JP2006037033A - Non halogen based surface material for floor material excellent in maintenance performance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non halogen based surface material for floor materials excellent in maintenance performance, antistatic property and having good designability, hard to generate toxic gas in burning, used for floor materials in public facilities like school, hospital, and buildings, apartment houses, houses, commercial facilities, and the like, and floor materials for traffic facilities like a rail road, a bus, and whose for air planes, and the like. <P>SOLUTION: This non halogen based surface material for floor materials is hard to generate toxic gas in burning and exhibits excellent performance in wear resistance, stain resistance, processing ability, antistatic property, designability and maintenance performance by adding an antistatic composition to a polyolefin resin, wherein the antistatic composition is obtained by treating an alkali metal anion and a copolymer composition composed of a thermoplastic polyurethane resin having polarity and a hydrogenated styrene-isobutylene elastomer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  This invention is used for flooring materials for buildings such as public facilities such as schools and hospitals, buildings, condominiums, houses, commercial facilities, etc., or for vehicles such as railways and buses, flooring materials for aircraft, etc. Non-halogen flooring material that does not generate toxic gases during combustion, has excellent wear resistance, contamination resistance, processability, and antistatic properties, and can be maintained with commercially available polymer wax for polymer floors It is about.

  Conventionally, building floor materials or vehicle floor materials are excellent in flame retardancy, wear resistance, heat resistance, etc., so from vinyl chloride resin (PVC) or vulcanized rubber with a large amount of plasticizer added. Many flooring materials were used. These are floor materials that exhibit a certain level of performance and are easy to process and economically excellent.

  However, PVC floor materials generate toxic gases such as hydrogen chloride along with a large amount of smoke when combusted, and in the event of a fire, evacuees inhale these toxic gases and the like, and human lives are at risk. The problem of disaster prevention and the incineration disposal process not only accelerates damage to the incineration facility due to its strong oxidizing action, but also causes inadequate incineration process to generate harmful dioxins and cause environmental pollution. was there.

  Furthermore, PVC flooring is produced by containing a large amount of volatile organic compounds (VOC) such as plasticizers at the time of production, and thus has a peculiar odor and is said to be a causative substance of sick house syndrome. Further, there have been a problem that the plasticizer is reduced in volatilization due to long-term use and the flexibility as a flooring material is lowered, and the plasticizer bleeds on the surface and tends to cause fogging, resulting in poor appearance. In addition, the vulcanized rubber flooring has a problem that the surface is easily contaminated and the design property is limited due to poor transparency, and the workability is poor due to being hard. Furthermore, the halogen-based flame retardant added for imparting flame retardancy has a problem in that toxic gas is generated during combustion, similar to PVC flooring.

Therefore, in recent years, instead of PVC materials and vulcanized rubber materials, the following materials that generate less toxic gas during combustion are used as constituents of flooring materials in JP-A-11-48416 and JP-A-2000-110339. Proposed. For example, ethylene-vinyl acetate copolymer, polypropylene resin, polyethylene resin, ethylene-vinyl alcohol copolymer resin, polyester resin, and the like can be mentioned. By using these polyolefin resins as constituent materials for flooring, toxic gas during combustion The problem of the occurrence of odor, the peculiar odor derived from the plasticizer, the generation of VOC, and the occurrence of fogging have been almost solved.
JP-A-11-48416 JP2000-110339

  However, in ordinary flooring materials, maintenance is generally performed with resin wax for the purpose of maintaining the aesthetics of the surface. Polyolefin resins represented by polypropylene resin and polyethylene resin are resins having no polar group. Therefore, the wetness index is as low as 30 to 32, and even if resin wax is applied, it is easily peeled off and has been difficult to maintain. (In the present invention, the wetting index refers to the wetting tension according to JIS 6768 plastic film and sheet “wetting tension test method”, and the wetting index as a flooring is preferably 36 to 45 mN / m.) These polyolefin resin systems Floor materials are charged by human walking, etc., causing not only unpleasant static electricity to the human body, but also inducing fire and equipment malfunctions. As a countermeasure, surfactants and carbon black are kneaded. However, a satisfactory antistatic effect cannot be obtained, and the design can be limited, so that a satisfactory one is not obtained. The present invention has been made in view of such a technical background, and provides a surface layer material of a non-halogen-based flooring material that is less likely to generate toxic gas during combustion, has excellent maintainability and antistatic properties, and has good design properties. The purpose is to do.

