JP2005238850A - Flame-retarding light-resisting polyolefin resin sheet and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin sheet, which has high flame and light resistances and is excellent in high-frequency fusion processability. <P>SOLUTION: The polyolefin resin coating layer formed on both sides of a base cloth comprises; (1) 100 wt. parts of a polyolefin resin blend, (2) 5-100 wt.parts of a flame retardant containing a halogen substituted organic compound and optionally an inorganic compound, and (3) 0.005-3.5 wt.parts of a light-resisting stabilizer, wherein the base cloth has a yarn cloth pre-treated by a composition containing a silicon compound. The resin blend (1) comprises (a) a main component comprising a linear low density polyethylene resin obtained by co-polymerizing ethylene and α-olefin in the presence of a metallocene catalyst and (b) a blend component comprising one or more of ethylene-vinyl acetate and/or (meth)acrylic acid (ester) copolymer resins. The total content of vinyl acetate and/or (meth)acrylic acid (ester) in the blend component is 5-30 wt.% relative to the polyolefin resin blend. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a flame-retardant light-resistant polyolefin resin sheet and a method for producing the same, and more particularly, to a fiber fabric-containing flame-retardant light-resistant polyolefin resin sheet and a method for producing the same that are suitably used for buildings and structures. . More specifically, the present invention is excellent in light resistance, flame retardancy, joint strength, and capable of high-frequency fusion, including a tent film material, a sheet warehouse film material, a building sheet curing sheet, The present invention relates to a flame-retardant light-resistant polyolefin resin sheet suitable for uses such as a sound insulation sheet for a construction site and a method for producing the same.

  Industrial material sheets used as members of buildings and structures, such as membrane materials for tents, film materials for sheet warehouses, curing sheets for building sites, and sound insulation sheets for building sites, are part of buildings and structures. Therefore, it is necessary to have the flameproof performance specified in the Fire Service Law. As industrial material sheets having flameproof performance that are currently used in these applications, sheet products in which a surface of a textile fabric is coated with a polyvinyl chloride resin occupy the mainstream. Recently, however, it has been argued that there is a suspicion of hormonal disruptors for phthalate esters contained as plasticizers in polyvinyl chloride resin products in applications other than buildings such as foodstuffs, household goods, and toys. In addition, polyvinyl chloride resin products containing phthalates are strongly interested in the possibility of generating dioxin derivatives during combustion. In particular, with regard to the dioxin problem, disposal processing such as open burning is prohibited for not only polyvinyl chloride resin products but also synthetic resin processed products in general, and flammability of these synthetic resin processed products is generally toxic from the viewpoint of evacuation safety. Suppressing the generation of combustible gases is a social requirement. Due to this social background, various measures to reduce the use of polyvinyl chloride resin products as much as possible have been developed in disposable applications. For example, products using polyolefin resins such as polyethylene resins and polypropylene resins are widely used instead. Have begun to do.

  As such social demands intensify, synthetic fiber woven fabric is the core material, especially as a membrane material suitable for buildings and structures such as tents, sheet warehouses, building site curing sheets, and sound insulation sheets for building sites. A fiber woven fabric reinforcing sheet having a surface coated with a polyvinyl chloride resin coating layer is used. These fiber fabric reinforcing sheets include canvas, tarpaulin and the like formed by coating or laminating a vinyl chloride resin composition layer on a fiber fabric. Since polyvinyl chloride resin itself has a high degree of flame retardancy, these canvas and tarpaulin for construction use 5-20 flame retardants such as antimony trioxide and aluminum hydroxide in polyvinyl chloride resin. It is possible to add a small amount of use by weight and pass the flameproof standard (Fire Law Enforcement Regulations Article 4: JIS Standard L-1091) stipulated in the Fire Service Law. However, when these canvas and tarpaulin coating resins are replaced with polyolefin resins, the polyolefin resins themselves are flammable, and by including a flammable synthetic fiber fabric, a high degree of flame retardancy is easy. This causes a problem that it cannot be obtained.

  In general, the flame retardancy of a polyolefin resin can be achieved by adding a commercially available flame retardant or flame retardant resin to the polyolefin resin. For example, halides such as organic chlorinated products and organic brominated products, phosphorus-containing compounds such as phosphate esters, phosphite esters and red phosphorus, and metal hydroxides are used as flame retardants. In order to avoid generation of hydrogen fluoride gas, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, and metal oxides such as antimony trioxide, zinc borate, and titanium dioxide are selected and used. (JP-A 63-20348 (Patent Document 1), JP-A 63-61055 (Patent Document 2), JP-A 63-128038 (Patent Document 3), JP-A 63-154760 Gazette (patent document 4), JP-A-3-20342 (patent document 5) and the like. However, in the case of these methods, in order to impart sufficient flame retardancy to the polyolefin-based resin, it is necessary to add a metal hydroxide and a metal oxide in a large amount of 100 to 300 parts by weight, As a result, the processability of the polyolefin resin composition is remarkably impaired, and at the same time, the mechanical strength of the processed product is greatly reduced. In particular, in the case of a sheet-like processed product, the texture is harder than that of a sheet made of a soft polyvinyl chloride resin, and there are significant problems in practical durability such as fatigue deterioration due to bending and surface scratches.

  In view of this, it has been proposed to use red phosphorus, heat-expandable graphite, or the like as a flame retardant aid in combination with the above metal hydroxide or metal oxide (Japanese Patent Laid-Open No. 1-4632). ), JP-A-6-184330 (Patent Document 7), JP-A-6-73251 (Patent Document 8), JP-A-6-25476 (Patent Document 9), JP-A-8-302202 (Patent Document) Reference 10)). With the combined use of these flame retardant aids, it is possible to certainly reduce the amount of metal hydroxide or metal oxide added to some extent to obtain a flame retardant polyolefin resin composition. The addition amount of metal hydroxide, metal oxide or the like is required to be 50 parts by weight or more, and it has not yet reached a level at which it is possible to effectively avoid deterioration of mechanical properties of the polyolefin resin composition. In addition, the reddish brown colorability of red phosphorus itself and the black colorability of heat-expandable graphite itself greatly affect the degree of freedom of moldability, so applications such as tents that require coloring and toning are required. It cannot be used at all.

  On the other hand, in applications such as electric wires and cables, a method of making flame retardant by blending a halogenated material such as an organic chlorinated material or an organic brominated material with a polyolefin-based resin as an insulating material or an outer covering material has been used for a long time (specialty). Japanese Utility Model Laid-Open No. 51-132254 (Patent Document 11), Japanese Patent Application Laid-Open No. 56-136862 (Patent Document 12), Japanese Patent Application Laid-Open No. 61-254646 (Patent Document 13), Japanese Patent Application Laid-Open No. 62-225541 ( Patent Document 14)). In these methods, it is possible to obtain a flame-retardant polyolefin resin composition with a small amount of added halide. However, this composition has a drawback that it tends to cause dripping during combustion. In addition, since these halides are inferior in light resistance, the halide-containing polyolefin resin composition has a drawback that it is easily discolored even for short-term outdoor use. This inferior light resistance is not a problem for underground electric wire applications or products colored in black, but is preferred for outdoor use, especially for applications such as tents where color is important. It is not a thing. In addition, these halides have a problem in that there are many troubles that bloom (powder) is generated on the surface of the polyolefin-based resin over time.

  In addition, a laminated sheet obtained by laminating a film made from a polyolefin resin composition flame-retardant with these halides and laminated with a synthetic fiber fabric is a tent, a sheet warehouse, a building site curing sheet, and a sound insulation sheet for a building site. When used for such applications, the dielectric loss factor of the polyolefin-based resin is too low, so that there is a disadvantage that a high-frequency fusion machine used for sewing a polyvinyl chloride resin sheet cannot be used. For this reason, a special heat-sealing machine is required to sew these sheets. However, in this case, the halide is used as a flameproof standard (Article 4 of the Fire Service Law Enforcement Regulations). : In order to reduce the strength of the polyolefin-based resin film and to deteriorate the adhesion to the synthetic fiber fabric at the same time, It had the disadvantage that breakage breakage was likely to occur. In addition, when kneading a compound containing these halides in a polyolefin resin, applying the conventional batch kneading method to this compound causes the halide powder to settle and aggregate in a kneader such as a Banbury mixer or kneader. For this reason, it is difficult to disperse a predetermined amount of the halide in the polyolefin-based resin. Therefore, there is a disadvantage that the flame retardant standard stipulated in the Fire Service Law cannot be stably passed.

Therefore, it can be obtained by making it flame retardant by blending a polyolefin resin with a halide such as an organic chlorinated product or an organic bromide, a phosphorous ester, a phosphorous ester, a phosphorus-containing compound such as red phosphorus, or a metal hydroxide. Even if there is a flameproof sheet product, it has sufficient flame retardancy, excellent mechanical strength, joint strength, wear resistance, workability, etc., and also excellent in light resistance and high frequency fusion properties Polyolefin-based canvas sheets and tarpaulin sheets have not yet been developed.
JP 63-20348 A JP 63-61055 A JP 63-128038 A JP 63-154760 A JP-A-3-20342 Japanese Unexamined Patent Publication No. 1-4463 JP-A-6-184330 JP-A-6-73251 JP-A-6-25476 JP-A-8-302202 JP 51-132254 A JP-A-56-136862 JP 61-254646 A Japanese Patent Laid-Open No. 62-225541

  The present invention has a high degree of flame retardancy and light resistance that could not be achieved with the above conventional flame retardant polyolefin resin sheet, and also has excellent high-frequency fusibility, and excellent workability, such as a tent, It is intended to provide a flame-retardant and improved light resistance polyolefin-based resin sheet suitable for industrial material sheets such as sheet warehouses, building site curing sheets, and sound insulation sheets for building sites, and a method for producing the same. is there.

