 to 90 parts by mass of the olefin resin component (B) and 100 to 300 parts by mass of the softener component (C) relative to 100 parts by mass of the thermoplastic elastomer component (A). [3] The resin composition for anti-slip mats according to [2] above, wherein the thermoplastic elastomer component (A) is at least one selected from a styrene-based elastomer, an olefin-based elastomer, and a hydrogenated styrene-based elastomer. [4] The resin composition for anti-slip mats according to [2] or [3] above, wherein the olefin-based resin component (B) is a polypropylene resin. [5] The resin composition for anti-slip mats according to any one of the above [2] to [4], wherein the softener component (C) is paraffin oil. [6] The resin composition for anti-slip mats according to any one of [1] to [5], wherein the elastomer composition further contains an anti-fungal agent, and the content of the anti-fungal agent is 0.01 to 10 parts by mass per 100 parts by mass of the thermoplastic elastomer component (A). [7] A molded product of the resin composition for anti-slip mats according to any one of [1] to [6] above, which contains 20 to 70 mass% of synthetic barium sulfate and has a type A durometer hardness of 20 to 80. [8] The anti-slip mat according to [7] above, wherein the specific gravity of the molded product is greater than 1.0 and less than 2.2. [9] A method for producing the resin composition for an anti-slip mat according to any one of [1] to [6] above, A method for producing a resin composition for an anti-slip mat, comprising a step of kneading using a continuous kneader.

[10] A method for manufacturing an anti-slip mat according to the above [7] or [8], A method for producing an anti-slip mat, characterized by subjecting the resin composition for an anti-slip mat according to any one of the above [1] to [6] to injection molding. [Effects of the Invention]

[0013] By using the resin composition for anti-slip mats of the present invention, an anti-slip mat can be obtained which has a moderately large specific gravity, can sink in water by itself, and is not excessively heavy, so that even elderly people and the like can easily handle it without hurting their legs and backs. Furthermore, since the resin composition for anti-slip mats of the present invention has excellent moldability, it is possible to produce anti-slip mats with high productivity that have flexibility that is comfortable to use, mechanical strength that can withstand use when people step on or sit on them, and excellent abrasion resistance.

[0014] The resin composition for an anti-slip mat of the present invention has good fluidity and can be produced using a continuous kneader such as an extruder. Furthermore, the resin composition for an anti-slip mat of the present invention is suitable for injection molding, resulting in excellent productivity for the anti-slip mat. Because the resin composition for an anti-slip mat of the present invention is a thermoplastic composition, the material from the molded product can be recycled.

[0015] The anti-slip mat of the present invention can be easily handled by even the elderly and others without accidents, and can be easily installed in the desired position by simply submerging it in water. It can also be easily installed in places where suction cups are difficult to attach. It also has excellent abrasion resistance and can be used for long periods of time. Furthermore, the anti-slip mat of the present invention can be manufactured by injection molding, resulting in high productivity. The anti-slip mat obtained from the resin composition for an anti-slip mat of the present invention has excellent mechanical strength and abrasion resistance, and is therefore suitable for use in bathrooms and bathtubs. Furthermore, the anti-slip mat of the present invention can be used as a fall prevention mat not only in bathrooms and bathtubs but also in wet environments such as poolsides and bath entrances. DETAILED DESCRIPTION OF THE INVENTION

[0016] The present invention will be described in detail below. The resin composition for anti-slip mats of the present invention (hereinafter also simply referred to as "resin composition") contains synthetic barium sulfate and a thermoplastic elastomer composition as essential components, and has a type A durometer hardness of 20 to 80. In the present invention, the thermoplastic elastomer composition preferably contains a thermoplastic elastomer component (A), an olefin-based resin component (B), and a softener component (C). That is, the resin composition of the present invention is preferably a resin composition containing synthetic barium sulfate, a thermoplastic elastomer component (A), an olefin resin component (B), and a softener component (C). Also, the resin composition of the present invention preferably further contains an antifungal agent.

[0017] Barium sulfate is broadly classified into synthetic barium sulfate and natural barium sulfate (also called elutriated barium sulfate or barite powder) depending on the manufacturing method, but the present invention uses synthetic barium sulfate.

[0018] The particle size of the synthetic barium sulfate used in the present invention affects flexibility, strength, abrasion resistance, and fluidity during injection molding, and is therefore preferably within the following particle size range. Specifically, the particle size at 10% undersize of the cumulative distribution on a volume basis (hereinafter referred to as "particle size D10") is preferably 0.01 to 5 μm. It is more preferably 0.05 to 3 μm, even more preferably 0.1 to 2 μm, and particularly preferably 0.2 to 1 μm. If the particle size D10 is less than 0.01 μm, the resulting anti-slip mat may become hard, resulting in a poor usability and poor fluidity of the resin composition, making it difficult to manufacture by injection molding. If the particle size D10 exceeds 5 μm, the strength and abrasion resistance of the resulting anti-slip mat may be reduced. Furthermore, the particle size at 50% undersize of the cumulative distribution on a volume basis (hereinafter referred to as "particle size D50" or "median size") is preferably 0.05 to 30 μm. It is more preferably 0.07 to 25 μm, even more preferably 0.1 to 20 μm, even more preferably 0.1 to 15 μm, particularly preferably 0.15 to 10 μm, and especially preferably 0.15 to 6 μm. If the particle size D50 is less than 0.05 μm, the resulting anti-slip mat may become hard, resulting in a poor feel in use and poor fluidity of the resin composition, making it difficult to produce by injection molding. If the particle size D50 exceeds 30 μm, the strength and abrasion resistance of the resulting anti-slip mat may decrease. Furthermore, the volume-based cumulative distribution undersize 90% (hereinafter referred to as "particle size D90") is preferably 0.1 to 50 μm. It is more preferably 0.3 to 40 μm, even more preferably 0.4 to 30 μm, and particularly preferably 0.5 to 20 μm. If the particle size D90 is less than 0.1 μm, the resulting anti-slip mat may become hard, resulting in a poor feel in use and poor fluidity of the resin composition, making it difficult to produce by injection molding. If the particle size D90 exceeds 20 μm, the strength and abrasion resistance of the resulting anti-slip mat may decrease. From the viewpoint that the smaller the difference between the particle diameter D10 and the particle diameter D90, the better the balance between the flexibility, strength, and flowability during injection molding of the resin composition, so the difference between the particle diameter D90 and the particle diameter D10 (particle diameter D90 - particle diameter D10) is preferably 20 μm or less, more preferably 10 μm or less, even more preferably 2 μm or less, still more preferably 1.5 μm or less, and particularly preferably 1 μm or less. The particle size can be measured using a particle size / particle size distribution measuring device.

[0019] The synthetic barium sulfate may be surface-treated to improve dispersibility in the resin composition. Examples of the surface treatment agent that can be used include coupling agents such as silane coupling agents and titanate coupling agents; and organic compounds containing polar groups such as carboxy groups, amino groups, epoxy groups, isocyanate groups, and hydroxyl groups (hereinafter referred to as "polar group-containing organic compounds").

[0020] Examples of the silane coupling agent include vinyl group-containing silane coupling agents such as vinyltrichlorosilane, vinyltriethoxysilane, and vinyl-tris(β-methoxyethoxy)silane; Epoxy group-containing silane coupling agents such as 3-glycidoxypropyltrimethoxysilane and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; silane coupling agents containing a methacryl group or an acryl group, such as 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-acryloxypropyltrimethoxysilane; amino group-containing silane coupling agents such as N-2-(aminoethyl)-3-aminopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; isocyanate group-containing silane coupling agents such as 3-isocyanatepropyltriethoxysilane; Isocyanurate group-containing silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; Ureido group-containing silane coupling agents such as 3-ureidopropyltrimethoxysilane styryl group-containing silane coupling agents such as p-styryltrimethoxysilane; Halogen-containing silane coupling agents such as 3-chloropropyltrimethoxysilane; Mercapto group-containing silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane etc.

