JP5590765B2 - Olefin flame retardant flooring - Google Patents

Description

  The present invention relates to flooring materials used in vehicles such as subways, railways, buses, public facilities such as airplanes, ships, schools, hospitals, and other fields where flame retardancy is required. More specifically, halogens such as chlorine are used. The present invention relates to an olefin-based flame retardant flooring that is mainly composed of a resin that does not contain and has excellent design properties.

  Conventionally, vinyl chloride resin is often used for flooring materials for vehicles such as subways, railways, buses, airplanes, ships, and public facilities. This is because the flooring material made of vinyl chloride resin has good handling and functionality and is relatively inexpensive. Furthermore, when a decoration such as a printed pattern is given, the surface layer made of vinyl chloride resin is excellent in transparency, so that the design is improved. On the other hand, since vinyl chloride resin generates a large amount of smoke containing a corrosive gas such as hydrogen chloride gas during combustion, a problem remains in the event of a fire. In addition, waste materials are mostly material recycling except for incineration and landfill treatment, but the recycling rate of building waste is still low. In recent years, technologies such as oiling and gasification have been developed and chemical recycling is being promoted, but there are problems with equipment corrosion and cost due to vinyl chloride. Accordingly, floor materials such as olefin resins have been proposed as an alternative to vinyl chloride floor materials.

  As a flame retardant flooring comprising an olefin resin as a constituent component, an olefin resin containing an inorganic filler or an inorganic flame retardant (Method A) (see Patent Document 1), an olefin resin as a surface layer, There is a laminate in which an intermediate layer added with an inorganic flame retardant is laminated on the lower surface (Method B) (see Patent Documents 2 and 3), and an olefin resin that does not contain an inorganic flame retardant but contains an organic filler and a flame retardant. (Method C) (see Patent Document 4). However, since the surface layer is not transparent in the A method and the C method, it is impossible to give a design by printing or the like, and the design is restricted. In the method B, the thickness of the surface layer is limited to a range in which the flame retardant of the intermediate layer can function during combustion (200 to 1000 μm).

JP 2005-163534 A Japanese Patent Laid-Open No. 07-89014 JP 2004-232334 A JP 11-512470 A

  Conventional flame retardant flooring containing olefinic resin as a constituent, olefinic resin containing inorganic filler or inorganic flame retardant, not containing inorganic flame retardant but containing organic filler and organic flame retardant Since the surface layer of the olefin-based resin is not transparent, it is impossible to give a design to the back surface layer by printing or the like, and the design surface is limited. Further, a laminate in which an olefin-based resin is used as a surface layer and an intermediate layer to which an inorganic flame retardant is added is laminated on the lower surface has a problem that the thickness is limited to a range in which the flame retardant of the intermediate layer can function during combustion. For example, in the case of a floor having a shape with deep irregularities on the surface layer, a surface layer with a thickness greater than the difference in height of the irregularities is required. In such a structure, the thickness of the surface layer is increased to increase transparency. It has been difficult to obtain flame retardancy while maintaining.

The object of the present invention is to solve the above-mentioned problems of the prior art, and without using a vinyl chloride resin or vulcanized rubber, there is almost no limitation on the thickness of the surface layer, and the design properties are maintained while maintaining the design properties. Is to provide flooring.

The present inventors have been studying olefin-based floor materials that can obtain flame retardancy while maintaining transparency using olefin-based resins, and do not need to contain inorganic or organic flame retardants. It was found that flammability can be obtained. That is, a transparent surface mainly composed of a copolymer resin of ethylene and an α-olefin having 8 to 10 carbon atoms and having a density of 9.05 × 10 ⁻⁴ g / mm ³ or more and containing substantially no flame retardant An olefin-based flame retardant flooring having at least a layer and a base material, wherein the surface layer has a thickness of 0.3 mm or more and the total thickness of the flooring is 0.8 mm or more; That is, the surface layer is an olefin flame retardant floor material containing 0.1 to 1.0 part by weight of a nucleating agent with respect to 100 parts by weight of the olefin resin.