The flame retardant light-resistant polyolefin resin sheet of the present invention is a fiber fabric that has been pretreated with a composition containing at least one silicon compound selected from synthetic amorphous silica, colloidal silica, and silane coupling agents. And a polyolefin resin coating layer formed on both sides of the base fabric, the polyolefin resin coating layer comprising (1) 100 parts by weight of a polyolefin resin blend,
(2) 5 to 100 parts by weight of a flame retardant containing at least one halogen-substituted organic compound, and (3) 0.005 to 3.5 parts by weight of a light-resistant stabilizer,
The polyolefin resin blend is
(A) a main component comprising a linear low-density polyethylene resin obtained by copolymerizing ethylene and an α-olefin in the presence of a metallocene catalyst, and (b) an ethylene-vinyl acetate copolymer resin and A blend component comprising at least one selected from ethylene- (meth) acrylic acid (ester) copolymer resins, and copolymerized vinyl acetate and (meth) acrylic acid (ester) contained in the blend component ) Is 5 to 30% by weight based on the weight of the polyolefin-based resin blend,
The light resistance stabilizer is at least one selected from a benzotriazole compound, a benzophenone compound, a cyanoacrylate compound, a salicylate compound, and a hindered amine compound, and an organic tin compound. , A zinc-based metal composite compound, metal soap, epoxidized oil and fat, hydrotalcite, and a light-resistant stabilizer component (B) composed of at least one selected from zeolite. .
In the flame-retardant light-resistant polyolefin resin sheet of the present invention, the flame retardant further contains at least one inorganic compound in addition to the at least one halogen-substituted organic compound, and the halogen-substituted compound. The total weight of the organic compound and the inorganic compound is preferably 5 to 100 parts by weight with respect to 100 parts by weight of the polyolefin resin blend.
In the flame retardant light-resistant polyolefin resin sheet of the present invention, the polyolefin resin coating layer contains 5 to 50 parts by weight of at least one phosphorus-containing compound with respect to 100 parts by weight of the polyolefin resin blend, Further, it may be included.
In the flame retardant light-resistant polyolefin resin sheet of the present invention, the halogen-substituted organic compound for the flame retardant may be selected from a bromine-substituted organic compound, a brominated polymer compound, and a chlorinated polymer compound. preferable.
In the flame retardant light-resistant polyolefin resin sheet of the present invention, the inorganic compound for a flame retardant may be selected from metal oxides, metal hydroxides, metal composite oxides, and metal composite hydroxides. preferable.
In the flame-retardant light-resistant polyolefin resin sheet of the present invention, the phosphorus-containing compound is selected from red phosphorus, inorganic phosphate, organic phosphate, phosphate ester, ammonium polyphosphate, and a phosphorus-nitrogen-containing composite. It is preferable that
In the flame-retardant light-resistant polyolefin resin sheet of the present invention, the hindered amine compound used for the light-resistant stabilizer component (A) has a piperidyl group, and its N-position is substituted with an alkyl group or an alkoxy group. Are preferably selected from the following compounds.
In the flame-retardant light-resistant polyolefin-based resin sheet of the present invention, the fiber fabric for base fabric is preferably made of filament yarn and has a porosity of 5 to 40%.
In the flame-retardant light-resistant polyolefin-based resin sheet of the present invention, the metallocene catalyst preferably includes an organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative and an alkylaluminoxane.
The method for producing a flame retardant light-resistant polyolefin resin sheet of the present invention includes the following steps: (A) (a) linear low-polymer obtained by copolymerizing ethylene and α-olefin in the presence of a metallocene catalyst. A polyolefin comprising a main component comprising a density polyethylene resin and (b) a blend component comprising at least one selected from an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer The total content of copolymerized vinyl acetate and (meth) acrylic acid (ester) contained in the blend resin component pellets is 5 to 30% by weight based on the weight of the polyolefin resin blend. (B) the polyolefin-based resin blend, and 100 parts by weight of the polyolefin resin blend, with a content exceeding 5 parts by weight, at least Preparing a flame retardant-containing pellet containing a flame retardant containing a halogen-containing organic compound of a kind, and (C) separately from the flame retardant-containing pellet, the polyolefin resin blend, A light-resistant stabilizer-containing pellet is prepared by blending a light-resistant stabilizer in an amount exceeding 0.05 parts by weight with respect to 100 parts by weight. At this time, as the light-resistant stabilizer, a benzotriazole compound, a benzophenone compound, cyano A light-resistant stabilizer component (A) comprising at least one selected from an acrylate compound, a salicylate compound, and a hindered amine compound; an organic tin compound; a zinc metal complex compound; a metal soap; an epoxidized oil; A mixture containing a site and a light stabilizer component (B) composed of at least one selected from zeolite, (D ) The flame retardant-containing pellets and the light stabilizer-containing pellets are blended, and the amount of the flame retardant is 5 to 100 weights with respect to 100 parts by weight of the total weight of the polyolefin resin blend, A compound is prepared by adjusting the blending amount of the light-resistant stabilizer to 0.005 to 3.5 parts by weight, (E) a film is produced from the compound, and (F) the film is a synthetic amorphous material. And laminating and bonding on both sides of a base fabric comprising a fiber fabric pretreated with a composition containing at least one silicon compound selected from porous silica, colloidal silica, and a silane coupling agent It is what.
In the production method of the present invention, in the compound preparation step (D), at least one pellet selected from a polyolefin resin blend, an ethylene-vinyl acetate copolymer resin, and ethylene- (meth) acrylic acid (ester) May be further blended.
In the production method of the present invention, in the flame retardant-containing pellet preparation step (B), the halogen-substituted organic compound-containing flame retardant further contains an inorganic compound in addition to the halogen-substituted organic compound. The total weight of the halogen-substituted organic compound and the inorganic compound exceeds 5 parts by weight with respect to 100 parts by weight of the polyolefin resin blend in the flame retardant-containing pellet, and the compound preparation step (D) It is preferable to adjust so that it may be 5-100 weight part with respect to the total weight of 100 weight part of the said polyolefin resin blend.
In the production method of the present invention, in the adjustment step (B) of the flame retardant-containing pellet, (1) a halogenated substituted organic compound-containing pellet containing the polyolefin-based resin blend and the halogen-substituted organic compound, and (2) preparing a mixture of an inorganic compound-containing pellet containing the polyolefin resin blend and at least one inorganic compound, provided that the total weight of the halogen-substituted organic compound and the inorganic compound is More than 5 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin blend in the flame retardant-containing pellets, and 5 to 5 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin in the compound. It is preferable to adjust so that it may be 100 weight part.
In the production method of the present invention, in the compound preparation step (D), a phosphorus-containing compound-containing pellet in which the polyolefin-based resin blend contains a phosphorus-containing compound in an amount exceeding 5 parts by weight with respect to 100 weight thereof. Further, it is preferable that the content of the phosphorus-containing compound in the compound obtained by further blending is adjusted so as to be 5 to 50 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin blend.
In the production method of the present invention, in the flame retardant-containing pellet preparation step (B), in addition to the flame retardant, the polyolefin-based resin blend further contains a phosphorus-containing compound. The blending amount is more than 5 parts by weight with respect to 100 parts by weight of the polyolefin resin blend, and 5 to 10 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin blend in the compound. It is preferable to adjust.
In the production method of the present invention, the halogen-substituted organic compound for a flame retardant is preferably selected from a bromine-substituted organic compound, a brominated polymer compound, and a chlorinated polymer compound.
In the production method of the present invention, the inorganic compound for a flame retardant is preferably selected from a metal oxide, a metal hydroxide, a metal composite oxide, and a metal composite hydroxide.
In the production method of the present invention, the phosphorus-containing compound is preferably selected from red phosphorus, inorganic phosphate, organic phosphate, phosphate ester, ammonium polyphosphate, and a phosphorus-nitrogen-containing composite.
In the production method of the present invention, the hindered amine compound used for the light-resistant stabilizer component (A) has a piperidyl group, and the N-position thereof is selected from compounds substituted with an alkyl group or an alkoxy group. preferable.
In the manufacturing method of this invention, it is preferable that the said fiber fabric for base fabrics consists of filament yarn, and has a porosity of 5 to 40%.
In the production method of the present invention, the metallocene catalyst preferably contains an organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative and an alkylaluminoxane.

  According to the present invention, a polyolefin resin sheet having excellent light resistance and excellent flame retardancy and capable of high frequency fusion, and a polyolefin type excellent in fracture strength and heat resistance creep resistance of a high frequency fusion part A resin sheet can be obtained easily. The polyolefin resin sheet obtained by the method and the production method of the present invention is a conventional soft polyvinyl chloride resin product such as a tent film material, a sheet warehouse film material, a building site curing sheet, and a building sound insulation sheet. It can be suitably used for applications that have been used, and can be used outdoors for a long period of time.

The flame retardant light-resistant polyolefin resin sheet of the present invention is a fiber fabric that has been pretreated with a composition containing at least one silicon compound selected from synthetic amorphous silica, colloidal silica, and silane coupling agents. And a polyolefin resin coating layer formed on both sides of the base fabric,
The polyolefin resin coating layer is
(1) 100 parts by weight of a polyolefin resin blend;
(2) 5 to 100 parts by weight of a flame retardant containing at least one halogen-substituted organic compound, and (3) 0.005 to 3.5 parts by weight of a light-resistant stabilizer,
The polyolefin resin blend is
(A) a main component comprising a linear low-density polyethylene resin obtained by copolymerizing ethylene and an α-olefin in the presence of a metallocene catalyst, and (b) an ethylene-vinyl acetate copolymer resin and A blend component comprising at least one selected from ethylene- (meth) acrylic acid (ester) copolymer resins, and copolymerized vinyl acetate and (meth) acrylic acid (ester) contained in the blend component ) Is 5 to 30% by weight based on the weight of the polyolefin resin blend.
The light-resistant stabilizer contained in the polyolefin-based resin coating layer is composed of at least one light-resistant stabilizer selected from a benzotriazole-based compound, a benzophenone-based compound, a cyanoacrylate-based compound, a salicylate-based compound, and a hindered amine-based compound. Mixture containing component (A) and light-resistant stabilizer component (B) comprising at least one selected from organotin compounds, zinc-based metal composite compounds, metal soaps, epoxidized oils and fats, hydrotalcite, and zeolites It is.

In the flame-retardant light-resistant polyolefin resin sheet of the present invention, the flame retardant may further contain at least one inorganic compound in addition to the at least one halogen-substituted organic compound. The total weight of the halogen-substituted organic compound and the inorganic compound may be 5 to 100 parts by weight with respect to 100 parts by weight of the polyolefin resin blend.
Furthermore, in the flame retardant light-resistant polyolefin resin sheet of the present invention, the polyolefin resin coating layer contains 5 to 50 parts by weight of at least one phosphorus-containing compound with respect to 100 parts by weight of the polyolefin resin blend. , May further be included.

  Here, (meth) acrylic acid (ester) includes acrylic acid, methacrylic acid, acrylic ester, and methacrylic ester.

  In the flame-retardant light-resistant polyolefin-based resin sheet of the present invention, the polyolefin-based resin blend used for the polyolefin-based resin coating layer includes (a) ethylene in the presence of a metallocene-based catalyst, and preferably 3 to 18 carbon atoms. A linear low-density polyethylene resin composed of one or more ethylene-α-olefin copolymer resins obtained by copolymerization with the α-olefin is produced. The ethylene-α-olefin copolymer resin is obtained by subjecting an ethylene monomer, preferably an α-olefin monomer having 3 to 18 carbon atoms, to a gas phase method, a slurry liquid phase method, or a high pressure method in the presence of a metallocene-based homogeneous catalyst. Obtained by polymerization. Examples of the α-olefin include propylene, butene-1,4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, tetradecene-1, hexadecene-1, and heptadecene- 1, octadecene-1 or the like is used, and an α-olefin having 4 to 10 carbon atoms is particularly preferably used. Further, an ethylene-α-olefin copolymer resin obtained by copolymerizing one or more of these α-olefins with an ethylene monomer is used.

  These ethylene-α-olefin copolymer resins can be used by blending not only one type but also two or more types of ethylene-α-olefin copolymer resins. It is suitable for the present invention that the melt index of the combined resin and the blend combination composition is 0.3 to 20 g / 10 min. If the melt index is less than 0.3 g / 10 min, resin kneading and molding with a halogen-substituted organic compound or a mixture of a halogen-substituted organic compound and an inorganic compound may be extremely difficult. When it is higher than 20 g / 10 min, the strength and heat resistance of the obtained flame-retardant light-resistant polyolefin resin film material may be insufficient, and the tackiness may be increased to cause blocking.

  As the metallocene catalyst that can be used for the polymerization of the ethylene-α-olefin copolymer resin used in the present invention, an organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative can be preferably used. The transition metal of the organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative is preferably selected from group IVB of the periodic table, for example, zirconium, titanium, and hafnium.

  Specific examples of the organic transition metal compound containing a cyclopentadienyl derivative include bis (n-propylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride, 1-methyl-1 ethylidene (cyclopentadienyl-1-fluorenyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4,5-trimethylcyclopentadienyl) hafnium dichloride, etc. It can be illustrated.

  Specific examples of organic transition metal compounds containing indenyl derivatives include ethylene bis (indenyl) zirconium dichloride, diphenylsilylene bis (indenyl) zirconium dichloride, 1,2-ethylenebis (tetrahydroindenyl) zirconium dichloride, bis (indenyl) titanium. Examples include dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, and the like.

  When the former metallocene catalyst containing a cyclopentadienyl derivative is used, the resulting copolymer resin has high syndiotacticity, and when the latter metallocene catalyst containing an indenyl derivative is used, the resulting copolymer is obtained. High isotacticity of resin. Therefore, the stereoregularity of the obtained ethylene-α-olefin copolymer resin can be controlled by properly using these metallocene catalysts.