[0021] Examples of the titanate coupling agent include tetraisopropyl titanate, tetra-normal-butyl titanate, tetraoctyl titanate, butyl titanate dimer, isopropyl triisostearoyl titanate, isopropyl tridodecylbenzenesulfonyl titanate, isopropyl-tris(dioctylpyrophosphate) titanate, and bis(dioctylpyrophosphate)oxyacetate titanate.

[0022] Examples of the polar group-containing organic compound include carboxy group-containing aliphatic organic compounds such as oleic acid, lauric acid, and stearic acid; Amine group-containing aliphatic organic compounds such as oleylamine, laurylamine, and stearylamine; Epoxy group-containing aliphatic compounds such as oleyl glycidyl ether, lauryl glycidyl ether, and stearyl glycidyl ether; isocyanate group-containing aliphatic organic compounds such as oleyl isocyanate, lauryl isocyanate, and stearyl isocyanate; Hydroxyl group-containing aliphatic organic compounds such as oleyl alcohol, lauryl alcohol, and stearyl alcohol etc.

[0023] From the viewpoints of compatibility and miscibility with the thermoplastic elastomer composition in the resin composition of the present invention, as well as strength and abrasion resistance, the surface treatment agent is preferably a carboxy group-containing aliphatic organic compound such as stearic acid, or an amino group-containing aliphatic organic compound such as stearylamine.

[0024] When kneading and producing a resin composition containing surface-treated synthetic barium sulfate, the synthetic barium sulfate, the surface treatment agent, and the raw materials for the thermoplastic elastomer composition, namely, the thermoplastic elastomer component (A), the olefinic resin component (B), and the softener component (C), can be simultaneously charged into a kneader and mixed. Alternatively, synthetic barium sulfate previously treated with the surface treatment agent can be used together with the thermoplastic elastomer component (A), the olefinic resin component (B), and the softener component (C). From the viewpoint of the abrasion resistance of the resin composition of the present invention, the above-mentioned surface treatment agent can be used in a range of 0.01 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of barium sulfate. From the viewpoint of compatibility and miscibility with the resin composition of the present invention, the lower limit is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more, even more preferably 0.07 parts by mass or more, and particularly preferably 0.1 parts by mass or more. On the other hand, from the viewpoint of the strength and abrasion resistance of the obtained anti-slip mat, the upper limit is preferably 60 parts by mass or less, more preferably 40 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 10 parts by mass or less.

[0025] Synthetic barium sulfate not only improves abrasion resistance but also increases the specific gravity of the resin composition of the present invention. Therefore, the amount of synthetic barium sulfate used is 20 to 70% by mass, assuming the entire resin composition to be 100% by mass. If the amount is less than 20% by mass, the specific gravity of the resin composition of the present invention is too low to sink in water. If the amount exceeds 70% by mass, the resulting anti-slip mat becomes heavy, making it difficult for the user to handle. The content is preferably 30 to 70% by mass, more preferably 40 to 70% by mass, and even more preferably 50 to 70% by mass.

[0026] The thermoplastic elastomer composition of the present invention preferably contains a thermoplastic elastomer component (A), an olefin resin component (B), and a softener component (C).

[0027] [Thermoplastic elastomer component (A)] The thermoplastic elastomer component (A) used in the present invention is not particularly limited as long as it is made of a thermoplastic elastomer. Examples of such thermoplastic elastomers include olefin-based elastomers, styrene-based elastomers, hydrogenated styrene-based elastomers, vinyl chloride-based elastomers, chlorinated polyethylene-based elastomers, ethylene-vinyl acetate-based elastomers, 1,2-polybutadiene-based elastomers, polyurethane-based elastomers, polyester-based elastomers, polyamide-based elastomers, and fluorine-based elastomers. From the viewpoint of the water resistance and anti-slip effect of the resulting anti-slip mat, preferred are olefin-based elastomers, styrene-based elastomers, hydrogenated styrene-based elastomers, vinyl chloride-based elastomers, and chlorinated polyethylene-based elastomers. Furthermore, from the viewpoint of flexibility, strength, and abrasion resistance of the anti-slip mat obtained when highly filled with barium sulfate, olefin-based elastomers, styrene-based elastomers, and hydrogenated styrene-based elastomers are more preferred, and from the viewpoint of resistance to chlorine water, styrene-based elastomers and hydrogenated styrene-based elastomers are particularly preferred.

[0028] The olefin-based elastomer is preferably a copolymer containing ethylene units or propylene units. Examples include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, ethylene-propylene-1-butene copolymer, ethylene-propylene-1-hexene copolymer, ethylene-propylene-1-octene copolymer, and ethylene-propylene-diene copolymer. Among these, ethylene-α-olefin copolymers containing ethylene units and structural units derived from α-olefins are preferred. Furthermore, ethylene-α-olefin copolymers in which the lower limit of the ethylene unit content is 60% by mass are particularly preferred.

[0029] The styrene-based elastomer is a copolymer having structural units derived from an aromatic vinyl compound. Typically, blocks containing structural units derived from an aromatic vinyl compound exhibit thermoplasticity and constitute hard segments. The monomer constituting the hard segment may be any aromatic vinyl compound, and the type thereof is not limited, but examples thereof include alkyl-substituted styrenes such as styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,5-dimethylstyrene, and 3,5-dimethylstyrene, vinylnaphthalene, vinylanthracene, etc. These aromatic vinyl compounds may be used alone or in combination of two or more. On the other hand, the blocks constituting the soft segments may be formed using any monomer as long as they exhibit elastomer properties and function as soft segments, but it is preferable to use conjugated dienes. Examples of conjugated dienes that form such soft segments include butadiene, isoprene, chloroprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-octadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-hexadiene, and 1,3-cyclohexadiene. These conjugated dienes may be used alone or in combination of two or more.

[0030] Examples of styrene-based elastomers made of styrene copolymers include styrene-isoprene-styrene block (SIS) copolymers, styrene-butadiene-styrene block (SBS) copolymers, and styrene-ethylene-propylene-styrene block (SEPS) copolymers. Furthermore, some or all of the styrene-derived structural units of these exemplified copolymers may be replaced with structural units derived from styrene derivatives such as α-methylstyrene. Such (non-hydrogenated) styrene-based elastomers may be used alone or in combination.

[0031] The hydrogenated styrene elastomer can be obtained by hydrogenating the styrene copolymer constituting the non-hydrogenated styrene elastomer, and examples thereof include styrene-ethylene-butylene-styrene block copolymer (SEBS) copolymer, hydrogenated styrene-butadiene-styrene block copolymer (HSBR), etc. Such hydrogenated styrene elastomers may be used alone or in combination of two or more.

[0032] The thermoplastic elastomer component (A) of the present invention may be an acid-modified thermoplastic elastomer or an amine-modified thermoplastic elastomer. Examples of such acid-modified thermoplastic elastomers include acid-modified styrene-based elastomers such as maleic acid-modified styrene-based elastomers and fumaric acid-modified styrene-based elastomers, and acid-modified olefin-based elastomers such as maleic acid-modified olefin-based elastomers and fumaric acid-modified olefin-based elastomers. Furthermore, such amine-modified thermoplastic elastomers are amine-modified styrene-based elastomers. Among these, acid-modified styrene-based elastomers are preferred. The thermoplastic elastomer component (A) contained in the thermoplastic elastomer composition may be one type or two or more types.