  As a result of intensive studies to solve such problems, the present inventors have determined that a polyolefin resin, a polar thermoplastic polyurethane elastomer, a hydrogenated styrene-isoprene elastomer copolymer composition, and an alkaline earth metal are used. By adding an antistatic composition obtained by treating the salt anion, it is less likely to generate toxic gases during combustion as a flooring material, and wear resistance, stain resistance, workability, antistatic properties, and design properties As a result, the inventors have found that it is possible to exhibit performance excellent in maintainability and have reached the present invention.

  That is, the first invention of the present invention is a flooring comprising a thermoplastic resin polymer, comprising a composition of a polyolefin resin and a polar-nonpolar block resin copolymer, wherein the polyolefin resin is 20 to 80% by weight. A non-halogen flooring material comprising the polar-nonpolar block resin copolymer of 80 to 20% by weight and a wetting index of 36 to 45 mN / m.

  According to a second aspect of the present invention, the nonpolar block resin copolymer is an addition polymerization block comprising an aromatic vinyl compound polymer block and a conjugated diene polymer block or a hydrogenated product thereof (hereinafter referred to as block a). And the polar block copolymer is a polyurethane block (hereinafter referred to as block b) composed of a polymer polyol, a chain extender, and an organic diisocyanate compound. It is a surface layer material. By adopting block a as the polar block and block b as the nonpolar block, the wetting index of the thermoplastic resin polymer is 36 to 45 mN / m, and maintenance by wax becomes possible, and the workability, wear resistance, and contamination resistance are improved. The properties and the like are remarkably improved.

  3rd invention contains 1-100 weight part of block a with respect to 100 weight part of compositions of the said polyolefin resin and polar-nonpolar block resin copolymer, and a wetting index is 36-45 mN / m. It is a surface layer material of a non-halogen-based flooring characterized by the above.

  The fourth invention relates to an ethylene copolymer, a rosin resin, a terpene resin, a petroleum resin and a chemical containing a polar group with respect to 100 parts by weight of the composition of the polyolefin resin and the polar-nonpolar block resin copolymer. A non-halogenous flooring material comprising at least one selected from petroleum resins having a polar group by modification in a proportion of 1 to 50 parts by weight and a wetting index of 36 to 45 mN / m. It is a surface material.

The fifth invention relates to a compound containing an ether bond and / or an ester bond, a compound containing an ether bond and / or an ester bond, based on 100 parts by weight of the composition of the polyolefin resin and the polar-nonpolar block resin copolymer. Containing 3 to 30 parts by weight of an antistatic composition containing at least one selected from any of the coalesced components and a component obtained by adsorbing an anion of an alkali metal or alkaline earth metal salt; It is a surface layer material of a non-halogen floor material characterized by having an electric resistivity of 10 ⁶ to 10 ¹¹ Ω and a wetting index of 36 to 45 mN / m.

  Since the surface layer material of the non-halogen floor material of the present invention uses only a resin having no chlorine atom in the chemical structure as the constituent material of the resin layer, the generation of toxic gas during combustion is small, and the combustion safety It is excellent in disaster prevention and can contribute to environmental conservation. Contains no fillers or plasticizers, so it has excellent wear resistance and stain resistance on the flooring surface, no odor, and no long-term fogging on the surface. Yes. In addition, since the floor material of the present invention contains a polar block resin, the wetting index is 36 to 45 mN / m, and maintenance with resin wax can be performed.