The present invention uses an olefin-based resin having a surface layer density of 9.05 × 10 ⁻⁴ g / mm ³ or more, and does not require the addition of a flame retardant, thereby obtaining flame retardancy while maintaining transparency. Olefinic flooring can be provided. Furthermore, since it is not necessary to add a flame retardant to the surface layer, the surface is excellent in scratch resistance and wear resistance, and it is possible to reduce the cost.

The olefin flame retardant flooring of the present invention is obtained by laminating a surface layer, an intermediate layer, a back layer, a base material, etc., but only the surface layer and the base material are essential layers, and only from the surface layer and the base material. The structure which becomes may be sufficient.
The olefin-based flame retardant flooring of the present invention does not require the addition of a flame retardant to the surface layer, intermediate layer, back layer, and the like. It was found that the flame retardancy is improved by the test method of “and standard”, but the present invention does not exclude the addition of the flame retardant, and the flame retardant is added to improve the flame retardancy more. It is also possible to do.
The form of the flooring according to the present invention is not particularly limited, such as a long flooring, a tile, or a mat.

  When the flooring is a flooring composed of three or more layers having a surface layer, a back layer, and a base material, the overall thickness should be 0.8 mm or more and the thickness of the surface layer must be 0.3 mm or more. The total thickness is preferably 1.0 mm or more and the thickness of the surface layer is preferably 0.4 or more, and the total thickness is 1.7 mm or more and the thickness of the surface layer is preferably 0.9 or more. preferable. In the case of forming irregularities on the surface of the surface layer, the height of the aperture is usually about 0.1 to 1.5 mm, and the thickness of the surface layer is a thickness obtained by adding 0.1 mm or more to the height of the aperture. preferable.

  The surface layer of the present invention is composed of an olefin resin mainly composed of a copolymer resin of ethylene and an α-olefin having 6 to 10 carbon atoms, and considering flame retardancy, ethylene and an α-carbon having 8 to 10 carbon atoms. A copolymer resin with olefin is preferred. In addition, other resins can be blended in the surface layer, and as the resin to be blended, polyethylene, polypropylene, polybutene-1, a copolymer resin of ethylene and an α-olefin having 3 or more carbon atoms, propylene and carbon Copolymer resin with α-olefin of 3 or more, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid copolymer Polymerized resins, olefinic thermoplastic elastomers, amorphous α-olefin resins and the like can be mentioned. These resins to be blended may be used alone or in combination of two or more.

Surface layer of the present invention, requires that there density 9.05 × 10 ^-4 g / mm ³ or more, the density is lower than 9.05 × 10 ^-4 g / mm ^3, the flame retardancy becomes poor . The melt flow rate (MFR) of the surface layer of the present invention is preferably 2 g / 10 minutes or less, more preferably 1 g / 10 minutes or less, considering flame retardancy.

  In the present invention, it is preferable to add a nucleating agent to the olefin resin of the surface layer in order to improve transparency. Examples of the nucleating agent include sorbitol nucleating agents, organophosphate nucleating agents, metal salt nucleating agents for carboxylic acids, rosin nucleating agents, polymer nucleating agents, and inorganic compounds. By using these nucleating agents, there is an effect of improving transparency by reducing the crystal size. Of the nucleating agents, sorbitol-based nucleating agents are preferable from the viewpoint of improving the transparency.

  Examples of sorbitol nucleating agents include dibenzylidene sorbitol, 1,3-di (methylbenzylidene) sorbitol, 2,4-di (methylbenzylidene) sorbitol, 1,3-di (ethylbenzylidene) sorbitol, 2,4 -Di (ethylbenzylidene) sorbitol, 1,3-di (butylbenzylidene) sorbitol, 2,4-di (butylbenzylidene) sorbitol, 1,3-di (methoxybenzylidene) sorbitol, 2,4-di (methoxybenzylidene) Examples include sorbitol, 1,3-di (ethoxybenzylidene) sorbitol, 2,4-di (ethoxybenzylidene) sorbitol, 1.3-chlorobenzylidene, 2.4-methylbenzylidene sorbitol, mono (methyl) dibenzylidene sorbitol, and the like. .