[0033] Commercially available products can be used as raw materials for the thermoplastic elastomer component (A). Specific examples of the styrene copolymer (styrene thermoplastic elastomer) include Kraton Polymer Japan's trade names "Kraton G" (G1642, G1652, G1730, etc.), Kraton Polymer Japan's trade names "Kraton D" (D1101, D1102, D1155, D1192, D1161, D1171, DKX405, DKX410, DKX415, etc.), JSR's trade names "JSR-TR" (JSR-TR1086, JSR-TR1600, etc.), JSR's trade names "JSR-SIS", JSR's trade names "Dynalon", Asahi Kasei's trade names " Examples of such products include those under the trade name "Tuftec" (Tuftec H series, Tuftec P series, etc.), Asahi Kasei Corporation's trade name "Tufprene" (Tufprene A, Tufprene 125, Tufprene 126S, etc.), Asahi Kasei Corporation's trade name "Asaprene", Asahi Kasei Corporation's trade name "Solprene", Kuraray Corporation's trade name "Septon", Kuraray Corporation's trade name "Hybler", Sumitomo Chemical Co., Ltd.'s trade name "Esporex SB", Mitsubishi Chemical Corporation's trade names "Labalon" and "Tefabloc", Denki Kagaku Co., Ltd.'s trade name "Denka STR", Nippon Zeon Corporation's trade name "Quintac", and Riken Technos Corporation's trade name "Leostomer". Examples of acid-modified styrene-based elastomers include "Tuftec M1913" manufactured by Asahi Kasei Corporation, and examples of acid-modified olefin-based elastomers include "Tafmer MP0610" manufactured by Mitsubishi Chemical Corporation. Examples of the amine-modified thermoplastic styrene elastomer include "Tuftec MP10" manufactured by Asahi Kasei Corporation. These may be used alone or in combination of two or more. These product names may also be registered trademarks.

[0034] [Olefin-based resin component (B)] The olefin-based resin component (B) of the present invention serves as a binder when kneading and preparing the resin composition of the present invention. It also imparts strength, abrasion resistance, etc. to the resin composition of the present invention and the resulting anti-slip mat, and has the effect of suitably controlling the specific gravity. It also has the function of improving moldability during injection molding.

[0035] The olefin resin component (B) is not particularly limited as long as it is a resin having an ethylene unit or an α-olefin unit, and examples thereof include resins made of low-density polyethylene, high-density polyethylene, linear low-density polyethylene, polypropylene, syndiotactic polypropylene, isotactic polypropylene, ethylene-α-olefin copolymer, etc., and modified resins thereof.

[0036] In the present invention, when the thermoplastic elastomer component (A) is a styrene-based elastomer, an olefin-based elastomer, or a hydrogenated styrene-based elastomer, the olefin-based resin component (B) is preferably a resin having an α-olefin unit, because of its excellent miscibility and compatibility. Polypropylene resin and ethylene-α-olefin copolymer (with the upper limit of the ethylene unit content being 40 mass%) are preferred, and polypropylene resin is particularly preferred.

[0037] When the olefin resin component (B) is a modified resin, an olefin resin containing a polar group such as a glycidyl group, a carboxy group, or an acid anhydride group can be used. Examples of glycidyl group-containing olefin resins include ethylene-glycidyl methacrylate copolymers. Examples of the olefin resin containing an acid anhydride group include maleic anhydride-modified polypropylene, maleic anhydride-modified polyethylene, and ethylene-maleic anhydride copolymer.

[0038] Commercially available products can be used as raw materials for the olefin resin component (B). Specific examples of maleic anhydride-modified polypropylene include "Admer QF" (trade name) manufactured by Mitsui Chemicals, Inc., "Eumex" (trade name) manufactured by Sanyo Chemical Industries, Ltd., and "Rikeaid MG" (trade name) manufactured by Riken Vitamin Co., Ltd. Specific examples of maleic anhydride modified polyethylene include "Admer LF, NF" manufactured by Mitsui Chemicals. Specific examples of ethylene-maleic anhydride copolymers include "LOTADER MAH" (trade name) manufactured by Arkema, and "BONDINE" (trade name) manufactured by Sumitomo Chemical Co., Ltd. Specific examples of ethylene-glycidyl methacrylate copolymers include "BONDFAST" (trade name) manufactured by Sumitomo Chemical Co., Ltd. and "LOTADER GMA" (trade name) manufactured by Arkema. These olefin resins may be used alone or in combination of two or more.

[0039] As the olefin-based resin component (B), ethylene-α-olefin copolymer, polypropylene resin, and maleic anhydride-modified polypropylene are preferred because of their low specific gravity, and polypropylene resin and maleic anhydride-modified polypropylene are more preferred because of their miscibility and compatibility with the thermoplastic elastomer component (A). The olefin resin component (B) is preferably a resin having a melt mass-flow rate (hereinafter also referred to as "MFR") of 1 to 100 g / 10 min. If the melt mass-flow rate is less than 1 g / 10 min, the fluidity of the resin composition of the present invention decreases, and moldability deteriorates. On the other hand, if the melt mass-flow rate exceeds 100 g / 10 min, the strength and abrasion resistance of the resulting anti-slip mat decrease. The rate is more preferably 3 to 70 g / 10 min, further preferably 5 to 50 g / 10 min, and particularly preferably 10 to 40 g / 10 min. The melt mass-flow rate depends on the molecular weight of the olefin resin component (B) and is an indicator of the moldability and strength of the resin composition. The melt mass-flow rate is measured in accordance with JIS K7201-1 at a temperature of 230°C and a load of 21.18 N. The raw material resin for the olefin resin component (B) may contain fillers such as talc, calcium carbonate, and glass fiber, antioxidants, weather resistance imparting agents, and the like.

[0040] [Softener component (C)] The softener component (C) is not particularly limited, but is preferably compatible with the thermoplastic elastomer component (A). This can prevent problems such as bleeding of the softener component (C) from the resulting molded article. From this perspective, preferred softener components (C) include rubber softeners such as paraffin oil, naphthenic oil, and aromatic oil. The softener component (C) contained in the thermoplastic elastomer composition may be one type or two or more types.

[0041] Among the thermoplastic elastomers, paraffin oil is preferred from the viewpoints that it has particularly good compatibility with styrene-based elastomers and is less likely to bleed. Such paraffin oil preferably has a high kinematic viscosity at 40°C. Specifically, 30mm paraffin oil is preferred because it prevents evaporation during heating and melting and improves bleeding resistance. 2 / s or more is preferable, 60 mm 2 / s or more is preferable, and 80 mm 2 / s or more is more preferable. Also, considering the case where it is combined with a polar resin, from the viewpoint of improving the fusion property, it is preferable to use a resin having a thickness of 150 mm 2 On the other hand, the kinematic viscosity is preferably 500 mm / s or more because it is easy to handle. 2 / s or less is preferable, 450 mm 2 / s or less is preferable, and 400mm 2 From the viewpoint of improving the abrasion resistance, it is particularly preferable that the friction coefficient is 200 mm / s or less. 2 / s or less. The kinematic viscosity is measured in accordance with JIS K2283.

[0042] The thermoplastic elastomer composition according to the present invention contains a thermoplastic elastomer component (A), an olefin resin component (B), and a softener component (C) in order to satisfy physical properties such as flexibility, strength, and abrasion resistance. The blending ratio of these components is such that, when the content of component (A) is 100 parts by mass, the content of component (B) is preferably 10 to 90 parts by mass, and the content of component (C) is preferably 100 to 300 parts by mass. The content of component (B) is more preferably 15 to 70 parts by mass, and even more preferably 15 to 50 parts by mass. The content of component (C) is more preferably 110 to 250 parts by mass, and even more preferably 110 to 200 parts by mass.