In the polymerization of the ethylene-α-olefin copolymer resin used in the present invention, the activity of polymerization can be improved by using an alkylaluminoxane as a co-catalyst for the metallocene catalyst. Examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane, and isobutylaluminoxane. For example, as the alkylaluminoxane,-(Al (CH ₃ ) -O-) _n -condensate obtained by condensation of trimethylaluminum or organic aluminum such as triethylaluminum with water can be used. The ratio of the number of metal atoms of the alkylaluminoxane to the metallocene catalyst (aluminum atom / transition metal atom of the metallocene catalyst) is preferably 100 to 1000. The amount of the metallocene catalyst used in the polymerization system is preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻³ gram atoms per 1 liter of polymerization volume. Further, if necessary, conventionally known protonic acid, Lewis acid, and Lewis acidic compound may be used in combination for the purpose of increasing the polymerization activity. There are no particular limitations on the type of protonic acid, Lewis acid, or Lewis acidic compound, but boron compounds are preferably used.

  Production of an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer resin (b) that can be used for the polyolefin resin coating layer of the flame retardant light-resistant polyolefin resin sheet of the present invention For this, a radical polymerization method can be used. Examples of the monomer capable of radical polymerization with the ethylene monomer include vinyl acetate, unsaturated carboxylic acids such as acrylic acid and methacrylic acid, and esterified products thereof. Examples of the esterified product of unsaturated carboxylic acid include methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, and the like. These monomers can be used alone or in combination of two or more. Specifically, the ethylene-vinyl acetate copolymer resin is obtained by polymerization of an ethylene monomer and a vinyl acetate monomer, and the ethylene- (meth) acrylic acid (ester) copolymer resin is an ethylene monomer. Ethylene-acrylic acid copolymer resin obtained by polymerization of acrylic acid monomer with ethylene monomer, ethylene-acrylic acid ester copolymer resin obtained by polymerization of ethylene monomer and acrylic acid ester monomer, ethylene monomer and methacrylic acid monomer Ethylene-methacrylic acid copolymer resin obtained by polymerization of ethylene, ethylene-methacrylic acid ester copolymer resin obtained by polymerization of ethylene monomer and methacrylic acid ester monomer, and a mixture of two or more of these Can be mentioned.

  The polyolefin copolymer resin contained as a blend component in the polyolefin resin coating layer of the flame retardant light resistant polyolefin resin sheet of the present invention is preferably ethylene-acetic acid having a vinyl acetate component content of 5 to 60% by weight. Vinyl copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin having 5 to 60% by weight of (meth) acrylic acid (ester) component content, and ethylene-vinyl acetate copolymer resin and (meth) acrylic The total amount of vinyl acetate component and (meth) acrylic acid (ester) component that are selected from a mixture of acid (ester) copolymer resin, preferably in a weight ratio of 100: 1 to 1: 100, It is preferably 5 to 60% by weight based on the weight of the polyolefin resin blend. The melt index of these blend components (polyolefin copolymer resin) is preferably 0.3 to 20 g / 10 min for the present invention. If the melt index is less than 0.3 g / 10 min, the resin kneadability and moldability of the halogen-substituted organic compound or the mixture of the halogen-substituted organic compound and the inorganic compound may be poor. On the other hand, if it is higher than 20 g / 10 min, the strength and heat resistance of the obtained flame-resistant light-resistant polyolefin resin sheet may be insufficient, and the tackiness may be increased to cause blocking.

  In the polyolefin resin coating layer of the flame retardant light resistant polyolefin resin sheet of the present invention, the weight ratio of the ethylene-α-olefin copolymer resin main component and the polyolefin copolymer resin blend component is 100: 10. The total content of vinyl acetate and (meth) acrylic acid (ester) in the blend component is preferably 5 to 30% by weight based on the polyolefin resin blend weight. When the weight ratio of the main component and the blend component is less than 100: 10, that is, the blend component is less than 10 parts by weight with respect to 100 parts by weight of the main component, the high-frequency fusion property and flame retardancy of the resulting polyolefin-based resin sheet The flexibility may be insufficient, and when it exceeds 100: 100, that is, when the blend component exceeds 100 parts by weight with respect to 100 parts by weight of the main component, the resulting coating resin for the polyolefin resin sheet Insufficient strength may cause scratches. At the same time, when the total content of copolymerized vinyl acetate and (meth) acrylic acid (ester) contained in the polyolefin resin blend is less than 5% by weight, the high frequency fusion property of the resulting polyolefin resin coating layer, In addition, flame retardancy and flexibility may be insufficient, and if it exceeds 30% by weight, the coating resin strength of the polyolefin resin sheet obtained may be insufficient and may be easily scratched. Moreover, the heat resistant creep property may be insufficient.

The blend density of the main component ethylene-α-olefin copolymer resin and the blend component polyolefin copolymer resin contained in the polyolefin resin coating layer of the flame retardant light-resistant polyolefin resin sheet of the present invention is: 0.913 to 0.938 g / cm ³ , and more preferably 0.916 to 0.933 g / cm ³ . When this density exceeds 0.938 g / cm ³ , the crystallinity of the resulting resin blend increases and the texture becomes hard, and the halogen-substituted organic compound and the light-resistant stabilizer are present on the surface of the polyolefin resin sheet. May bloom and cloud the appearance. When the density is less than 0.913 g / cm ³ , the resulting coating layer has good bloom resistance, but the film strength and heat resistance are lowered, and sufficient wear strength may not be obtained. The fusibility may be insufficient.

  The polyolefin resin coating layer of the flame retardant light resistant polyolefin resin sheet of the present invention may contain an additional component as another metallocene catalyst polyolefin resin, which is a propylene monomer in the presence of a metallocene catalyst. It includes an isotactic polypropylene resin obtained by self-polymerization of the above, or a syndiotactic polypropylene resin. These additional components are used for the purpose of improving the impact resistance strength and the resin wear strength of the resulting resin coating layer, and the content thereof is about 5 to 10% by weight of the total weight of the resin coating layer. preferable.

  Examples of the halogen-substituted organic compound for the flame retardant contained in the polyolefin resin coating layer of the flame-retardant light-resistant polyolefin resin sheet of the present invention include bromine-substituted organic compounds, brominated polymer compounds, and chlorinated polymers. Compounds.

  Bromine substituted organic compounds include hexabromobiphenyl, decabromodiphenyl, pentabromoethylbenzene, decabromodiphenyl oxide, hexabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromodiphenyl oxide, pentabromocyclohexane, bistribromophenoxyethane, tri Bromophenol, ethylenebispentabromodiphenyl, hexabromobenzene, hexabromocyclododecane, octabromonaphthalene, tetrabromobisphenol A, and derivatives thereof such as tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromobisphenol A- Bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl) Ether), tetrabromobisphenol A-bis (allyl ether, etc.) tetrabromobisphenol S and its derivatives, such as tetrabromobisphenol S-bis (hydroxyethyl ether), tetrabromobisphenol S-bis (2,3-dibromopropyl ether) Bromine-containing inorganic phthalic acid derivatives such as tetrabromophthalic anhydride, tetrabromophthalimide, ethylenebistetrabromophthalimide, and ethylenebispentabromophthalimide, such as ethylenebis (5,6-dibromonorbornel-2,3) -Dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, Diels-Alder adduct of hexabromocyclopentadiene, tribromophenylglycidyl ether, Bromophenyl acrylate, ethylene bistribromophenyl ether, ethylene bispentabromophenyl, ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, 1,2-bis (tribromophenoxy) ethane, tris (2,3-dibromopropyl -1) Isocyanurate, tris (2,4,6-tribromophenoxy) isocyanurate and the like.

  Also, bromine-substituted phosphates such as tris (2,3-dibromopropyl) phosphate, tris (2,4,6-tribromophenyl) phosphate, tris (tribromoneopentyl) phosphate, and the like can be used.

  Examples of the brominated polymer compound include brominated polystyrene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, brominated polyurethane, brominated polyester, and TBA polycarbonate oligomer.

  Examples of the chlorinated polymer compound include low chlorinated polyethylene having a chlorine content of 25 to 45% by weight obtained by chlorinating polyethylene and highly chlorinated polyethylene having a chlorine content of 60% by weight or more. A low chlorinated polyethylene having a rate of 30 to 45% by weight and a crystallinity of 25% or less can be preferably used. In addition, a chlorinated ethylene resin obtained by chlorinating ethylene-α-olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin as chlorinated polyethylene. It can also be used. Examples of the chlorinated polypropylene include low chlorinated polypropylene having a chlorine content of 30 to 45% by weight obtained by chlorinating polypropylene and highly chlorinated polypropylene having a chlorine content of 65% by weight or more. It can be preferably used.

  Examples of the inorganic compound for the flame retardant contained in the polyolefin resin coating layer of the flame retardant light-resistant polyolefin resin sheet of the present invention include metal oxides, metal hydroxides, metal composite oxides, and metal composite hydroxides. Such as things. Specifically, these include metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zirconium hydroxide, basic magnesium carbonate, dolomite, hydrotalcite, zinc hydroxystannate, tin oxide Hydrates, metal composite hydroxides such as borax, aluminum oxide, magnesium oxide, barium oxide, titanium oxide, zinc oxide, tin oxide, zirconium oxide, molybdenum oxide, antimony oxide and other metal oxides, zinc borate And metal composite oxides such as zinc metaborate, barium metaborate, aluminum borate, potassium titanate, and zirconium-antimony.

  The particle size of these inorganic compounds varies depending on the type of the compound, but for example, those having an average particle size of 20 μm or less, preferably 10 μm or less are preferable in terms of processability and dispersibility. Further, the inorganic compounds used in the present invention include fatty acids such as stearic acid, oleic acid, and palmitic acid or metal salts thereof, paraffin wax, polyethylene wax, or modified products thereof, organic borane, organic titanate, and silane coupling. It is preferable to use a material that has been surface-coated, surface-treated or modified with an agent. These inorganic compounds may be used alone or in combination of two or more.

  In particular, in the flame retardant light-resistant polyolefin resin sheet of the present invention, 5 to 100 parts by weight, preferably one or more of these halogen-substituted organic compounds for flame retardants, based on 100 parts by weight of the polyolefin resin blend, Is blended in an amount of 10 to 50 parts by weight, or a mixture of one or more halogen-substituted organic compounds for flame retardant and one or more inorganic compounds in an amount of 5 to 100 parts by weight based on 100 parts by weight of the polyolefin resin blend. Parts, preferably 10 to 60 parts by weight. The combination ratio of the halogen-substituted organic compound for the flame retardant and the inorganic compound is not particularly limited, but depending on the halogen content contained in the halogen-substituted organic compound, the halogen-substituted organic compound: the inorganic compound The weight ratio is preferably 5: 1 to 1: 1, more preferably 3: 1 to 2: 1. As the inorganic compound used in combination with the halogen-substituted organic compound, it is particularly preferable to use antimony oxide such as antimony trioxide and antimony pentoxide.

  Moreover, the polyolefin resin coating layer of the flame retardant light-resistant polyolefin resin sheet of the present invention may further contain 5 to 50 parts by weight of a phosphorus compound with respect to 100 parts by weight of the polyolefin resin blend. Examples of the phosphorus compound include red phosphorus, inorganic phosphate, organic phosphate, phosphate ester, ammonium polyphosphate, melamine polyphosphate, and phosphorus-nitrogen-containing composite. As red phosphorus, yellow phosphorus can be converted into red phosphorus by heating at 250 to 350 ° C. in an inert gas atmosphere, and powdered red phosphorus having an average particle diameter of 5 to 25 μm can be used. In addition, as the red phosphorus used in the present invention, thermosetting of aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide inorganic compound, or formalin resin, phenol resin, melamine resin, urea resin, epoxy resin It is preferable to use powdered red phosphorus particles whose surface is coated with at least one selected from resins and whose average particle diameter is 5 to 25 μm. In particular, white-treated red phosphorus whose surface is coated with titanium oxide can be preferably used in terms of the colorability of the flame-retardant light-resistant polyolefin-based resin sheet of the present invention.