  Examples of the organic phosphate nucleating agent include sodium bis (4-t-butylphenyl) phosphate, lithium bis (4-t-butylphenyl) phosphate, and bis (4-t-butylphenyl). Aluminum phosphate, 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate sodium salt, 2,2′-methylene-bis (4,6-di-t-butylphenyl) Lithium phosphate, 2,2′-methylene-bis (4,6-di-t-butylphenyl) aluminum phosphate, 2,2′-methylidene-bis (4,6-di-t-butylphenyl) Calcium phosphate, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate sodium salt, 2,2′-ethylidene-bis (4,6-di-t-butylphenyl) phosphate Lithium salt, 2,2'-ethyl Examples thereof include den-bis (4,6-di-t-butylphenyl) phosphoric acid aluminum salt, bis- (4-t-butylphenyl) phosphoric acid calcium salt, and the like.

  Examples of the carboxylic acid metal salt nucleating agent include aluminum benzoate, potassium benzoate, sodium benzoate, lithium benzoate, aluminum di-para-t-butylbenzoate, titanium di-para-t-butylbenzoate. , Chromium di-para-t-butylbenzoate, aluminum hydroxy-di-t-butylbenzoate, Al-p-butylbenzoate, sodium β-naphthoate, sodium cyclohexanecarboxylate, sodium cyclopentanecarboxylate, aluminum adipate , Sodium sebacate, potassium sebacate, aluminum sebacate and the like.

  Examples of rosin nucleating agents include rosin acid metal salts, and examples of rosin acid metal salts include rosin acid sodium salt, rosin acid potassium salt, and rosin acid magnesium salt.

  Examples of the polymer nucleating agent include high-density polyethylene, 3,3-dimethylbutene-1, 3-methylbutene-1, 3-methylpentene-1, 3-methylhexene-1, and 3,5,5-trimethyl. Examples thereof include 3-position branched olefins having 5 or more carbon atoms such as hexene-1, vinylcycloalkane polymers such as vinylcyclopentane, vinylcyclohexane and vinylnorbornene.

  Examples of inorganic compound nucleating materials include silica, mica, titanium dioxide, talc, alum and the like.

  These nucleating agents may be used alone, or two or more of them may be used in combination regardless of the same or different nucleating agents. The addition amount of the nucleating agent is 0.1 to 1.0 part by weight, preferably 0.2 to 0.5 part by weight based on 100 parts by weight of the olefin resin. Even if 1.0 part by weight or more is added, the effect of improving transparency cannot be expected. Moreover, transparency is further improved by using a sorbitol nucleating agent and an inorganic compound in combination. The nucleating agent is preferably added after preparing a master batch, but it is desirable to sufficiently disperse the mixture by kneading it sufficiently during the kneading of the resin composition.

  Transparency was measured with NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd. and evaluated by haze value. When there is a design such as printing on the back side of the surface layer, if the haze value exceeds 60%, printing on the back side becomes blurred and becomes a practical problem, and it is necessary to make it 60% or less. 50% or less is preferable and 40% or less is more preferable. If it is 40% or less, the printing on the back layer can be seen clearly.

  In addition, the olefin-based resin of the surface layer includes coloring agents, lubricants, various antioxidants such as phenol-based, phosphorous acid-based, thioether-based antioxidants, hydrotalcite, etc., as long as transparency is not impaired. Neutralizing agents, ultraviolet absorbers such as benzophenone-based, benzotriazole-based, salicylate-based, hindered amine-based light stabilizers, antibacterial agents, bactericides, dispersants, antistatic agents, and the like can be added.