[0043] From the viewpoints of moldability and the abrasion resistance and flexibility of the resulting anti-slip mat, the content of the thermoplastic elastomer composition constituting the resin composition for anti-slip mats of the present invention is 80% by mass or less, preferably 26 to 80% by mass, more preferably 30 to 75% by mass, and even more preferably 35 to 70% by mass, based on 100% by mass of the resin composition for anti-slip mats. If the content of the thermoplastic elastomer composition is less than 26% by mass, the content of the thermoplastic elastomer component (A) will be too low, and the moldability may be insufficient.

[0044] [Anti-mold agent] When the resin composition for an anti-slip mat of the present invention contains an anti-fungal agent, it can prevent the growth of fungi, such as mold, on the anti-slip mat after it comes into contact with water. Therefore, when an anti-slip mat containing the anti-fungal agent is used on a poolside, pool bottom, in a bathroom, a bathtub, or the like, it is hygienic because it can prevent the growth of mold. The above antifungal agent is not particularly limited, but is preferably one that has good compatibility and dispersibility with the components (A) and (C) that constitute the thermoplastic elastomer composition.

[0045] The antifungal agent may be either a synthetic antifungal agent or a natural antifungal agent. Examples of synthetic antifungal agents include thiabendazole; pyrithione metal salts such as pyrithione zinc salt; imidazole compounds such as methyl-2-benzimidazole carbamate, methyl-1-(butylcarbamoyl)benzimidazole-2-carbamate, and enilconazole; phthalimide compounds such as N-(trichloromethylthio)phthalimide; amine compounds such as N-nitrosocyclohexylhydroxylamine aluminum; nitrile compounds such as 2,4,5,6-tetrachloroisophthalonitrile; benzothiazole compounds such as 2-(thiocyanomethylthio)benzothiazole; thiocyanate compounds such as methylene bisthiocyanate; orthophenylphenol (OPP) compounds such as orthophenylphenol sodium salt; phenylpyrrole compounds such as fludioxonil; anilinopyrimidine compounds such as pyrimethallyl; methoxyacrylate compounds such as azoxystrobin; and halogenated phenol compounds such as parachlorometaxylenol. Examples of natural antifungal agents include hinokitiol, thymol, and d-limonene. The above antifungal agents may be used alone or in combination of two or more kinds. Among the above antifungal agents, thiabendazole and metal pyrithione salts are preferred from the viewpoints of compatibility with the thermoplastic elastomer composition and dispersibility in the resin composition for an anti-slip mat of the present invention.

[0046] As the antifungal agent, commercially available synthetic antifungal agents can be used. Examples of commercially available synthetic antifungal agents include those manufactured by Sumika Environmental Science Co., Ltd. under the trade names "Neosynthol," "Synthol," and "Biomessenger," those manufactured by MIC Co., Ltd. under the trade name "Pacific Beam," those manufactured by Fuji Chemical Co., Ltd. under the trade name "Bactekiller," those manufactured by San-ai Oil Co., Ltd. under the trade name "Sanaizol," and those manufactured by Lanxess AG under the trade name "Preventol."

[0047] When the resin composition for anti-slip mats of the present invention contains an anti-fungal agent, the content thereof is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 8 parts by mass, even more preferably 0.03 to 7 parts by mass, and particularly preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the thermoplastic elastomer component (A) constituting the thermoplastic elastomer composition. If the content of the anti-fungal agent exceeds 10 parts by mass, the resin composition for anti-slip mats of the present invention may become sticky, blooming may occur in the molded product, deteriorating the appearance, and the abrasion resistance may be deteriorated.

[0048] If desired, other compounding components may be added to the resin composition for anti-slip mats of the present invention within the range that does not impair the physical properties. Examples of other additives include, but are not limited to, fillers, weather resistance agents, antioxidants, lubricants, pigments and dyes, polar group-containing resins, processing aids, and the like. This will be explained in detail below.

[0049] [Filler] The resin composition for an anti-slip mat of the present invention may contain other fillers to adjust the strength and specific gravity. Examples of other fillers include metal powders such as tungsten alloys, stainless steel alloys, copper, iron, and aluminum; inorganic fillers such as heavy calcium carbonate, light calcium carbonate, magnesium carbonate, magnesium hydroxide, aluminum hydroxide, antimony trioxide, titanium oxide, talc, mica, and clay; and reinforcing fibers such as rock wool, slag wool, glass wool, and glass fiber.

[0050] [Weather resistance imparting agent] When the resin composition for anti-slip mats of the present invention contains a weather resistance imparting agent, when an anti-slip mat is hung outside to dry after being used outdoors or after being used indoors, it is exposed to sunlight, and light degradation of the anti-slip mat can be suppressed. Examples of weather resistance imparting agents include ultraviolet absorbers such as benzotriazoles, benzophenones, benzoates, and cyanoacrylates, and light stabilizers such as HALS (hindered amines).

[0051] [Antioxidants] When heat is applied to the resin composition for anti-slip mats of the present invention during the process of producing the resin composition for anti-slip mats using a kneader or during the process of producing anti-slip mats by injection molding, an antioxidant can be used to suppress deterioration of physical properties and color tone. Examples of antioxidants include hindered phenol compounds, amine compounds, phosphite compounds, phosphate compounds, sulfur compounds, etc. These antioxidants can be used alone or in combination of two or more.

[0052] Hindered phenol antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxymethyl-2,6-di-t-butylphenol, 2,6-di-t-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4'-bis(2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), 4,4 '-Methylene-bis(6-t-butyl-o-cresol), 4,4'-methylene-bis(2,6-di-t-butylphenol), 2,2'-methylene-bis(4-methyl-6-cyclohexylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol), bis(3-methyl-4-hydroxy-5-t-butylbenzyl) sulfide, 4,4'-thiobis(6-t-butyl-o-cresol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, 3,5-di-t-butyl-4-hydroxybenzenesulfonic acid diethyl ester, 2,2'-dihydroxy-3,3'-di(α-methylcyclohexyl)-5,5'-dimethyl-diphenylmethane, α-octadecyl-3(3',5'-di-t-butyl-4'-hydroxyphenyl)propionate, 6-(hydroxy-3,5-di-t-butylanilino)-2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol Bis[β-(3,5-di-t-butyl-4-hydroxyphenol)propionate], N,N'-hexamethylene-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide), 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid dioctadecyl ester, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-di-t-butylphenyl)butane, tris(3,5-di-t-butyl-4-hydroxyphenyl)isocyanurate, tris[β-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxyethyl]isocyanurate, etc. Among these, those having a molecular weight of 500 or more, such as tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, are preferred.

[0053] Examples of the amine antioxidant include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and 4-isopropoxydiphenylamine.

[0054] Phosphite antioxidants include tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-1,6-hexamethylene-bis(N-hydroxyethyl-N-methylsemicarbazide)-diphosphite, tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-1,10-decamethylene-dicarboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, and tetrakis[2-t-butyl-4-thio(2'-methyl-4 tetrakis[2-t-butyl-4-thio(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-5-methylphenyl]-N,N'-bis(hydroxyethyl)oxamide-diphosphite, and the like. In the present invention, phosphite compounds in which at least one PO bond or P=O bond is bonded to an aromatic group are preferred.

[0055] Phosphite compounds include tris(2,4-di-t-butylphenyl)phosphite, tetrakis(2,4-di-t-butylphenyl)4,4'-biphenylenephosphonite, bis(2,4-di-t-butylphenyl)pentaerythritol-diphosphite, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol-diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octylphosphite, 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl)phosphite, tris(2-methyl-4-ditridecylphosphite-5-t-butyl-phenyl)butane, tris(mixed mono- and di-nonylphenyl)phosphite, tris(nonylphenyl)phosphite, 4,4'-isopropylidenebis(phenyl-dialkylphosphite), 3,9-bis(2,6-di-t-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane, and the like. In addition to the above antioxidants, other antioxidants such as phosphate compounds and sulfur compounds can also be used.