  In the present invention, phosphoric acid includes phosphoric acid, phosphorous acid, and hypophosphorous acid, and inorganic phosphate includes phosphoric acid, phosphorous acid, and metal salts of hypophosphorous acid. Examples of the metal that forms a salt with phosphoric acid include Na, K, Li, Ca, Ba, Mg, Al, and Zn. Examples of the organic phosphate include metal salts of (alkyl) phosphorous monoalkyl esters and metal salts of (alkyl) phosphorous dialkyl esters. Examples of the metal forming the organic phosphate include sodium, potassium, lithium, calcium, barium, magnesium, aluminum, and zinc.

  Examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, chain alkyl phosphate ester compounds such as dimethyl ethyl phosphate, methyl dibutyl phosphate, triphenyl phosphate, triphenyl phosphate, Aromatic phosphate ester compounds such as cresyl phosphate, diphenyloctyl phosphate, p-pentylphenyl phosphate, and hydroxyphenyl diphenyl phosphate, and oligomeric condensates of these compounds can be used. Examples of the oligomeric condensates include bisphenol A bis (diphenyl phosphate), bisphenol A tetraphenyl diphosphate, bisphenol A tetracresyl diphosphate, 1,3-phenylene bis (diphenyl phosphate), resorcinol diphosphate, resorcinol bis ( Oligomeric aromatic phosphate ester condensates such as diphenyl phosphate and trioxybenzene triphosphate can be used.

  As the ammonium polyphosphate compound, a condensed phosphate compound composed of a condensate of ammonium orthophosphate and a nitrogen-containing compound can be used. Examples of the condensed phosphate compound include ammonium polyphosphate, melamine-modified ammonium polyphosphate, and melamine polyphosphate. As the ammonium polyphosphate, those having a polymerization degree of 200 or more are preferably used, and the surface of the ammonium polyphosphate is surface-treated with a thermosetting resin such as a melamine resin, urea resin, triazine resin, or phenol resin to form water. Those hardly soluble are preferably used. When the polymerization degree of ammonium polyphosphate is less than 200, the ammonium polyphosphate is water-soluble and is eluted in water, and as a result, the sustainability of the flame retarding effect is lost. For this reason, it is inappropriate for applications exposed to rainfall. As the condensed phosphorus compound that can be used in the flame-retardant light-resistant polyolefin-based resin sheet of the present invention, ammonium polyphosphate having a polymerization degree of 600 to 1200 that has been surface-coated with a melamine resin can be preferably used.

  Examples of phosphorus-nitrogen compounds used in the present invention include melamine, melamine sulfate, trimethylol melamine, cyanuric acid trimethyl ester, cyanuric acid triethyl ester, ammelin, ammelide, and cyanuric acid derivatives such as 2,4,6-trioxycyanidine. And polyphosphoric acid composites, and (iso) cyanuric acid derivatives and polyphosphoric acid composites such as isoammelin, isomelamine, isoammelide, trimethylcarbodiimide, triethylcarbodiimide, and tricarbimide, dicyandiamide, dicyandiamidicin, guanidine, Complexes of cyanamide derivatives such as guanidine sulfamate, guanidine phosphate, and diguanide with polyphosphoric acid, urea, dimethylolurea, diacetylurea, trimethylurea, N-benzoylurea, and Composite of urea derivative and polyphosphoric acid such as an acid guanyl urea, thiourea, ammonium, compound with sulfur compounds and polyphosphoric acid and ammonium sulfamate and the like.

  In the polyolefin resin coating layer of the flame retardant light resistant polyolefin resin sheet of the present invention, (A): a light stabilizer that acts on a polyolefin resin blend, and (B): a halogen-substituted organic system as a light stabilizer. 0.05 to 3.5 parts by weight of one or more light stabilizers acting on the compound is contained with respect to 100 parts by weight of the polyolefin resin blend. Examples of the light-resistant stabilizer (A) for polyolefin resin blends include benzotriazole compounds, benzophenone compounds, cyanoacrylate compounds, salicylate compounds, and hindered amine compounds. Examples of the benzotriazole compounds include 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′- Ditert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotrial, 2- (2′-hydroxy-3 ′, 5′-ditert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-ditert-butylphenyl) benzotriazole, 2- (2 '-Hydroxy-4'-octoxyphenyl) benzotriazole, 2- (4'-octoxy-2-hydroxyphenyl) Nzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (2-phenylisopropyl) ) Benzotriazole, 2- [2′-hydroxy-3 ′-(3 ″, 4 ″, 5 ″, 6 ″ -tetrahydrophthaloid-methyl) -5′-methylphenyl] benzotriazole, 2, 2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-tert-butyl-5- (2H -Benzotriazol-2-yl) -4-hydroxyphenyl] propionate and polyethylene glycol (molecular weight 300).

  Examples of the benzophenone compounds include 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2′-dihydroxy-4-n-octoxybenzophenone, and 2,4′-dihydroxy. Examples include benzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone. Furthermore, examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate. Further, examples of the salicylate compounds include phenyl salicylate, 4-t-butyl-phenyl salicylate, 4-t-octyl-phenyl salicylate, and bisphenol A-disalicylate.

  Further, the hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bisdecanedioic acid bis. (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, dimethyl succinate and 4-hydroxy-2,2,6,6 A condensate of tetramethyl-1-piperidineethanol, N, N ′, N ″, N ′ ″-tetrakis [4,6-bis [butyl (N-methyl-2,2,6,6) Tetramethylpiperidin-4-yl) amino] triazin-2-yl] -4,7-diazadecane-1,10-diamine, 2,2,4,4-tetramethyl-7-oxa-3,20-diazadispiro [ 5.11.2] -Heneicosan-21-one, 2,2,4,4-tetramethyl-21-oxo-7-oxa-3,20-diazadispiro [5.1.1.12] -heneicosane -20-propanoic acid dodecyl ester / tetradecyl ester, 2,2,4,4-tetramethyl-7-oxa-3,10-diaza-20 (2,3-epoxypropyl) dispiro [5.1.11. 2] -Heneicosan-21-one polycondensate, propandioic acid [(4-methoxyphenyl) -methylene] -bis (1,2,2,6,6-pentamethyl-4-piperazinyl Ester, 1,3-benzenedicarboxamide-N, N′-bis (2,2,6,6-tetramethyl-4-piperazinyl), poly [[6- (1,1,3,3-tetramethyl Butyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetra Methyl-4-piperidyl) imino]], dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylenediamine -A polycondensate of N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine is exemplified.

  As a light-resistant stabilizer (A) which acts on a polyolefin-type resin blend, it can also be used combining the single type of the said compound, or 2 or more types. In particular, those having a melting point of 150 ° C. or less are preferable in terms of dispersibility when kneading with a polyolefin resin blend. When a hindered amine compound is used, the N-position hydrogen of the piperidyl group is a methyl group or the like. It is particularly preferable to use an alkyl group-substituted one or an methoxy group-substituted one substituted with an alkoxy group such as a methoxy group, regardless of the type of the halogen-substituted organic compound used in combination therewith.

  Examples of the light-resistant stabilizer (B) acting on the halogen-substituted organic compound include organotin compounds, zinc-based metal composite compounds, metal soaps, epoxidized oils and fats, hydrotalcite, and zeolites. Examples of the organotin compounds include butyltin malate, dibutyltin malate, butyltin laurate, dibutyltin laurate, dibutyltin malate laurate, dibutyltin dimaleate, dibutyltin dilaurate, dioctyltin malate, And dioctyltin laurate compounds, alkyltin malate polymers such as butyltin malate polymer, octyltin malate polymer, alkyltin laurate compounds, methyltin mercapto, butyltin mercapto, dioctyltin mercapto, mono-dioctyl Alkyl tin mercapto compounds such as tin mercapto, octyl tin mercaptomalate, octyl tin mercapto laurate, zinc-magnesium containing octyl tin mercapto, other butyl tin thiopropionate, dibutyl tin thiopropiate Emissions salt, octyl tin dithio propionate, etc. (di) alkyl tin (di) thiopropionic acid salts such as dioctyl tin dithio propionate and the like.

A plurality of metals including zinc as the zinc-based metal complex compound, ricinoleic acid, oleic acid, 2-Echiruhekisoen acid, C ₈ -C ₁₂ mixed acid, naphthenic acid, organic acids such as resin acids, and phenols, benzoic acid , Compounds obtained by metal saponification with aromatic acids such as salicylic acid and derivatives thereof, for example, calcium-zinc composite system, barium-zinc composite system, magnesium-zinc composite system, barium-magnesium-zinc composite system compound Is mentioned. Examples of the metal soap include zinc stearate, calcium stearate, magnesium stearate, lithium stearate, barium stearate, aluminum stearate, strontium stearate, sodium stearate and the like. Further, as the epoxidized fats and oils, epoxidized vegetable oils obtained by epoxidizing dry oil or semi-dry oil containing oleic acid, oleic acid, linoleic acid such as soybean oil, linseed oil, safflower oil, sunflower oil with peracid Compound, oleic acid, tall oil fatty acid, nuka oil fatty acid, soybean oil fatty acid, linseed oil fatty acid etc. esterified with epoxidized fatty acid ester compound obtained by epoxidation, other epoxidized alicyclic compound, bisphenol A di Examples thereof include glycidyl ether and epoxidized butadiene.

Examples of the hydrotalcite include compounds represented by [M _1-x M ′ _x (OH) ₂ Ax / n · mH ₂ O]. (In the formula, M is selected from Mg, Mn, Fe, Co, Ni, Cu and Zn, M ′ is selected from Al, Fe, Cr, Co and In, and A is H, F, Cl and Br. , NO ₂ , CO ₃ , SO ₄ , Fe (CN) ₆ , and CH ₂ COO) hydrotalcite (M = Mg, M ′ = Al, A = CO ₃₎ preferable. The crystal structure of the brucite-type hydrotalcite has a multilayer structure in which positively charged Mg (OH) ₂ layers and negatively charged intermediate layers composed of CO ₃ anions and interlayer water are alternately arranged. These average particle diameters are preferably 0.1 to 1.0 μm, and the BET specific surface area is preferably 5 to 25 m ² / g. It is also possible to use hydrotalcite represented by _{[M 1-x M 'x (} OH) 2 Ax / n · Ax / nmH 2 O ]. Examples of the zeolite include A-type zeolite crystal structure represented by _{^{[M 2 / nO · Al 2 O}} 3 · xSiO 2 · yH 2 O ].

  As the light-resistant stabilizer (B) acting on the polyolefin resin blend, a single type selected from the above compounds, or a combination of two or more types can also be used. The polyolefin-based resin coating layer of the flame-retardant light-resistant polyolefin-based resin sheet of the present invention has (A): a light-resistant stabilizer acting on a polyolefin-based resin blend, and (B): a halogen-substituted organic compound as a light-resistant stabilizer. It is preferable that two or more kinds selected from light-resistant stabilizers that act on the light-sensitive stabilizer are included, and the total amount of light-resistant stabilizers (A) and (B) is 0 with respect to 100 parts by weight of the polyolefin resin blend. 0.005 to 3.5 parts by weight, preferably 0.05 to 3.5 parts by weight. If the addition amount is less than 0.05, the light resistance of the resulting resin coating layer is insufficient, and if it exceeds 3.5 parts by weight, the light resistance will be sufficient. The improvement in light resistance commensurate with the increase in amount cannot be obtained, causing troubles such as blooming and bleeding of the light-resistant stabilizer. Moreover, although there is no limitation in particular in the combined ratio of a light-resistant stabilizer (A) and (B), generally it is preferable to be used by 2: 1-1: 2 (weight ratio).

  The polyolefin resin coating layer of the flame retardant light resistant polyolefin resin sheet of the present invention may be colored (including white) with an organic pigment and / or an inorganic pigment. Conventionally known organic pigments can be used, such as azo pigments, phthalocyanine pigments, dyed lake pigments, anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments. Examples thereof include pigments, isoindolinone pigments, quinophthalone pigments, and other nitroso pigments, alizarin lake pigments, metal complex azomethine pigments, aniline pigments, and the like.