  The non-halogen floor material according to the present invention is composed of a resin composition containing only a resin having no chlorine atom in its chemical structure. Here, the “resin composition” includes those composed only of a single resin, and is a resin that does not have a chlorine atom in its chemical structure.

  Examples of the polyolefin resin as a resin having no chlorine atom in the chemical structure include an ethylene-vinyl acetate copolymer, a polypropylene resin, and a polyethylene resin. Among them, it is preferable to use a polypropylene resin or a polyethylene resin as a main component of the resin component because the wear resistance and stain resistance of the floor material surface can be remarkably improved.

  The nonpolar portion of the polar-nonpolar block resin copolymer is referred to as block a, and specifically includes olefin elastomers, styrene elastomers, and the like. Of these, polypropylene resin and polyethylene resin are preferably used because of their good processability.

  The polar portion of the polar-nonpolar block resin copolymer is referred to as a block b, and specifically includes polyurethane elastomer, polyester elastomer, ethylene vinyl acetate elastomer, and the like. Among them, it is preferable to use a polyurethane elastomer or a polyester elastomer because processability and chemical resistance can be remarkably improved.

  Examples of the ethylene-based copolymer containing a polar group include ethylene methyl methacrylate, ethylene vinyl acetate, ethylene acrylic acid, ethylene methacrylate, ethylene acrylate, and ethylene methyl acrylate. Among them, it is preferable to use ethylene methyl methacrylate and ethylene vinyl acetate because processability can be improved.

  As the rosin resin containing a polar group, a rosin ester resin, a hydrogenated rosin ester resin, or the like can be used, and these may be used alone or in combination of two or more.

  Moreover, as a terpene resin containing a polar group, a terpene resin, a hydrogenated terpene phenol resin, or the like can be used.

  Examples of petroleum resins containing polar groups include C5 petroleum resins, C9 petroleum resins, and hydrogenated products thereof.

  In the present invention, an antistatic composition comprising the following composition is mixed in order to impart antistatic properties. As a compound containing an ether bond and / or an ester bond, a compound containing a-{O (AO) n}-group (A is an alkylene group having 2 to 4 carbon atoms, and n is an integer of 1 to 7); As a polymer containing an ether bond and / or an ester bond, at least one resin selected from polyester resins, polyamide resins, polyurethane resins, polyalkylene oxides, polyether ester amides, and the like, and alkali metal or alkaline earth metal salts An antistatic composition containing a component obtained by adsorption treatment of the anion is mixed.

In order to set the volume electrical resistivity to 10 ⁶ to 10 ¹¹ Ω, 3 to 30 weights of the antistatic composition is added to 100 parts by weight of the composition of the polyolefin resin and the polar-nonpolar block resin copolymer. It is necessary to contain in the ratio of parts. If the amount is less than 3 parts by weight, the antistatic property becomes difficult. If the amount exceeds 30 parts by weight, the workability, heat resistance, strength, and residual dent properties are lowered, and therefore, the material becomes unsuitable as a flooring material.

  In the present invention, various additives such as an antioxidant, an ultraviolet absorber, a lubricant, a heat stabilizer, a light stabilizer, a colorant, and a pattern material (for the purpose of improving design properties) may be appropriately contained.

  Moreover, you may form a membrane | film | coat by coating a processing agent on the surface of the surface layer material of this invention as needed. For example, from the viewpoint of improving the wear resistance, a film may be formed on the upper surface of the flooring material of the present invention using a film mainly composed of urethane resin or acrylic resin as a surface resin layer. Such a film is generally formed to a thickness of 50 μm or less.

  Moreover, you may laminate | stack and integrate the backer layer which makes resin the composition which does not have a chlorine atom in a chemical structure, and also a nonwoven fabric on the back surface of the surface layer material of this invention by heat-melting. By using a non-woven fabric, the adhesion with the adhesive during construction is improved by the anchor effect from the impregnation of the non-woven fabric with the adhesive.