[0056] [Lubricant] The resin composition for the anti-slip mat of the present invention may contain a lubricant for the purpose of improving molding processability when producing the resin composition for the anti-slip mat of the present invention, or for the purpose of improving releasability from a mold when producing the anti-slip mat of the present invention. Examples of lubricants include fatty acids, fatty acid amides, esters, alcohols, metal soaps, silicone oils, silicone resins, and fluorine-based resins. Examples of fatty acid lubricants include myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid. Examples of fatty acid amide lubricants include stearylamide, palmitylamide, oleylamide, methylenebisstearamide, and ethylenebisstearamide. Examples of the ester-based lubricant include lower alcohol esters of fatty acids, polyhydric alcohol esters of fatty acids, and fatty acid polyglycol esters. Examples of alcohol-based lubricants include cetyl alcohol, stearyl alcohol, and polyethylene glycol. Examples of metal soap lubricants include zinc stearate, calcium stearate, aluminum stearate, zinc 12-hydroxystearate, and calcium 12-hydroxystearate. In addition to the above, silicone oil, silicone resin, fluorine resin, etc. can also be used.

[0057] [Colorants (pigments and dyes)] When it is desired to color the anti-slip mat of the present invention in any color, a coloring agent can be used. As a coloring method, there is a method in which, when producing the resin composition for the anti-slip mat of the present invention, a colorant such as a pigment or dye, or a colorant masterbatch, etc. is added. Alternatively, there is a method in which the resin composition of the present invention is produced in a natural color without adding a colorant, and when producing the anti-slip mat of the present invention, a colorant such as a pigment or dye, or a colorant masterbatch, etc. is added. As such pigments and dyes, organic and inorganic types are known, and any common type can be used as long as it can withstand the heat during molding.

[0058] [Polar group-containing resin] The resin composition for an anti-slip mat of the present invention may contain a polar group-containing resin for the purpose of increasing the tension of the molten material and improving the extensibility during production of the anti-slip mat or during production of the anti-slip mat. The polar group-containing resin is a resin other than an acid-modified thermoplastic elastomer and a polar group-containing olefin resin, and specific examples thereof include polyester resin, polyamide resin, polycarbonate resin, and the like.

[0059] The resin composition for anti-slip mats of the present invention may contain processing aids such as acrylic-modified polytetrafluoroethylene and high-molecular-weight special acrylic resins. Antistatic agents, flame retardants, oil repellents, chelating agents, pigment dispersants, etc. may also be added.

[0060] When the resin composition for anti-slip mats of the present invention contains other additives (excluding antifungal agents), the content of these additives in the resin composition for anti-slip mats is preferably 10% by mass or less. If the content exceeds 10% by mass, the surface of the resulting molded product may become sticky, and the strength, abrasion resistance, anti-slip properties, etc. of the molded product may be reduced.

[0061] From the viewpoint of moldability, the resin composition for an anti-slip mat of the present invention preferably has a melt mass flow rate of more than 0.1 g / min at a temperature of 230° C. and a load of 98 N measured in accordance with JIS K7210-1. The melt mass-flow rate is more preferably 0.2 g / 10 min or more, even more preferably 0.5 g / 10 min or more, and particularly preferably 1 g / 10 min or more. When the melt mass-flow rate exceeds 0.1 g / 10 min, moldability during injection molding becomes good.

[0062] The resin composition for anti-slip mats of the present invention can be produced by mixing and kneading synthetic barium sulfate with the thermoplastic elastomer component (A), olefin-based resin component (B) and softener component (C) that constitute the thermoplastic elastomer composition, and, if necessary, various additives (such as anti-mold agents). To mix the raw material components, a mixing device such as a Henschel mixer, a super mixer, or a tumbler mixer is used. The resulting mixture is usually melt-kneaded using an extruder and extruded into strands, which are then cooled in cold water and cut into pellets using a cutter. The resulting pellets are usually made into a desired molded product by injection molding or extrusion molding. The kneaded composition can also be pelletized using a rudder or the like to be used as a raw material for molding processing. In order to improve the productivity of the resin composition for anti-slip mats of the present invention, the kneading device used is preferably a continuous type such as an extruder. Such an extruder may be a single-screw extruder or a multi-screw extruder such as a twin-screw extruder or a four-screw extruder. From the viewpoints of kneading power and productivity, a twin-screw extruder is more preferable. The resin composition for an anti-slip mat produced as described above has a type A durometer hardness of 20-80.

[0063] The anti-slip mat of the present invention is a molded product containing the resin composition for an anti-slip mat of the present invention. The resin composition for an anti-slip mat of the present invention and an anti-slip mat containing the resin composition for an anti-slip mat of the present invention are characterized by a Type A durometer hardness of 20 to 80 measured in accordance with JIS K6253. Because the Type A durometer hardness is within the above range, the molded anti-slip mat is not too soft, and there is no feeling of hitting the bottom or discomfort when used. In addition, the anti-slip mat can be easily folded or rolled up. The type A durometer hardness is preferably 30-70, more preferably 40-70, and particularly preferably 50-70.

[0064] Since the anti-slip mat containing the resin composition for anti-slip mats of the present invention may be used by immersing it in a bathtub or a pool, it is preferable that it has a large specific gravity. However, if it is too heavy, it may be difficult for elderly people to carry and there is a risk of injury to the legs and back when handling it. Furthermore, there is a risk of dropping it while handling it and causing injury. Therefore, the specific gravity of the resin composition for anti-slip mats and the anti-slip mat of the present invention is preferably more than 1.0 and less than 2.2. If it is 1.0 or less, it will not sink in water. If it is 2.2 or more, it will be difficult for elderly people to handle. A more preferred range is greater than 1.1 and less than 2.1, a more preferred range is greater than 1.2 and less than 2.0, and a particularly preferred range is greater than 1.4 and less than 1.9. The specific gravity of the resin composition for anti-slip mats and the anti-slip mat of the present invention can be selected from the above range depending on the intended use so that the anti-slip mat has a short self-settling time and is easy to handle, and can be controlled by the amount of synthetic barium sulfate or olefin-based resin used.

[0065] An anti-slip mat containing the resin composition for an anti-slip mat of the present invention must have wear resistance that can withstand repeated actions such as rubbing and pushing when a user sits or walks. The abrasion resistance required for the composition for an anti-slip mat of the present invention is such that the abrasion loss mass of the resin composition for an anti-slip mat in a Taber abrasion test according to JIS K7204 is preferably less than 1000 mg, more preferably less than 800 mg, even more preferably less than 500 mg, and particularly preferably less than 200 mg. Such low wear loss mass can be achieved by using synthetic barium sulfate.

[0066] The anti-slip mat containing the resin composition for anti-slip mats of the present invention preferably has a self-sinking rate of less than 8 seconds. From the viewpoint of ease of use for users, it is more preferably less than 6 seconds. It is even more preferably less than 5 seconds, and particularly preferably less than 4 seconds. If the self-sinking rate exceeds 8 seconds, there is a possibility that a user may step on the mat before it has sunk sufficiently, which may result in the user's foot slipping.