Examples of inorganic pigments include zinc oxide (zinc white), titanium oxide (rutile type, anatase type), antimony trioxide, iron oxide, lead oxide, chromium oxide, zirconium oxide, and spinel type (XY ₂ O ₄ ) structure. Metal oxides such as oxides, rutile-type [Ti (XY) O ₂ ] structure oxides, composites of zinc sulfide and barium sulfate (lithopone), metal sulfides such as calcium sulfide and zinc sulfide, barium sulfate, calcium sulfate , Metal sulfate such as lead sulfate, barium carbonate, calcium carbonate, magnesium carbonate, metal carbonate such as composite of lead carbonate and lead hydroxide (lead white), magnesium hydroxide, aluminum hydroxide (alumina white), water Composites of aluminum oxide and calcium sulfate (satin white), composites of aluminum hydroxide and barium sulfate (gross white), etc. Metal hydroxide, metal chromate such as lead chromate (yellow lead), barium chromate, other carbon black, titanium black, acetylene black, graphite, white carbon, diatomaceous earth, talc, clay, aluminum powder, coloring Examples include aluminum powder, crushed metal vapor deposited film, silver-white mica titanium, colored mica titanium, and dichroic interference mica titanium. These pigments can be used alone or in combination of two or more, and the addition amount is not limited. Moreover, the combination in which the hue, density | concentration, saturation, etc. of the polyolefin resin coating layer of the front and back differed may be sufficient.

The method for producing the flame-retardant light-resistant polyolefin resin sheet of the present invention includes the following steps:
(A) (a) a main component comprising a linear low density polyethylene resin obtained by copolymerizing ethylene and an α-olefin in the presence of a metallocene catalyst;
(B) a blend component consisting of at least one selected from ethylene-vinyl acetate copolymer resin and ethylene- (meth) acrylic acid (ester) copolymer;
Polyolefin resin blend pellets containing
The total content of copolymerized vinyl acetate and (meth) acrylic acid (ester) contained in the blend component is adjusted to 5 to 30% by weight based on the weight of the polyolefin resin blend,
(B) A flame retardant comprising the polyolefin resin blend and a flame retardant containing at least one halogen-substituted organic compound having a content exceeding 5 parts by weight with respect to 100% by weight thereof. Preparing the containing pellets,
(C) Separately from the flame retardant-containing pellets, the polyolefin-based resin blend is blended with a light-resistant stabilizer in an amount exceeding 0.05 parts by weight with respect to 100 parts by weight of the light-resistant stabilizer-containing pellets. Prepared,
(D) The flame retardant-containing pellets and the light-resistant stabilizer-containing pellets are blended, and the blend amount of the flame retardant is 5 to 100 weights with respect to 100 parts by weight of the total weight of the polyolefin resin blend. The compound is prepared by adjusting the light stabilizer so that the blending amount is 0.005 to 3.5 parts by weight,
(E) Make a film from the compound,
(F) laminating and bonding the film on both sides of a base fabric made of fiber fabric;
It is characterized by including.
In the compound preparation step (D) of the production method of the present invention, at least one pellet of a polyolefin resin blend, an ethylene-vinyl acetate copolymer resin, and an ethylene- (meth) acrylic acid (ester) copolymer resin May be further blended.
In addition, in the flame retardant-containing pellet preparation step (B) of the production method of the present invention, the halogen-substituted organic compound-containing flame retardant is added to the halogen-substituted organic compound, and further contains an inorganic compound. The total weight of the halogen-substituted organic compound and the inorganic compound exceeds 5 parts by weight with respect to 100 parts by weight of the polyolefin resin blend in the flame retardant-containing pellet,
And in the said compound preparation process (D), it is preferable to adjust so that it may be 5-100 weight part with respect to the total weight of 100 weight part of the said polyolefin resin blend.
In the adjustment step (B) of the flame retardant-containing pellet of the production method of the present invention, (1) a halogenated substituted organic compound-containing pellet containing the polyolefin resin blend and the halogen-substituted organic compound, and ( 2) preparing a mixture of the polyolefin resin blend and an inorganic compound-containing pellet containing at least one inorganic compound, provided that the total weight of the halogen-substituted organic compound and the inorganic compound is More than 5 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin-based resin blend in the flame retardant-containing pellets, and 5 to 100 weights with respect to 100 parts by weight of the total weight of the polyolefin-based resin in the compound. It is preferable to adjust so that it is a part.
In addition, in the compound preparation step (D) of the production method of the present invention, a phosphorus-containing compound-containing pellet in which the polyolefin-based resin blend contains a phosphorus-containing compound in an amount exceeding 5 parts by weight with respect to 100 weight thereof. Further, it is preferable that the content of the phosphorus-containing compound in the compound obtained by further blending is adjusted so as to be 5 to 50 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin blend.
Furthermore, in the production method of the present invention, in addition to the flame retardant, the flame retardant-containing pellet further contains a phosphorus-containing compound, and the compounding amount of the phosphorus-containing compound is determined according to the polyolefin resin blend 100. It is preferable to adjust to 5 to 10 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin blend in the compound, exceeding 5 parts by weight.

  The film for a polyolefin-based resin coating layer of the flame-retardant light-resistant polyolefin-based resin sheet of the present invention can be produced by a conventionally known film forming processing method, for example, a T-die extrusion method, an inflation method, a calendar method, or the like. The compound of polyolefin resin blend is melt kneaded by, for example, a Banbury mixer or a kneader, and this kneaded material is melt-kneaded by a calendar molding method or using a twin-screw kneader etc. The obtained pellets can be formed into a film by a method such as T-die extrusion molding or inflation molding. The film for a polyolefin resin coating layer of the flame retardant light-resistant polyolefin resin sheet of the present invention includes a halogen-substituted organic compound-containing flame retardant, a polyolefin resin blend pellet containing a high concentration, or a halogen-substituted organic film. Pellets of polyolefin resin blends containing high concentrations of inorganic compounds and inorganic compounds separately are prepared in advance, and this is used as part of a compound composition resin for forming a film for polyolefin resin coating layers. It can be blended and melt-kneaded with a Banbury mixer, kneader or the like, and the kneaded product can be subjected to a calendering method to form a film. This method is preferable in order to ensure quantitative dispersion of the halogen-substituted organic compound and the inorganic compound. In the conventional batch kneading method, these halogen-substituted organic compound and inorganic compound powders sometimes settle and aggregate in a kneader such as a Banbury mixer or kneader, and therefore remain in the polyolefin resin blend. On the other hand, the quantitative dispersion of halogen-substituted organic compounds and inorganic compounds is incomplete, and as a result, it does not conform to the flame proof standard (Article 4 of the Fire Service Act: JIS Standard L-1091) stipulated in the Fire Service Act. May be. Further, the compound composition resin for forming the polyolefin resin coating layer film may further contain a phosphorus-containing compound, and the phosphorus-containing compound contains a single phosphorus-containing compound in the polyolefin resin blend. Pellets contained at a high concentration or pellets contained at a high concentration together with the halogen-substituted organic compound-containing flame retardant are preferred. These pellets may contain a colorant such as an organic pigment and an inorganic pigment in addition to the flame retardant and a light-resistant stabilizer, and may be melt-kneaded and granulated into pellets.

  The film for a polyolefin-based resin coating layer of the flame-retardant light-resistant polyolefin-based resin sheet of the present invention can be manufactured by a processing technique such as a T-die extrusion method, an inflation method, a calendar method, etc., using the above compound, In particular, when a calendar method is used for the production of a film colored with an organic pigment, an inorganic pigment, or the like, or for a process with many color changing operations, there is an advantage that it is simple with less compound loss. In the molding by the calendering method of the polyolefin resin coating layer film of the flame retardant light resistant polyolefin resin sheet of the present invention, it is preferably performed in a temperature range of 100 to 200 ° C., and the workability and film appearance at the time of molding In order to improve the above, a phosphate ester-based, aliphatic amide-based, and / or montanic acid-based lubricant may be added. The thickness of the polyolefin resin coating layer film obtained by calendering is preferably 80 to 500 μm, particularly preferably 130 to 300 μm. If the thickness of the film is less than this range, the molding process is difficult, and when laminated to the fiber cloth, the film may be cut off at the woven intersection of the fiber cloth, and the waterproof property may be impaired. The durability of the sheet may be insufficient. Although there is no restriction | limiting in the thickness of the flame-retardant light-resistant polyolefin-type resin sheet of this invention, It is preferable to laminate | stack the film for polyolefin-type resin coating layers of thickness 80-500 micrometers on a fiber fabric base fabric. In particular, it is preferable that a polyolefin-based resin coating layer is formed on both sides of a fiber fabric base fabric using two films having a thickness of 130 to 300 μm.

  The fiber fabric that can be used as the base fabric of the flame retardant light-resistant polyolefin resin sheet of the present invention may be either a woven fabric or a knitted fabric. Examples of the woven fabric include plain weave, twill weave, satin weave, etc. When a woven fabric is used, the obtained polyolefin resin sheet has an excellent balance of warp and weft properties. The yarn for warp and weft of the fiber fabric may be any of synthetic fiber, natural fiber, semi-synthetic fiber, inorganic fiber, or a mixed fiber composed of two or more of these, but has excellent processability and versatility. Threads such as polypropylene fiber, polyethylene fiber, vinylon fiber, polyester fiber, aromatic polyester fiber, nylon fiber, aromatic polyamide fiber, acrylic fiber, and polyurethane fiber are preferably used. These fiber yarns can be used in any shape such as multifilament yarns, short fiber spun yarns, monofilament yarns, split yarns, tape yarns, etc., but multifilament yarns are most preferred. As the inorganic fibers, multifilament yarns such as glass fibers, silica fibers, alumina fibers, and carbon fibers can be used. As the fiber woven fabric used as the base fabric of the high-frequency fusible polyolefin resin sheet of the present invention, plain weaving with multifilament fiber yarns comprising polyester fibers, nylon fibers, polypropylene fibers, vinylon fibers, and mixed fibers thereof is used. A woven fabric is preferred.

  As a spinning method for multifilament yarns, the above-mentioned thermoplastic resins such as polyester, polypropylene, and nylon are heated to a temperature equal to or higher than the melting temperature (melting point) to become a fluid viscous melt and liquefied. Conventionally, it is passed through a spinneret having a large number of fine pores of about 0.2 to 0.6 mmφ and extruded into an inert cooling medium such as air, nitrogen, water, etc., and rapidly cooled and solidified to form a long fiber spinning base yarn. Examples thereof include a production method using a known melt spinning method and equipment. This unstretched long fiber spinning yarn is stretched 3.0 to 5.0 times by heat stretching at 80 to 100 ° C. or cold stretching near room temperature, and the microstructure of the fiber is arranged and crystallized to form fibers. Strength can be given. This drawing process may be incorporated in the spinning process, and it is preferable that the drawing process and the multifilament twisting process are performed simultaneously. Further, heat treatment or / and two-stage stretching may be performed as necessary. These melt spinning speeds are not particularly specified because the spinning speeds differ depending on the type and equipment of the thermoplastic resin to be used. For example, the spinning speed in the case of melt spinning from a polyester resin is 1000 to 10,000 m / min, In particular, those spun at a speed of 2000 to 6000 m / min can be preferably used.

  The multifilament yarn used for the fiber fabric of the flame retardant light-resistant polyolefin resin sheet of the present invention is 138.9 to 2222.2 dtex (125 to 2000 denier), particularly 277.8 to 1111.1 dtex ( 250-1000 denier) multifilament yarn can be used. If the multifilament yarn is less than 138.9 dtex (125 denier), the tear strength of the resulting sheet may be insufficient, and if it exceeds 2222.2 dtex (2000 denier), the breaking strength of the resulting sheet and Although the tear strength is improved, the yarn diameter becomes thicker and the sheet becomes thicker. At the same time, the unevenness at the woven intersection of the fiber fabric is increased, and the smoothness is lowered. Moreover, it is preferable that the fiber fabric used as a base fabric for the high-frequency fusible polyolefin resin sheet of the present invention is a hollow plain weave. The number of warp yarns and weft yarns of the fiber fabric is not particularly limited, but multifilament yarns of 138.9 to 2222.2 dtex (125 to 2000 denier) can be obtained by driving 8 to 38 yarns per inch of warp and weft yarns. For example, in the case of 555.6 dtex (500 denier) multifilament yarn, in the case of a plain woven fabric obtained with 14 to 24 yarns per inch, 1111.1 dtex (1000 denier) multifilament yarn A plain woven fabric obtained by driving about 12 to 22 per inch can be exemplified.