  The back layer used in the present invention is composed of an olefin resin composition. Examples of the olefin resin include polyethylene, polypropylene, polybutene 1, copolymer resin of ethylene and α-olefin having 3 or more carbon atoms, propylene and carbon number. Copolymer resin with 3 or more α-olefin, ethylene-propylene rubber, ethylene-propylene-diene rubber, ethylene-butene rubber, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid ester copolymer resin, ethylene-methacrylic acid copolymer Examples thereof include resins, olefinic thermoplastic elastomers, and amorphous α-olefin resins. You may use these individually by 1 type or in combination of 2 or more types.

  Since the back layer does not need to be transparent, various conventionally known fillers can be further added. For example, calcium carbonate, mica, talc, silica, barium sulfate, calcium sulfate, kaolin, clay, zeolite, ferrite, calcium silicate, magnesium carbonate, titanium oxide, iron oxide, gypsum, glass beads, glass powder, glass balloon, glass Examples thereof include fiber, quartz, quartz glass, glass fiber, and potassium titanate fiber. You may use these individually by 1 type or in combination of 2 or more types.

  In addition, as necessary, the back layer may include a colorant, a lubricant, various antioxidants such as phenols, phosphorous esters, thioethers, neutralizers such as hydrotalcite, benzophenones, benzotriazoles, salicylates. Ultraviolet absorbers such as those, hindered amine light stabilizers, antibacterial agents, rust inhibitors, dispersants, antistatic agents, and the like can be added.

  The olefin-based flame retardant flooring of the present invention needs to be provided with a base material in at least one place between the layers and / or the outermost surface, thereby improving dimensional stability in addition to flame retardancy. . Examples of the base material to be used include woven or non-woven fabrics such as synthetic fibers, natural fibers, glass fibers, and carbon fibers, paper, metal foil, and the like.

  Furthermore, the olefin-based flame retardant flooring of the present invention can be made into a flooring material having excellent design properties by providing a printed pattern or a marble pattern on the surface or the surface of the surface layer or the surface of the layer in contact with the surface layer. . When the printed surface is the back surface of the surface layer or the surface of the layer in contact with the surface layer, the surface layer needs to be a transparent or translucent layer in which a pattern can be recognized. Although there is no restriction | limiting in particular in printing ink, For example, varnishes, such as polyester isocyanate, polyether isocyanate, an acrylic resin, a urethane resin, and a cellulose derivative, can be individual or mixed and it can be colored by adding various colorants. In addition, when another layer is stacked on the surface to be printed, the adhesion between the layers can be improved by performing corona discharge treatment, electron beam treatment, plasma treatment, or the like. It is also possible to provide a primer layer after performing corona discharge treatment, electron beam treatment, plasma treatment or the like. Known primers can be used, for example, urethane-based, epoxy-based, acrylic-based, and halogen-resin-based primers are generally used.

  The olefin-based flame retardant flooring of the present invention can be molded with known equipment such as a roll, a calender device, an extruder, and a laminating device. Furthermore, it is possible to give a marble-like pattern or to give unevenness to the surface by embossing.

  The adhesive for applying the olefin flame retardant flooring of the present invention to the base may be either a solvent type or an emulsion type, and is usually an epoxy adhesive, urethane adhesive, acrylic adhesive, vinyl acetate. -Based adhesives, SBR-based adhesives, chloroprene-based adhesives, and the like can be used. Among them, epoxy adhesives and urethane-based adhesives are preferable in view of adhesive strength.