[0067] The shape and size of the anti-slip mat of the present invention are appropriately determined depending on the location and purpose of use. For example, in the case of a bathroom or bathtub, from the viewpoint of weight and portability, it is generally plate-shaped, with a width of 10 to 100 cm, a length of 20 to 200 cm, and a thickness of 0.05 to 2 cm. The projected shape of the width and length may be square, rectangular, circular, oval, or any other shape. When used in a bathroom, bathtub, etc., the width is preferably 15 to 80 cm, more preferably 20 to 60 cm, and even more preferably 25 to 50 cm. The length is preferably 30 to 160 cm, more preferably 40 to 120 cm, and even more preferably 50 to 100 cm. The thickness is preferably 0.07 to 1.5 cm, more preferably 0.1 to 1 cm, and even more preferably 0.15 to 0.8 cm. From the viewpoint of ease of handling by users, the mass of the anti-slip mat of the present invention is preferably less than 5 kg, more preferably less than 4 kg, even more preferably less than 3 kg, and most preferably less than 2 kg.

[0068] The color tone of the anti-slip mat of the present invention can be determined arbitrarily, but generally, conspicuous colors such as red, green, and blue are preferred so that the mat can be easily recognized at a glance. In addition, to further enhance the anti-slip effect, the surface and / or back surface of the anti-slip mat of the present invention may be provided with convex or concave portions having a grid, concentric circle, or dot pattern by embossing or the like. As described above, the anti-slip mat of the present invention preferably has a specific gravity of more than 1.0 and less than 2.2, and preferably has an abrasion loss mass of less than 1000 mg in the Taber abrasion test. The anti-slip mat of the present invention is useful for preventing falls on wet floors or in water, and can be used in bathrooms, bathtubs, poolsides, pool bottoms, toilet floors, as well as entrances and bus entrances that are easily wetted by rainwater. Among these, it is suitable for use in bathrooms and bathtubs where falls by elderly people and others are common, and is particularly suitable for use in bathtubs.

[0069] The method for producing the anti-slip mat of the present invention is not particularly limited and can be appropriately selected depending on the shape and size. In the present invention, press molding, injection molding, and extrusion molding can be used. Among these, injection molding is preferred from the viewpoints of productivity and economy.

[0070] In the case of injection molding, the specifications of the mold used in the injection molding machine can be set arbitrarily. It is preferable to optimize the cavity structure within the mold by optimizing the flow ratio (L (flow distance) / t (wall thickness)), where L represents the farthest point within the cavity that should be filled from the gate opening where the molten resin flows into the mold. In the present invention, L / t is preferably less than 155 when t is 0.5 to 5 mm. If L / t is 155 or more, the resin composition for an anti-slip mat of the present invention may not be able to completely fill the mold, making it impossible to obtain a molded product of the desired shape and size. From the viewpoint of the appearance of the molded product (flow marks, etc.), L / t is more preferably less than 145, and even more preferably less than 140. [Example]

[0071] The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0072] [Production conditions for thermoplastic elastomer composition] A thermoplastic elastomer (component (A)), an olefin resin (component (B)), barium sulfate, an antifungal agent if necessary, and other components were dry-blended, and the mixture was impregnated with a softener (component (C)). The mixture was then melt-kneaded in an extruder under the following conditions to produce a base material (pellets) for the thermoplastic elastomer composition. Twin-screw extruder: KZW32TW-60MG (product name, manufactured by Technovel Co., Ltd.) Cylinder temperature: 180~220℃ Screw rotation speed: 300 rpm

[0073] [Injection molding conditions for test sheet 1] Injection molding was carried out under the following conditions to obtain a test sheet 1 having a thickness of 2 mm, a width of 125 mm, and a length of 125 mm. Injection molding machine: Mitsubishi Heavy Industries, Ltd. "100MSIII-10E" (model name) Injection molding temperature: 230℃ Injection pressure: 39MPa Injection time: 10sec Mold temperature: 40℃ Mold shape: Cavity shape; cuboid with thickness 2 mm, width 125 mm, and length 125 mm Gate position: Top of cavity (L / t=62.5) Gate shape: Film gate The formulation and the measurement and evaluation results are shown in Tables 1 to 3.

[0074] [Injection molding conditions for test sheet 2] Injection molding was carried out under the following conditions to obtain a test sheet 2 having a thickness of 3 mm, a width of 380 mm and a length of 200 mm. Injection molding machine: Mitsubishi Heavy Industries, Ltd. "100MSIII-10E" (model name) Injection molding temperature: 230℃ Injection pressure: 40MPa Injection time: 10sec Mold temperature: 40℃ Mold shape: Cavity shape; rectangular parallelepiped with a thickness of 3 mm, width of 380 mm, and length of 200 mm Gate location: Center of cavity plane diagonal (L / t=71.6) Gate shape: Pinpoint gate The formulation and the measurement and evaluation results are shown in Tables 1 to 3.

[0075] [Physical property measurement method] The physical properties of the evaluation samples were measured as follows: The mass of the sample was measured using an electronic balance "GF-203A" (model name) manufactured by A&D Co., Ltd. (1) Type A durometer hardness Three 2mm thick test sheets 1 were stacked (total thickness 6mm) and left to condition for one day in a room at a temperature of 23°C and humidity of 50%. The Type A durometer hardness was measured 15 seconds after the start of measurement in accordance with JIS K6253. The measuring device was a constant pressure loader "CL-150L" (model name) equipped with a digital rubber hardness tester "DD4-2" (model name) manufactured by ASKER. The load was 1000g. (2) Specific gravity Test sheet 1 was left to condition for one day in a room at a temperature of 23°C and a humidity of 50%, and then a test piece measuring 3 cm x 3 cm was cut out from the test sheet and measured in accordance with JIS K 7112. The measuring device was an electronic hydrometer "SD-200L" (model name) manufactured by Alpha Mirage. (3) Tensile test (tensile strength and elongation at break) Test sheet 1 was left to condition for one day in a room at 23°C and 50% humidity. A die-cutting machine was used to prepare No. 3 test specimens as specified in JIS K7113. A gauge line was drawn at ±10 mm from the center of the parallel part of the dumbbell (total gauge width: 20 mm). Next, using a Shimadzu Corporation tensile tester "Autograph AG-50ND" (model name), the test specimen was pulled at a speed of 500 mm / min at a temperature of 23°C. The stress (MPa) at the time of specimen break was recorded as the tensile strength. At the same time, the distance between the gauge lines of the parallel part of the dumbbell at break was measured and subtracted from the initial value of 20 mm to calculate the elongation at break. The higher the tensile strength, the better the mechanical strength. (4) Taber abrasion test Test sheet 1 was left to condition for one day in a room at 23°C and 50% humidity, and a 10.8cm diameter disk was punched out from it. An abrasion test was conducted in accordance with JIS K7204 at 23°C using an H-22 abrasion wheel, a rotation speed of 72 rpm, 1000 rotations, and a load of 1000g. The abrasion loss mass (mg) was measured from the difference in the sample's mass before and after the test. The measuring device was a rotary abrasion tester "TS-2" (model name) manufactured by Toyo Seiki Seisakusho Co., Ltd. (5) Melt mass flow rate Using the base material (pellets), measurements were taken at a temperature of 230°C and a load of 21.18N in accordance with JIS K7210-1. Data less than 0.1g / 10min were recorded as "NF," and the load was changed to 49.18N and the measurement was repeated. Again, data less than 0.1g / 10min were recorded as "NF," and the load was changed to 98.18N and the measurement was repeated. Again, data less than 0.1g / 10min were recorded as "NF." (Here, "NF" stands for "not flowing.") The measuring device used was a "Melt Indexer" (trade name) manufactured by Toyo Seiki Seisakusho, Ltd. (6) Slippage test A test piece measuring 135 mm in length and 90 mm in width was cut out from Test Sheet 2, and the slip resistance coefficient (CSR·B value) was determined in accordance with JIS A1509-12 "Test methods for ceramic tile - Part 12: Test method for slip resistance." A weight of 4.31 N was used as the load. (7) Self-sinking test Using a test sheet 2 measuring 380 mm wide x 200 mm long x 3 mm thick, a transparent acrylic resin container (500 mm wide x 500 mm long x 500 mm high) was filled with water to a depth of 30 cm. One end of the sample (the 200 mm long side) was attached to the bottom of the container, and the other end was held at the water surface level, so that the sample was placed in a cantilevered position in the water. Thereafter, the end on the water surface side was released from the holding, and the time until that end sank to the bottom of the container was measured. (8) Chlorine water test One tablet of "Furosui Wonder" (trade name) manufactured by Kao Corporation was added to 50 L of warm water (40°C). Test sheet 1 was then immersed in this warm water and the temperature (40°C) was maintained. After 4 hours, test sheet 1 was removed and water droplets were wiped off. Next, the test sheet was left in a room at a temperature of 23°C and a humidity of 50% for 24 hours to condition it. After the condition adjustment, a sensory test was performed on the stickiness by touching with a finger.