  Moreover, it is preferable that the porosity (missing) of these fiber fabrics is 5 to 30%. The porosity can be obtained as a value obtained by subtracting 100 from the percentage of the area occupied by the fiber yarn in the unit area of the fiber fabric. It is preferable that the porosity is obtained by using a unit area of 10 cm in the warp direction × 10 cm in the weft direction. If the porosity of the fiber fabric for the base fabric is less than 5%, the yarn density may be too high, and the flexibility of the resulting sheet may be insufficient, and the two sheets formed on the front and back surfaces of the fiber fabric The bridge-bonding property between the polyolefin resin coating layers may be insufficient, and the dynamic durability may be insufficient. If the porosity exceeds 30%, the flexibility and the film fusing ability are improved, but the content of the fiber yarns in the weft direction becomes too small, resulting in poor dimensional and shape stability of the obtained sheet. It may be sufficient, the tear strength of the sheet becomes insufficient, and the practicality may be unsatisfactory.

Moreover, the fiber fabric used as a base fabric for the flame-retardant light-resistant polyolefin-based resin sheet of the present invention is pretreated with a silicon compound-containing treatment agent. The silicon compound-containing treatment agent includes a composition comprising at least one selected from synthetic amorphous silica, colloidal silica, and silane coupling agent, and includes synthetic amorphous silica, colloidal silica, and silane coupling agent. The composition which consists of 1 or more types selected and a thermoplastic resin may be sufficient. Among these silicon compounds, as synthetic amorphous silica, adsorbed water on the surface of silica particles produced by a dry method by heating at high temperature of 1000 ° C. or higher, anhydrous silica having a low hydroxyl group content, sodium silicate, Silica obtained by an airgel method that produces silica gel from mineral acid, and the organosol in which the water in silica gel is replaced with an organic solvent such as alcohol is dried, and wet that reacts sodium silicate with mineral acid and salts in an aqueous solution Silica obtained by the method can be used. These silicas preferably have an average particle size of about 1 to 20 μm. In the preparation of the fiber fabric, for example, a silicon compound-containing treatment agent is uniformly dispersed in water, the SiO ₂ content concentration is adjusted to 10 to 30% by weight, and the base fabric fiber fabric is immersed in the treatment bath. At the same time, it is allowed to pass through a nip roll to remove excess treatment liquid and dry the moisture. The adhesion rate of the silicon compound to the fiber fabric is not particularly limited, but the adhesion rate is preferably 3 to 10% by weight. At this time, it is preferable to use synthetic amorphous silica and a silane coupling agent in combination.

Colloidal silica is obtained by cation exchange of a sodium silicate solution, and a water dispersion medium colloidal silica sol (SiO ₂ ) having an average BET particle diameter of 10 to 50 nm or an organic solvent as a dispersion medium. Colloidal silica sol (SiO ₂ ) having a BET average particle size of 10 to 50 nm can be used. In the preparation of the fiber cloth, the fiber cloth is immersed in a colloidal silica bath having a SiO ₂ concentration of 5 to 30% by weight, pulled up from the bath and simultaneously passed through a nip roll to remove excess colloidal silica, It can be performed by drying the organic solvent. The adhesion rate to the fiber fabric is not particularly limited, but the adhesion rate is preferably 3 to 10% by weight. At this time, it is preferable to use colloidal silica and a syring coupling agent in combination.

As a silin coupling agent, a compound having two or more different reactive groups in a molecule represented by the general formula: XR-Si (Y) ₃ , for example, X = amino group, vinyl group, epoxy group, R = alkyl chain, Y = methoxy group, ethoxy group, etc., such as chloro group and mercapto group. These hydrolysates and cohydrolyzed compounds with alkoxysilane compounds can also be used. Specific examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ- Aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γchloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like, particularly epoxy silane cups It is preferred to use a ring agent.

  The silane coupling agent is used at a concentration of 1 to 5% by weight, and is preferably adjusted to a pH of 3 to 5 using an acid such as formic acid or acetic acid. The preparation of the fiber cloth is performed by immersing the fiber cloth in a silane coupling agent aqueous solution bath, pulling it up from the bath and simultaneously passing through a nip roll, removing excess silane coupling agent aqueous solution, and drying the moisture. Can do. At this time, it is preferable to use synthetic amorphous silica or colloidal silica in combination, and the adhesion rate to the fiber fabric is not particularly limited, but the adhesion rate is preferably 3 to 10% by weight.

  As a thermoplastic resin used with a silicon compound as a pretreatment agent for the above-mentioned textile fabric for base fabric, an aqueous dispersion such as an emulsion or dispersion of a thermoplastic resin, or a solubilized in an organic solvent. Can be used, ionomer resin, allyl resin, vinyl acetate resin, polyvinyl alcohol resin, ethylene-vinyl acetate copolymer resin, polyurethane resin, polystyrene resin, saturated polyester resin, polyamide resin and these The modified resin can be used. In particular, it is preferable to use an ethylene copolymer resin and an acrylic copolymer resin modified with glycidyl methacrylate, dimethylaminoethyl methacrylate, itaconic anhydride, maleic anhydride, N-methylmaleimide, or the like. If necessary, thermosetting resins such as phenolic resins, melamine resins, urea resins, unsaturated polyester resins, epoxy resins, thermosetting polyurethane resins, and allyl phthalate resins may be blended. . The fiber fabric is pretreated by immersing the fiber fabric in a water-based treatment liquid bath in which these thermoplastic resin emulsions or dispersions and the silicon compound are mixed. It can be performed by removing the pretreatment liquid and drying the moisture. In the case of a solvent-based thermoplastic resin, the pretreatment can be performed by the same method. Although there is no restriction | limiting in particular in the solid content weight ratio of thermoplastic resin solid content and a silicon compound, Generally it is preferable that it is about thermoplastic resin: silicon compound (synthetic amorphous silica) / 10-50: 90-50 weight%. .

  It is preferable to laminate a polyolefin-based resin coating layer film containing 3 to 25% by weight of the synthetic amorphous silica on the fiber fabric for base fabric that has been pretreated with these silicon compound-containing treatment agents. In the present invention, the silicon compound-containing treatment agent having a thermoplastic resin: silicon compound mixing ratio of 10 to 50:90 to 50% by weight contains at least a silane coupling agent, and a film layer for a polyolefin resin blend coating layer However, the synthetic amorphous silica is preferably contained in an amount of 3 to 25% by weight.

  The flame retardant light-resistant polyolefin resin sheet of the present invention has a polyolefin resin coating layer film laminated on both sides of a base fabric made of the above-mentioned fiber woven fabric. As a laminating method, an adhesive layer may be provided between the polyolefin resin coating layer film and the fiber fabric, or laminating and fusing without an adhesive may be performed. In the laminating method used for the flame retardant light-resistant polyolefin resin sheet of the present invention, a molding process for a film for polyolefin resin coating layer and a calender topping method for simultaneously laminating on each surface of a fiber fabric, or T-die extrusion A laminating method may be used, or a film for a polyolefin resin coating layer is once molded by a calendar method, a T-die extrusion method, an inflation method, etc., and then two polyolefin resin coating layers using a laminator For example, a method for laminating a film for heat-resistant thermal compression and laminating with a fiber fabric, and the like. Is the production method by thermocompression bonding of the layer film and the fiber fabric efficient? Economical, it is preferably used. At this time, since the two polyolefin resin blend films on the front and back sides are hot-melt bridged through the gaps in the fiber fabric for the base fabric, no special adhesive application and extra steps are required. Good adhesion and durability.

  The flame-retardant light-resistant polyolefin resin sheet of the present invention can be easily joined by fusion using a high-frequency welder. Specifically, as the high-frequency welder joining method, two or more sheets of the polyolefin resin sheet of the present invention or a part of other thermoplastic resin moldings that can be heat-sealed with the polyolefin resin sheet of the present invention are used. The electrodes are placed between two electrodes (one electrode is a weld bar), and a potential difference that oscillates at a high frequency (1 to 200 MHz) is applied to the electrode while pressing the weld bar at the junction. These superposed portions are thermally fused and bonded and sealed by the molecular frictional heat of the thermoplastic resin generated in the portions that are pressurized and applied in step (b). In this case, the dielectric loss factor of the thermoplastic resin, that is, the product (ε.tan δ) of the dielectric constant (ε) and the dielectric loss tangent (tan δ) is related to the magnitude of internal molecular frictional heat oscillated by high frequency. . The dielectric loss tangent is a function of the portion where high-frequency electromagnetic radiation energy absorbed by the thermoplastic resin is converted into heat, and the dielectric loss factor is preferably at least 0.01 or more. As a high-frequency welder fusion machine, commercially available models such as YC-7000FT and YF-7000 of Yamamoto Vinita Co., Ltd., KM-5000TA and KA-7000TE of Seidensha Electronics Co., Ltd. LW-4000W, LW-4060S, etc. of Co., Ltd. can be used.

  The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to the scope of these examples.

  In the following examples, reference examples and comparative examples, evaluation of flame resistance, evaluation of light resistance, evaluation of workability, evaluation of high-frequency welder fusing property, evaluation of joint strength, etc. The following test method was used.

(I) Evaluation of flame resistance of polyolefin-based resin sheet Tests were conducted in accordance with Article 4 of the Fire Service Act Enforcement Regulations (JIS Standard L-1091: A-2 Method Category 3: 2 minutes heating) and evaluated according to the following criteria.
○: Carbonization area of 40 cm ² or less, afterflame time of 5 seconds or less, residual time of 20 seconds or less, and carbonization distance of 20 cm or less.
×: One or more items of carbonization area, afterflame time, residual time, and carbonization distance exceed the standard values.

(II) Evaluation of light resistance of polyolefin resin sheet A light resistance acceleration test (JIS standard L-0842) using a sunshine carbon weather meter is conducted for 500 hours, and the color change of the discoloration color of the surface of the sample is based on the sample before the acceleration. It was digitized as ΔE (JIS standard Z-8729), and the discoloration was evaluated according to the following criteria.
ΔE = 0 to 2.9: Good without any discoloration. The initial state is maintained.
ΔE = 3 to 7.9: Δ = Slightly discolored, but no problem in practical use.
ΔE = 8˜: × = discoloration is noticeable and practically difficult to use.
Further, the residual strength after a 500-hour light resistance acceleration test for a 0.3 mm thick film was measured, and the strength retention rate was determined. (JIS standard K-6301)

(III) Evaluation of high frequency welder fusion property The ends of two polyolefin resin sheets are linearly overlapped with a width of 4 cm and a weld bar of 4 cm × 30 cm (tooth shape: convex portions are linearly shaped with a 4 cm width at regular intervals 9 High frequency welder fusion machine (Yamamoto Vinita) (equipment: 25.4mm, height of convex part 0.5mm: concave part is 4cm wide, linearly shaped 9 pieces / 25.4mm, concave part depth 0.5mm) Using a YF-7000 type manufactured by Kogyo Co., Ltd. (output: 7 kW), high-frequency fusion bonding was performed on the overlapping portion of the polyolefin resin sheet. Further, a sample having a width of 3 cm including the fusion bonded portion was collected, a shear test (JIS standard 1-1096) of the fusion bonded portion was performed, and the fracture state of the bonded portion was evaluated according to the following criteria.
<High frequency fusion property>
○: Fusing is easy.
* Welder fusion conditions: fusion time 5 seconds, cooling time 5 seconds
Anode current 0.8A, weld bar temperature 40-50 ° C
(Triangle | delta): It can melt | fuse by making fusion conditions strong and long.
* Welder fusion conditions: fusion time 10 seconds, cooling time 5 seconds
Anode current 1.0A, weld bar temperature 40-60 ° C
X: Even if the fusion conditions are strong and set long, no fusion occurs.
* Welder fusion conditions: fusion time 10 seconds, cooling time 5 seconds
Anode current 1.3A, weld bar temperature 40-60 ° C

(IV) Evaluation of joint strength From the welder fusion sheet of (III), a test piece including a 4 cm wide overlap part, a test piece width of 3 cm, and a test piece length of 30 cm was collected, and a tensile tester (Toyo Seiki Seisakusho ( The test piece was pulled until it broke using Strograph V10).
○: Destructed except at the joint.
Δ: Some thread breakage was broken at the joint.
X: Yarn breakage at the joint was broken.