  Examples of the nonwoven fabric composed of a resin having no chlorine atom in the chemical structure include a polypropylene resin nonwoven fabric, a polyester resin nonwoven fabric, and a nylon resin nonwoven fabric. Among them, a spunbond type nonwoven fabric that can be thinned is preferable, and polypropylene spunbond is particularly preferable.

  Although the thickness of the non-halogenous flooring material using the present invention as a surface layer material is not particularly limited, it is generally 2 to 6 mm. Moreover, it may be configured as a sheet-like flooring (for example, a long sheet having a width of about 600 to 2,500 mm) or a tile-like flooring. There is no particular limitation.

  In addition, it does not specifically limit as a manufacturing apparatus of the non-halogen-based flooring which concerns on this invention, For example, it can manufacture with well-known apparatuses, such as a calender processing machine and an extrusion processing machine.

Next, specific examples of the present invention will be described.
<Example 1>
As shown in Table 1, 40% by weight of high-density polyethylene (HDPE) is used as the polyolefin resin, and 40 polymer composition (TPUE-SIS) of thermoplastic polyurethane and styrene-based elastomer is used as the polar-nonpolar block copolymer. A composition consisting of% by weight was kneaded with a Banbury mixer, and a sheet having a thickness of 2.0 mm was prepared using a tester of a calender molding machine having a set temperature of 160 ° C. and a diameter of 25 cm. Next, on the lower side of the surface layer material, 20% by weight of Tuftec H1062 (manufactured by Asahi Kasei Co., Ltd.), 20% by weight of EVATATE (manufactured by Sumitomo Chemical Co., Ltd.) as EVA resin, and 50% by weight of calcium carbonate having a particle size of 25 μm. %, A backer layer containing 10% by weight of carbon black, and a polypropylene spunbonded nonwoven fabric (weight per unit area: 35 g / m ² ) were laminated to obtain a non-halogen floor material.

<Examples 2 to 6>
Each flooring was obtained in the same manner as in Example 1 except that the composition conditions of each resin were set as shown in Table 1. In Example 2, Tuftec H1062 (manufactured by Asahi Kasei Co., Ltd.) is used as the block a, P125 (manufactured by Yashara Chemical Co., Ltd.) is used as the terpene resin in Example 3, and Evaate (as EVA resin is used in Example 4). In Examples 5 and 6, Saikonol SMB85 (manufactured by Sanko Chemical Co., Ltd.) was used as an antistatic composition.

<Comparative Examples 1-2>
As shown in Table 1, in Comparative Example 1, the blending amount of ethylene vinyl acetate (EVA) resin as a polyolefin resin was 100% by weight, and in Comparative Example 2, thermoplastic polyurethane and styrene were used as polar-nonpolar block copolymers. Although the polymer composition (TPUE-SIS) of the base elastomer was 10% by weight, a good sheet could not be obtained in both cases. That is, if the blending amount of the polar-nonpolar block copolymer resin was too small, it could not be processed as a sheet.

<Abrasion resistance test>
In accordance with the building material and building component partial friction test method according to JIS A 1453, wear wheels with a predetermined abrasive paper wrapped around the surface of each flooring material are rotated 1,000 times with a Taber abrasion tester to reduce wear. Was measured, and less than 300 mg was “◯”, and 300 mg or more was “x”.

<Contamination resistance test>
In accordance with the contamination test method of the polymeric upholstery flooring test method according to JIS A 1454, 2 ml of the contaminating material is dropped on the surface of each flooring, left to stand for 24 hours, and washed with water containing a neutral detergent. Further, after washing with alcohol, wiped off with gauze, allowed to stand for 1 hour, and visually observed changes in color, gloss and swelling of the dripping part. Those that did not change by observation were marked with “◯”, and those that changed at least one were marked with “x”.

<Maintenance test>
When the wetting index measured in accordance with JIS K 6768 is 36 to 45 (mN / m), “◯”, and less than 36 (mN / m) and more than 45 (mN / m) are “x”. .