[0076] (9) Antifungal test Test pieces measuring 3 cm x 3 cm were cut out from the above test sheet 1, and in accordance with JIS Z2911 (mold resistance test method, Appendix A: Testing of plastic products), a suspension of a complex of five fungi was dropped onto each test piece on an agar medium, and the test pieces were cultured for 4 weeks at a specified temperature and humidity, and the growth state of the mycelia on the test pieces was evaluated. The evaluation was carried out on a scale of 0 to 5, as shown below. "0": No mold growth is observed with the naked eye or under a microscope. "1": No mold growth is visible to the naked eye, but is clearly visible under a microscope. "2": Mold growth is visible to the naked eye, and the area of ​​growth is less than 25% of the total area of ​​the sample. "3": Mold growth is visible to the naked eye, and the area of ​​growth is 25% or more but less than 50% of the total sample area. is. "4": Mycelia grow well, and the growth area is 50% or more of the total sample area. "5": The mycelium is growing vigorously, and the entire surface of the sample is covered with mold.

[0077] [Materials used in the test] The materials used in the tests in Tables 1 to 3 (materials used in producing the resin compositions for anti-slip mats) are as follows. (1) Thermoplastic elastomer A1: SEBS "GLOBALPRENE 7551U" (trade name) manufactured by LCY CHEMICAL, hydrogenated styrene-butadiene-styrene block copolymer, styrene content 33% by mass, weight average molecular weight 200,000 (2) Thermoplastic elastomer A2: Kraton D1102 (trade name) manufactured by Kraton Polymers, a non-hydrogenated styrene-butadiene-styrene block copolymer, styrene content 30% by mass, weight average molecular weight 110,000 (3) Thermoplastic elastomer A3: Ethylene-1-octene copolymer elastomer manufactured by Dow Chemical Company, 1-octene content 22% by mass (4) Olefin resin: IRPC Public Company's "POLIMAXX 1100RC" (trade name), polypropylene (homopolymer), melt mass flow rate: 20 g / 10 min (230 °C, 21.18 N load) (5) Softener: Paraffin oil "LW500" (trade name) manufactured by Japan Sun Oil Co., Ltd., kinematic viscosity: 99.3 mm 2 / s(40℃) (6) Antioxidant (phenolic): "Tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane" (trade name) manufactured by Songwon International AG (7) Antioxidant (phosphite type): Tris(2,4-di-t-butylphenyl) phosphite "SONGNOX 1680" (trade name) manufactured by Songwon International AG (8) Lubricant (amide type): Oleic acid amide "Neutron" (trade name) manufactured by Nippon Fine Chemical Co., Ltd. (9) Synthetic barium sulfate 1: "Variace B-34" (trade name) manufactured by Sakai Chemical Industry Co., Ltd., surface treatment grade, particle size: D10 = 0.1 μm, D50 = 0.2 μm, D90 = 0.4 μm (10) Synthetic barium sulfate 2: "Precipitated Barium Sulfate 300" (trade name) manufactured by Sakai Chemical Industry Co., Ltd., particle size: D10 = 0.4 μm, D50 = 0.7 μm, D90 = 1.6 μm (11) Synthetic barium sulfate 3: "Barium sulfate B-1B" (trade name) manufactured by Sakai Chemical Industry Co., Ltd., particle size: D10 = 0.5 μm, D50 = 0.8 μm, D90 = 1.6 μm (12) Synthetic barium sulfate 4: "BMH-100" (trade name) manufactured by Sakai Chemical Industry Co., Ltd., particle size: D10 = 1.5 μm, D50 = 11.6 μm, D90 = 28 μm (13) Natural barium sulfate 1: "Elutriated barium sulfate BA" (trade name) manufactured by Sakai Chemical Industry Co., Ltd., particle size: D10 = 1.8 μm, D50 = 11.2 μm, D90 = 30.3 μm (14) Natural barium sulfate 2: "Barium sulfate W-1" (trade name) manufactured by Takehara Chemical Industry Co., Ltd., particle size: D10 = 0.3 μm, D50 = 1.5 μm, D90 = 4.1 μm (15) Antifungal agent: Thiopentazoline "Synthol M-100" (trade name) manufactured by Sumika Environmental Science Co., Ltd. (16) Antifungal agent: Pyrithione metal salt "Neosintol AF-80" (trade name) manufactured by Sumika Environmental Science Co., Ltd. (17) Antifungal agent: Diiodomethyl-p-tolylsulfone "Pacific Beam MOLD PBM-OK" (trade name) manufactured by MIC Co., Ltd.

[0078] 1. Production and evaluation of resin compositions for anti-slip mats Tables 1 and 2 show comparisons between synthetic barium sulfate and natural barium sulfate, the amount of synthetic barium sulfate used, the type of thermoplastic elastomer, and the amount of olefin resin and softener used for Examples 1 to 14 and Comparative Examples 1 to 6. The raw materials listed in Tables 1 and 2 were kneaded in the extruder to produce resin compositions for anti-slip mats of Examples 1 to 14 and Comparative Examples 1 to 6. Then, Type A durometer hardness, specific gravity, and MFR were measured, and a tensile test, Taber abrasion test, slip test, self-settling test, and chlorine water resistance test were conducted. The results are shown in Tables 1 and 2.

[0079] [Table 1]

[0080] [Table 2]

[0081] Table 3 shows a comparison of Examples 15 to 20, showing whether or not an antifungal agent was used and the amount used. The antifungal agent shown in Table 3 was added to the resin composition for anti-slip mats of Example 1, and the resulting composition was kneaded in the extruder to produce the resin compositions for anti-slip mats of Examples 15 to 20. The amount of the antifungal agent shown in Table 3 is the amount added relative to 100 parts by mass of the thermoplastic elastomer (A1) of Example 1. Then, an antifungal test was carried out under the same conditions as in Example 1, and the results are shown in Table 3.