(V) Evaluation of workability A gap between rolls was set to 1 mm, and 100 g of a polyolefin resin compound to be tested was put into a 6-inch diameter two roll (test roll) set at a heating temperature of 140 ° C. Kneading was performed for 5 minutes. Next, the critical oxygen index defined in JIS standard K-7231 was measured using a 1 mm thick sheet obtained by kneading.
○: Kneading was easy and completed within 5 minutes. The critical oxygen index of the obtained compound was less than ± 2% of the designed value.
Δ: Complete mixing was difficult within 5 minutes, and powder spilled under the roll. The critical oxygen index of the obtained compound was ± 2 to 5% of the designed value.
X: Complete kneading was difficult within 5 minutes, and powder spilled under the roll. The critical oxygen index of the obtained compound was ± 5% of the designed value.

(VI) Abrasion resistance of sheet JIS standard L-1096: Wear strength test C method (taper type method: wear wheel CS-18: load 1 kg) was used to determine the weight loss and evaluated according to the following criteria.
○: Abrasion loss 30 mg or less △: Abrasion loss 31-99 mg
×: Wear loss of 100 mg or more

(VII) Evaluation of sheet bloom resistance (bleed) A 10 cm × 10 cm size sample was taken from the sheet of (V), left in a refrigerator at 0 ° C. for 24 hours, and then set to 40 ° C. It was left to stand in a gear oven for 24 hours. With this as one cycle, the environmental temperature change of 0 ° C. → 40 ° C. → 0 ° C. → 40 ° C. → 0 ° C. was continued and the surface of the sample of the fifth cycle was visually observed.
○: Bloom is not confirmed (appearance is leaning)
Δ: Slight bloom is observed (appearance is cloudy)
×: Bloom is remarkable (surface is white)

Reference example 1
30 parts by weight of linear low density polyethylene resin (1) obtained by polymerization in the presence of a metallocene catalyst (Trademark: Kernel KF360: MFR2.0: Density 0.898: manufactured by Nippon Polychem Co., Ltd.), ethylene -Vinyl acetate copolymer resin (1) (Trademark: Evertate K2010: MFR3.0: VA content 25% by weight: manufactured by Sumitomo Chemical Co., Ltd.) 40 parts by weight of polyolefin resin blend consisting of 40 parts by weight bromine Compound organic compound (1) (trademark SAYTEX8010: ethylenebispentabromodiphenyl: bromine content 82 wt%: manufactured by Albemarle Asano Co., Ltd.) 35 parts by weight was blended, and the resulting resin compound was twin-screw extruder (Thermo Bromine substituted organic compound (Plastics Industries Co., Ltd .: TPP-20F: Hot Cut Pelletizing Device) ) Was granulated 3.5mm angle cubic pellets containing 33.3 weight% concentration.

  Next, linear low density polyethylene resin (1) (trademark: Kernel KF360: MFR2) obtained by polymerization in the presence of a metallocene catalyst with respect to 105 parts by weight of the resulting bromine-substituted organic compound (1) -containing pellets. 0.0: Density 0.898: manufactured by Nippon Polychem Co., Ltd.) and light stabilizer (A-1) (trademark: Biosorb 510: 2- (2′-hydroxy-4′-octoxyphenyl) benzo Triazole: manufactured by Kyodo Yakuhin Co., Ltd.) 0.5 parts by weight and light stabilizer (A-2) (Trademark: Tinuvin 765: Bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate: 0.5 parts by weight of Ciba Specialty Chemicals Co., Ltd.) and light stabilizer (B-1) (trademark: KS-1010A-1: dioctyl tin malate polymer: manufactured by Kyodo Pharmaceutical Co., Ltd.) Parts by weight, 1.0 part by weight of a phosphate ester lubricant (trade name: LTP-2: manufactured by Kawaken Fine Chemical Co., Ltd.), and a colored pigment-containing resin pellet [(organic pigment colored pellet: trademark: HCM1617 blue: cyanine Blue (α) content 20 wt%: manufactured by Dainichi Seika Kogyo Co., Ltd.) and inorganic pigment colored pellets: Trademark: HCM2060 White: Titanium dioxide (R) 60 wt%: Dainichi Seika Kogyo Co., Ltd. 2 parts by weight) 3 parts by weight.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (Nishimura Seisakusho Co., Ltd .: 2 rolls of 6 inches diameter), and then the roll interval of the test rolls was adjusted to 0.17 mm, A polyolefin resin coating film having a thickness of 0.17 mm and containing 10% by weight of a vinyl acetate component and having a LOI value of 32.4 was obtained. Next, this film was made into a polyester plain woven fabric (277.8 dtex (250 denier) polyester multifilament: yarn density warp 20 / 2.54 cm × weft 21 / 2.54 cm, porosity 20%, mass 55 g / m ^2. ) Were bonded together using a laminator having a heat roll set to 140 ° C. and a pressure-bonding roll pair. A polyolefin resin sheet having a thickness of 0.45 mm and a mass of 465 g / m ² was obtained.

Reference example 2
20 parts by weight of linear low-density polyethylene resin (2) (trademark: Evolue SP2020: MFR1.7: density 0.917: manufactured by Mitsui Chemicals, Inc.) obtained by polymerization in the presence of a metallocene catalyst, ethylene -70 parts by weight of a polyolefin-based resin blend comprising 50 parts by weight of vinyl acetate copolymer resin (2) (trademark: EVAFLEX P1905, MFR2.5, VA content 19% by weight, manufactured by Mitsui DuPont Polychemical Co., Ltd.) On the other hand, a compound was prepared by blending 35 parts by weight of a bromine-substituted organic compound (1) (trademark: SAYTEX 8010, ethylene bispentabromodiphenyl, bromine content 82% by weight, manufactured by Albemarle Asano Co., Ltd.). Using a screw extruder (same as in Reference Example 1), the bromine-substituted organic compound (1) was added at a concentration of 33.3% by weight. Has, to granulate the 3.5mm angle cube-shaped pellets.

  Next, to 105 parts by weight of the obtained bromine-substituted organic compound (1) -containing pellets, linear low-density polyethylene resin (2) obtained by polymerization in the presence of a metallocene catalyst (trademark: Evolu SP2020: MFR1.7). : Density 0.917: Mitsui Chemicals Co., Ltd.) 30 parts by weight and light stabilizer (A-1) (trademark: Biosorb 510: 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole: 0.5 parts by weight of Kyodo Yakuhin Co., Ltd.) and light stabilizer (A-2) (Trademark: Tinuvin 765: Bis (1,2,2,6,6-pentamethyl-4-piperidyl)) Sebacate: Ciba 0.5 parts by weight of Specialty Chemicals Co., Ltd.) and light stabilizer (B-1) (trademark: KS-1010A-1, dioctyltin malate polymer, joint product Co., Ltd.) 1.0 weight And 1.0 part by weight of a phosphate ester lubricant (trademark: LTP-2, manufactured by Kawaken Fine Chemical Co., Ltd.) and colored pigment pellets [(organic pigment colored pellets, trademark: HCM1617 blue, cyanine blue (α) Content 20% by weight: Dainichi Seika Kogyo Co., Ltd.) 1 part by weight + inorganic pigment colored pellets, trademark HCM2060 white, titanium dioxide (R) 60% by weight, Dainichi Seika Kogyo Co., Ltd.] 2 parts by weight 3 parts by weight were blended.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (same as in Reference Example 1), then the roll interval of the test roll was adjusted to 0.17 mm, and the thickness was 0.17 mm by calendar rolling. A polyolefin resin coating film containing 10% by weight of the vinyl acetate component and having a LOI value of 32.3 was formed. Next, this film was made into a polypropylene plain woven fabric (377.8 dtex (340 denier) polypropylene multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 18%, mass 65 g / m ^2. ) Were bonded by thermocompression bonding with a laminator set at 140 ° C. to produce a polyolefin resin sheet having a thickness of 0.46 mm and a mass of 480 g / m ² .

Reference example 3
Polyolefin resin blend comprising 30 parts by weight of the linear low density polyethylene resin (1) obtained by polymerization in the presence of a metallocene catalyst and 40 parts by weight of the ethylene-vinyl acetate copolymer resin (1) Bromine-substituted organic compound (1) (trademark: SAYTEX8010, ethylenebispentabromodiphenyl, bromine content: 82% by weight, manufactured by Albemarle Asano Co., Ltd.) and 70 parts by weight of inorganic compound (trademark: Patox) L, antimony trioxide, manufactured by Nippon Seiko Co., Ltd.) and 10 parts by weight of the compound obtained, and the resulting compound using a twin-screw extruder (same as in Reference Example 1), the bromine-substituted organic compound (1) And 3.5 mm square cubic pellets containing the inorganic compound in a total amount of 33.3% by weight.

  Next, with respect to 105 parts by weight of the obtained pellets, 30 parts by weight of the linear low density polyethylene resin (1) obtained by polymerization in the presence of a metallocene catalyst, and the light stabilizer (A-1) 0 0.5 parts by weight and a light-resistant stabilizer (A-3) (trademark: Tinuvin 114, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.5 parts by weight of the light stabilizer (B-1), and phosphoric acid 1.0 part by weight of an ester lubricant (same as in Reference Example 1) and 3 parts by weight of colored pigment pellets (pigment colored pellets: the same as in Reference Example 1) were blended.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (same as in Reference Example 1), then the roll interval of the test roll was adjusted to 0.17 mm, and the thickness of 0.17 mm was adjusted by calendar rolling. A film for polyolefin resin coating layer containing 10% by weight of a vinyl acetate component and having a LOI value of 35.6 was obtained. Next, the obtained film was made into a polyester plain woven fabric (277.8 dtex (250 denier) polyester multifilament, yarn density warp 20 / 2.54 cm × 21 weft / 2.54 cm, porosity 17%, mass 55 g / The both sides of m ² ) were bonded together using a laminator having a heat roll set at a temperature of 140 ° C. and a pressure-bonding roll pair to produce a polyolefin resin sheet having a thickness of 0.45 mm and a mass of 465 g / m ² .

Reference example 4
Polyolefin resin blend 70 comprising 20 parts by weight of the linear low density polyethylene resin (2) obtained by polymerization in the presence of a metallocene catalyst and 50 parts by weight of the ethylene-vinyl acetate copolymer resin (2). Bromine-substituted organic compound (1) (trademark: SAYTEX8010, ethylenebispentabromodiphenyl, bromine content 82% by weight, manufactured by Albemarle Asano Co., Ltd.) and inorganic compound (trademark: Patox L, relative to parts by weight) Using a twin screw extruder (same as in Reference Example 1), a bromine substituted organic compound (1) and an inorganic compound were blended with 10 parts by weight of antimony trioxide, manufactured by Nippon Seiko Co., Ltd. A 3.5 mm square cubic pellet containing a total concentration of 33.3% by weight was granulated.