Examples The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. The materials used in the examples and comparative examples are shown in Table 1, the surface layer formulations in Tables 2 and 3, the back layer formulations in Table 4, and the evaluation results of each Example and Comparative Example in Tables 5, 6 and 7. Show.
Samples obtained in Examples and Comparative Examples described later were evaluated by the following evaluation methods and evaluation criteria. In addition, Example 11 shall be read as Reference Example 11.
[Evaluation method and evaluation criteria]
<Transparency>
Only the surface layer of each Example and Comparative Example was sheeted to 1.0 mm, and the haze was measured with a color computer and evaluated according to the following criteria.
A: Haze value of 40% or less (printing on the back side looks clear)
○: Haze value is over 40% and 50% or less (printing on the back side is not clear)
Δ: Haze value is over 50% and 60% or less (printing on the back side is slightly blurred, but there is no practical problem)
×: Haze value exceeds 60% (printing on the back side is blurred, causing practical problems)
<Flame retardance>
The combustion test is conducted in accordance with the Ministry of Land, Infrastructure, Transport and Tourism “Flameability test and standards for railway vehicle materials”. The floor test materials obtained in each of the examples and comparative examples are subjected to a 5 point combustion test. It was evaluated with.
○: All 5 points are flame retardant.
Δ: 1 to 4 points flame retardant.
X: 5 points are not flame retardant.

<Examples 1-3, Comparative Example 1>
Examples 1 to 3 and Comparative Example 1 are flooring materials without a back layer, and the resin composition of the surface layer corresponding formulation Nos. In Tables 5 and 7 was kneaded with a roll at 190 ° C. to obtain polyester (75%) / rayon. (25%) An olefin flooring was obtained by laminating on a knitted base material composed of blended yarn.

<Examples 4 to 19 and Comparative Examples 2 to 6>
First, the resin composition of the back layer composition (formulation No. 18) in Table 4 was kneaded with a roll of 165 ° C., and then laminated on a base material of a knitted fabric made of polyester (75%) / rayon (25%) blended yarn. . Subsequently, the resin composition of the corresponding formulation Nos. In Tables 5, 6, and 7 was kneaded with a roll at 190 ° C., and the olefin-based flooring was laminated on the base material on which the back layer was laminated, as a surface layer. Obtained.

As is apparent from the table, it is understood that those within the scope of claim 1 have flame retardancy and transparency. Moreover, about the copolymer resin of ethylene and C6-C10 alpha-olefin, compared with Example 7, 11, the copolymer resin of ethylene and C6-alpha-olefin compared with ethylene and carbon number. It can be seen that the copolymer resin with an α-olefin of 8 has better flame retardancy, and the density of the copolymer resin of ethylene and an α-olefin having 8 carbon atoms is From 9.05 × 10 ⁻⁴ g / mm ³ , 9.08 × 10 ⁻⁴ g / mm ³ is better, and when the copolymer resin is an α-olefin having the same carbon number, it is understood that a higher density is better.

  From the comparison of Examples 6 and 9, it can be seen that the transparency is improved by the addition of the nucleating agent, and further, the comparison of Examples 6 and 11 to 19 shows that the effect of the sorbitol nucleating agent is large. Further, it can be seen from Comparative Examples 4 and 5 that the transparency is not improved even when a small amount of LDPE or HDPE is added to a copolymer resin of ethylene and an α-olefin having 8 carbon atoms.

  The flame retardant flooring of the present invention is mainly composed of a resin containing no halogen such as chlorine, and is excellent in flame retardancy and design without containing a flame retardant. It can be widely used in fields where flame retardancy is required such as ships, schools, hospitals and other public facilities.

Claims (2)

An olefin-based material having at least a transparent surface layer and a base material, the main component of which is a copolymer resin of ethylene and an α-olefin having 8 to 10 carbon atoms, and the density is 9.05 × 10 ⁻⁴ g / mm ³ or more. A flame retardant flooring, wherein the surface layer contains substantially no flame retardant, the thickness of the surface layer is 0.3 mm or more, and the thickness of the entire flooring is 0.8 mm or more. Olefin-based flame retardant flooring. The said surface layer contains 0.1-1.0 weight part of nucleating agents with respect to 100 weight part of olefin resin, The olefin type flame-retardant flooring of Claim 1 characterized by the above-mentioned.