[0082] [Table 3]

[0083] From Tables 1 to 3, the evaluation results can be summarized as follows: (1) In Examples 1, 3, 4, 5, and 7, which used synthetic barium sulfate with a particle size D50 of less than 10 μm and a styrene-based elastomer or a hydrogenated styrene-based elastomer as the thermoplastic elastomer, the wear loss mass was less than 200 mg, and the wear resistance was particularly good. (2) A comparison between Example 2 (using synthetic barium sulfate with a particle size D50 of 11.6 μm) and Comparative Example 1 (using natural barium sulfate with a particle size D50 of 11.2 μm) showed that the use of a resin composition containing synthetic barium sulfate enabled the production of molded articles with excellent abrasion resistance. (3) Comparing Examples 3 to 5 with Comparative Example 3, even when the type of synthetic barium sulfate with a different particle size was changed and the amount was increased from Example 1 (Examples 3 to 5, increased from 54% by mass to 66% by mass in the mat resin composition), flexibility, high specific gravity, and abrasion resistance (around 110 mg) were good. On the other hand, Comparative Example 3, which used an increased amount of natural barium sulfate compared to Comparative Example 1 (2329 mg), had poor abrasion resistance, similar to Comparative Example 1. (4) A comparison between Example 6 (using synthetic barium sulfate with a particle size D50 of 11.6 μm) and Comparative Example 4 (using natural barium sulfate with a particle size D50 of 1.5 μm) shows that even when a resin composition containing synthetic barium sulfate with a large particle size is used, a molded product with excellent wear resistance can be obtained. (5) In Examples 7 and 8, in which an olefin-based elastomer or a non-hydrogenated styrene-based elastomer was used as the thermoplastic elastomer instead of a hydrogenated styrene-based elastomer, flexibility and a high specific gravity were excellent. However, in Example 8, stickiness occurred in the chlorine water resistance test. (6) Comparing Example 9 with Comparative Examples 5 and 6, Example 9, in which the amount of synthetic barium sulfate used in Example 1 was reduced (reduced from 54% by mass to 30% by mass in the resin composition for matting), also had excellent flexibility and abrasion resistance. Although the specific gravity decreased and the self-settling time increased, this was within the practical range. On the other hand, in Comparative Example 5, the synthetic barium sulfate content was excessively increased (75% by mass), resulting in an excessive increase in Type A durometer hardness (83%) and a significant decrease in abrasion resistance (1497 mg).Furthermore, the melt mass-flow rate decreased, i.e., the fluidity decreased, and moldability deteriorated. Comparative Example 6 is an example in which the content of synthetic barium sulfate was set low (15 mass %), outside the range of the present invention, but the specific gravity was less than 1, and the product did not precipitate in water. (7) Examples 10 to 12 are examples in which the amount of olefin-based resin used was reduced or increased compared to Example 1. In particular, Example 10 (reduced from 40 parts by mass in Example 1 to 15 parts by mass) and Example 11 (increased from 40 parts by mass in Example 1 to 50 parts by mass) showed excellent flexibility, high specific gravity, and abrasion resistance. (8) Examples 13 and 14 are examples in which the amount of softener was increased or decreased (in Example 13, the amount used was reduced from 140 parts by mass in Example 1 to 120 parts by mass, and in Example 14, the amount was increased to 180 parts by mass), but both had excellent flexibility, high specific gravity, and abrasion resistance. (9) Example 8 is an example in which an olefin-based elastomer was used instead of the styrene-based elastomer of Example 4, and was excellent in flexibility, strength, and abrasion resistance. (10) Examples 15 to 20 are examples in which a resin composition containing an antifungal agent was used. Compared to Example 1 in which no antifungal agent was used, the use of 0.1 parts or more of the antifungal agent suppressed the growth of mold.

[0084] 2. Manufacturing and evaluation of anti-slip mats The resin composition for an anti-slip mat of the present invention (Example 4) was injection molded under the following conditions to obtain an anti-slip mat. [Injection molding conditions for anti-slip mats] Using the resin composition for anti-slip mats obtained in Example 4, an injection molding test was carried out under the following conditions using an injection molding machine equipped with a mold shown in Table 4 (Examples 21 to 23, Comparative Example 7). Then, the injection moldability was evaluated. The results are shown in Table 4. Injection molding machine: Shibaura Machine Co., Ltd. "IS1600DF" (model name) Injection molding temperature...230℃ Injection pressure: 40 MPa Injection time...10sec Mold temperature: 40°C

[0085] [Table 4]

[0086] As can be seen from Table 4, when L / t was 158.2 (Comparative Example 7), spaces where the resin composition was not fully filled were observed at each of the four corners of the cavity (referred to as "incomplete filling"). On the other hand, when L / t was 96.3 to 132.7 (Examples 21 to 23), the resin composition was completely filled in the mold (cavity) (referred to as "complete filling").

[0087] Next, the anti-slip mat of Example 23 obtained by injection molding was used to test its usability in a bathtub. [Bathtub anti-slip mat test] A bathtub (model number EXL30032) attached to a unit bath "Sazanna HBV1620UT" (product name) manufactured by TOTO Corporation was filled with hot water at 40°C. The anti-slip mat obtained in Example 23 was submerged in the bathtub, and a test subject bathed and sat on the mat to check the feel and anti-slip effect. A good feel and anti-slip effect were confirmed. [Industrial Applicability]

[0088] The resin composition for anti-slip mats of the present invention is excellent not only in Type A durometer hardness and strength but also in abrasion resistance, and is suitable as a molding material for anti-slip mats that can be used repeatedly. Furthermore, when producing anti-slip mats, not only extruders but also injection molding can be applied, so the resin composition of the present invention is excellent in productivity and recyclability. Furthermore, the anti-slip mat of the present invention sinks in water by itself, so it can be fixed in place by its own weight, and is not excessively heavy, making it easy for even elderly people to handle. Therefore, the anti-slip mat of the present invention is not only suitable for use in bathrooms and bathtubs where elderly people and others are prone to falls, but can also be used on poolsides, pool bottoms, entrances, and bus entrances, and is particularly suitable for use in bathtubs.

Claims

1. A resin composition for an anti-slip mat, comprising synthetic barium sulfate and a thermoplastic elastomer composition as essential components, and containing 20 to 70 mass % of the synthetic barium sulfate, a molded article made of the resin composition for an anti-slip mat has a type A durometer hardness of 20 to 80; The thermoplastic elastomer composition includes a thermoplastic elastomer component (A) (excluding a polyurethane resin), The resin composition for anti-slip mats has a melt mass flow rate of more than 0.1 g / min at a temperature of 230°C and a load of 98 N, measured in accordance with JIS K7210-1.

2. the thermoplastic elastomer composition further comprises an olefin-based resin component (B) and a softener component (C), A resin composition for anti-slip mats as described in claim 1, containing 10 to 90 parts by mass of the olefin resin component (B) and 100 to 300 parts by mass of the softener component (C) relative to 100 parts by mass of the thermoplastic elastomer component (A).

3. 3. The resin composition for an anti-slip mat according to claim 1, wherein the thermoplastic elastomer component (A) is at least one selected from the group consisting of styrene-based elastomers, olefin-based elastomers, and hydrogenated styrene-based elastomers.

4. 3. The resin composition for an anti-slip mat according to claim 2, wherein the olefin-based resin component (B) is a polypropylene resin.

5. 5. The resin composition for an anti-slip mat according to claim 2, wherein the softener component (C) is paraffin oil.

6. The thermoplastic elastomer composition further contains an anti-fungal agent, and the content ratio of the anti-fungal agent is 0.01 to 10 parts by mass per 100 parts by mass of the thermoplastic elastomer component (A). A resin composition for anti-slip mats according to any one of claims 1 to 5.

7. A molded product of the resin composition for anti-slip mats according to any one of claims 1 to 6, comprising 20 to 70% by mass of synthetic barium sulfate and having a type A durometer hardness of 20 to 80.

8. 8. The anti-slip mat according to claim 7, wherein the specific gravity of the molded product is greater than 1.0 and less than 2.

2.

9. A method for producing the resin composition for an anti-slip mat according to any one of claims 1 to 6, A method for producing a resin composition for an anti-slip mat, comprising a step of kneading using a continuous kneader.

10. A method for manufacturing an anti-slip mat according to claim 7 or 8, A method for producing an anti-slip mat, comprising subjecting the resin composition for an anti-slip mat according to any one of claims 1 to 6 to injection molding.

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