<Processability>
When each composition is made into a sheet using a two-roll calender molding tester with a diameter of 25 cm set at 160 ° C., it is stably tested at a speed of 20 m / min or more without blurring, plate-out, and surface roughness. The items that can be used are “○”, and the others are “×”.

<Chargeability test>
The volume resistance value was measured according to JIS A 1454, and 10 ⁶ to 10 ¹¹ Ω was defined as “◯”.

  As is apparent from Table 1 above, in Examples 1 to 6 of the present invention, excellent wear resistance, stain resistance, maintainability and workability were obtained, and in Examples 5 and 6, antistatic properties were further obtained. Also good results were obtained.

  On the other hand, the flooring materials of Comparative Examples 1 and 2 that deviate from the polar-nonpolar block copolymer below the specified range are both inferior in processability, and ethylene vinyl acetate ( The flooring material of Comparative Example 1 in which the blending amount of the EVA) resin was 100% by weight was inferior in wear resistance and stain resistance. Further, the flooring material of Comparative Example 2 having a small blending amount of the polar-nonpolar block copolymer was inferior in maintainability although it had good wear resistance and stain resistance.

  Further, the flooring material of Example 1 was subjected to an NBS combustion test and a flameproof test (fire fighting method). These results are shown in Table 3.

  The NBS combustion test method is a method in which a sample is placed vertically in a closed smoke box, and burner flame is applied to the smoke generated in the smoke box while radiant heat is applied from the heater in front of the sample. On the other hand, the light transmittance is measured by a phototube, and the smoke density (Ds) is calculated from the light transmittance (T) based on the following calculation formula.

Ds = 132 log (100 / T)
A Ds value and a maximum Ds value of 4 minutes after the start of the test were determined. Furthermore, the gas in the smoke box was collected in a collection bag and analyzed with a detector tube.

  As is clear from Tables 2 and 3, it was confirmed that the flooring of the present invention has low smoke generation during combustion and hardly generates toxic gas.

Claims (5)

  A flooring comprising a thermoplastic resin polymer, comprising a composition of a polyolefin resin and a polar-nonpolar block resin copolymer, wherein the polyolefin resin is 20 to 80% by weight, the polar-nonpolar block resin copolymer A surface layer material of a non-halogen floor material, wherein the coalescence is 80 to 20% by weight and the wetting index is 36 to 45 mN / m.   The nonpolar block resin copolymer is an addition polymerization block composed of an aromatic vinyl compound polymer block and a conjugated diene polymer block or a hydrogenated product thereof (hereinafter referred to as block a), and the polar The surface layer material of a non-halogen-based flooring according to claim 1, wherein the block copolymer is a polyurethane block (hereinafter referred to as a block b) composed of a polymer polyol, a chain extender, and an organic diisocyanate compound.   Non-halogen, characterized by containing 1 to 100 parts by weight of block a and a wetting index of 36 to 45 mN / m with respect to 100 parts by weight of the composition of the polyolefin resin and polar-nonpolar block resin copolymer. Surface material for flooring.   100 parts by weight of the composition of the polyolefin resin and the polar-nonpolar block resin copolymer are given an ethylene copolymer containing a polar group, a rosin resin, a terpene resin, a petroleum resin, and a polar group by chemical modification. A surface layer material for a non-halogen floor material, comprising 1 to 50 parts by weight of at least one selected from any of petroleum oils having a wetness index of 36 to 45 mN / m. The compound is selected from a compound containing an ether bond and / or an ester bond and a polymer containing an ether bond and / or an ester bond with respect to 100 parts by weight of the composition of the polyolefin resin and the polar-nonpolar block resin copolymer. 3 to 30 parts by weight of an antistatic composition containing at least one of the above and a component obtained by adsorbing an anion of an alkali metal or alkaline earth metal salt, and having a volume electrical resistivity of 10 ^6. A surface layer material of a non-halogen-based flooring characterized in that it has a wetting index of 36 to 45 mN / m at -10 ¹¹ Ω.