  Next, with respect to 105 parts by weight of the obtained pellets, 30 parts by weight of the linear low-density polyethylene resin (2) obtained by polymerization in the presence of a metallocene catalyst, and the light stabilizer (A-1) 0 .5 parts by weight and light stabilizer (A-3) (Trademark: Tinuvin 114, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- Dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.5 parts by weight of the light stabilizer (B-1), and phosphoric acid 1.0 part by weight of an ester lubricant (same as in Reference Example 1) and 3 parts by weight of colored pigment pellets (pigment colored pellets: as in Reference Example 1) were blended.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (same as in Reference Example 1), then the roll interval of the test roll was adjusted to 0.17 mm, and the thickness of 0.17 mm was adjusted by calendar rolling. A polyolefin resin coating film containing 10% by weight of a vinyl acetate component and having a LOI value of 35.5 was obtained. Next, the obtained film was made into a polypropylene plain woven fabric (377.8 dtex (340 denier) polypropylene multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 18%, mass 65 g / A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 480 g / m ² was prepared on both sides of m ² ) by thermocompression bonding using a laminator set at a temperature of 140 ° C.

Reference Example 5
Polyolefin resin blend comprising 50 parts by weight of the linear low density polyethylene resin (1) obtained by polymerization in the presence of a metallocene catalyst and 20 parts by weight of the ethylene-vinyl acetate copolymer resin (1) 70 parts by weight obtained by blending 35 parts by weight of a bromine-substituted organic compound (2) (trademark: SAYTEX-BT-93, ethylenebistetrabromophthalimide, bromine content 67% by weight, manufactured by Albemarle Asano Co., Ltd.) Using a twin screw extruder (same as in Reference Example 1), 3.5 mm square cubic pellets containing the bromine-substituted organic compound (2) at a concentration of 33.3% by weight were granulated.

  Next, to 105 parts by weight of the obtained pellets, ethylene-methyl methacrylate copolymer resin (trademark: ACRIFTH WH206, MFR2.0, MMA content 20% by weight, manufactured by Sumitomo Chemical Co., Ltd.) 30 weights, 0.5 parts by weight of the light-resistant stabilizer (A-1) and 0.5 parts by weight of the light-resistant stabilizer (A-2) are mixed with the light-resistant stabilizer (B-2) (trademark: Alkamizer I, synthetic hydrotal Site: 1.0 part by weight of Kyowa Chemical Industry Co., Ltd.), 1.0 part by weight of a phosphate ester lubricant (same as in Reference Example 1), and colored pigment color pellets (pigment colored pellets: same as in Reference Example 1) ) 3 parts by weight.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (same as in Reference Example 1), the roll interval of the test roll was adjusted to 0.17 mm, and the thickness of 0.17 mm was adjusted by calendar rolling. A polyolefin resin coating layer film having a total content of a vinyl acetate component and a methyl methacrylate component of 11% by weight and a LOI value of 30.2 was obtained. Next, the obtained film was made into a polyester plain woven fabric (555.6 dtex (500 denier) polyester multifilament, yarn density warp 20 / 2.54 cm × weft 21 / 2.54 cm, porosity 19%, mass 75 g / m. ² ) was laminated with a laminator having a hot roll set at 140 ° C. and a pressure-bonding roll pair on both sides to produce a polyolefin resin sheet having a thickness of 0.46 mm and a mass of 485 g / m ² .

Reference Example 6
Polyolefin resin blend comprising 50 parts by weight of the linear low density polyethylene resin (1) obtained by polymerization in the presence of a metallocene catalyst and 20 parts by weight of the ethylene-vinyl acetate copolymer resin (1) 70 parts by weight of a bromine-substituted organic compound (2) (trademark: SAYTEX-BT-93, ethylenebistetrabromophthalimide, bromine content 67% by weight, manufactured by Albemarle Asano Co., Ltd.) and an inorganic compound ( Trademark: Patox L, antimony trioxide, manufactured by Nippon Seiko Co., Ltd. (10 parts by weight) were blended, and the resulting compound was brominated with an organic compound (2) using a twin-screw extruder (same as in Reference Example 1). ) And an inorganic compound in a total concentration of 33.3% by weight were granulated into 3.5 mm square cubic pellets.

  Next, with respect to 105 parts by weight of the obtained pellets, ethylene-methyl methacrylate copolymer resin (trademark: ACRIFTH WH206, MFR2.0, MMA content 20% by weight, manufactured by Sumitomo Chemical Co., Ltd.) 30 weights, 0.5 part by weight of the light stabilizer (A-1), 0.5 part by weight of the light stabilizer (A-2), and light stabilizer (B-2) (trademark: Alkamizer I, synthetic hydrotal Site, manufactured by Kyowa Chemical Industry Co., Ltd.) 1.0 part by weight, phosphate ester lubricant (same as in Reference Example 1) 1.0 part by weight, and as colored pigment pellets (pigment colored pellets, same as Reference Example 1) ) 3 parts by weight.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (same as in Reference Example 1), then the roll interval of the test roll was adjusted to 0.20 mm, and the thickness was adjusted to 0. A polyolefin resin coating layer film having a total content of vinyl acetate component and methyl methacrylate component of 11% by weight and a LOI value of 33.1 was prepared. Next, the obtained film was made into a polyester plain woven fabric (833.3 dtex (750 denier) polyester multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 22%, mass 95 g / m. ² ) was laminated with a laminator having a heat roll set at 140 ° C. and a pair of pressure-bonding rolls on both sides to prepare a polyolefin resin sheet having a thickness of 0.50 mm and a mass of 535 g / m ² .

Reference Example 7
Polyolefin resin blend 70 comprising 50 parts by weight of the linear low-density polyethylene resin (1) obtained by polymerization in the presence of a metallocene catalyst and 20 parts by weight of the ethylene-vinyl acetate copolymer resin (1). Bromine-substituted organic compound (1) (trademark: SAYTEX8010, ethylenebispentabromodiphenyl, bromine content 82% by weight, manufactured by Albemarle Asano Co., Ltd.) and 10 parts by weight of inorganic compound (trademark: Patox L) 5 parts by weight of antimony trioxide, manufactured by Nippon Seiko Co., Ltd.) and 5 parts by weight of phosphorus-containing compound (1) (trademark: Nova Excel ST300, red phosphorus, manufactured by Rin Chemical Industry Co., Ltd.) The resulting compound was combined with a bromine-substituted organic compound (1), an inorganic compound and a phosphorus-containing compound (1) using a twin-screw extruder (same as in Reference Example 1). Content to granulate the 22.2 wt% of 3.5mm square cubic pellets.

  Next, to 90 parts by weight of the obtained pellets, ethylene-methyl methacrylate copolymer resin (trademark: ACRIFTH WH206, MFR2.0, MMA content 20% by weight, manufactured by Sumitomo Chemical Co., Ltd.) 30 weights, 0.5 parts by weight of the light-resistant stabilizer (A-1), 0.5 parts by weight of the light-resistant stabilizer (A-3), 1.0 part by weight of the light-resistant stabilizer (B-2), and the phosphate ester 1.0 part by weight of a lubricant (same as in Reference Example 1) and 2 parts by weight of colored pigment pellets ((organic pigment colored pellets, trademark: HCM1717 black, carbon content 10% by weight, manufactured by Dainichi Seika Kogyo Co., Ltd.) Part + inorganic pigment colored pellets, trademark: HCM2060 white, titanium dioxide (R) 60% by weight, manufactured by Dainichi Seika Kogyo Co., Ltd.] 2 parts by weight] and 4 parts by weight.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (same as in Reference Example 1), the roll distance of the test roll was adjusted to 0.17 mm, and the thickness was 0.17 mm by calendar rolling. A polyolefin resin coating layer film having a total content of vinyl acetate component and methyl methacrylate component of 11% by weight and a LOI value of 36.3 was obtained. Next, the obtained film was applied to both sides of a polyester plain woven fabric (500 denier polyester multifilament, yarn density warp 20 / 2.54 cm × weft 21 / 2.54 cm, porosity 19%, mass 75 g / m ² ). A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 485 g / m ² was obtained by laminating with a laminator having a heat roll set to 140 ° C. and a pressure-bonding roll pair.

Reference Example 8
Polyolefin resin blend comprising 50 parts by weight of the linear low density polyethylene resin (1) obtained by polymerization in the presence of a metallocene catalyst and 20 parts by weight of the ethylene-vinyl acetate copolymer resin (1) 70 parts by weight of a bromine-substituted organic compound (1) (trademark: SAYTEX8010, ethylenebispentabromodiphenyl, bromine content 82% by weight, manufactured by Albemarle Asano Co., Ltd.) and an inorganic compound (trademark: Patox L 5 parts by weight of antimony trioxide, manufactured by Nippon Seiko Co., Ltd., and 10 parts by weight of phosphorus-containing compound (2) (trademark: Terrage C60, microencapsulated ammonium polyphosphate, manufactured by Chisso Corporation) . Using the twin screw extruder (same as in Reference Example 1), the total amount of the bromine-substituted organic compound (1), the inorganic compound, and the phosphorus-containing compound (2) is 30% by weight. A 3.5 mm square cubic pellet was granulated.

  Next, with respect to 100 parts by weight of the obtained pellets, ethylene-methyl methacrylate copolymer resin (trademark: ACRIFTH WH206, MFR2.0, MMA content 20% by weight, Sumitomo Chemical Co., Ltd.) 30%, 0.5 part by weight of light stabilizer (A-1), 0.5 part by weight of light stabilizer (A-3), 1.0 part by weight of light stabilizer (B-2), and phosphoric acid 1.0 part by weight of an ester lubricant (same as in Reference Example 1) and 3 parts by weight of colored pigment pellets (pigment colored pellets: the same as in Reference Example 1) were blended.

The obtained compound was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (same as in Reference Example 1), then the roll interval of the test roll was adjusted to 0.20 mm, and the thickness was 0.20 mm by calendar rolling. A polyolefin-based resin coating layer film having a total content of vinyl acetate component and methyl methacrylate component of 11% by weight and an LOI value of 32.7 was obtained. Next, the obtained film was made into a polyester plain woven fabric (833.3 dtex (750 denier) polyester multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 22%, mass 95 g / m. ² ) was laminated with a laminator having a hot roll set at a temperature of 140 ° C. and a pressure-bonding roll pair to prepare a polyolefin resin sheet having a thickness of 0.50 mm and a mass of 535 g / m ² .

  The test results of Reference Examples 1 to 8 are shown in Table 1.

Effects of Reference Examples 1 to 8 The polyolefin resin sheets of Reference Examples 1 to 8 all have a flameproof property that complies with the Fire Service Law, and using a conventional high-frequency welder dedicated to polyvinyl chloride resin. It was possible to facilitate fusion bonding (anode current value was 0.8 A, fusion time 5 seconds, cooling time 5 seconds, weld bar temperature 40 to 50 ° C.). In addition, the state of shear fracture of these joints did not reach the main body with partial thread breakage failure, but it has 85% or more of the main body fracture strength, so that there is no practical problem at all. It was not. Furthermore, when the heat-resistant creep resistance test was evaluated, all of the polyolefin resin sheets of Reference Examples 1 to 8 passed the heat-resistant creep test of 60 ° C. × 25 kgf load × 24 hours. The polyolefin resin sheets of Reference Examples 1 to 8 were also excellent in light resistance, and the color change ΔE value in the accelerated test for 500 hours by the sunshine carbon weather meter was 3 or less. In addition, the film residual strength retention after 500 hours of accelerated light resistance is 90% or more, and all these sheets have a soft texture and are not inferior to the texture of the sheet made of soft polyvinyl chloride resin. Therefore, it was confirmed that the polyolefin resin sheets of Reference Examples 1 to 8 were suitable for outdoor use. In particular, the polyolefin resin sheets of Reference Examples 1 to 8 are excellent in processability during production, and the kneadability of halogen-substituted organic compounds, inorganic compounds, and phosphorus-containing compounds is efficient and It was confirmed that the flame resistance of the obtained sheet was not varied because it was carried out accurately, and that the flame resistance was reliable.

Example 1
Polyester plain woven fabric of Reference Example 1 (277.8 dtex (250 denier) polyester multifilament: yarn density warp 20 / 2.54 cm × 21 weft / 2.54 cm: porosity 17%: mass 55 g / m ² ) A polyolefin resin sheet having a thickness of 0.45 mm and a mass of 468 g / m ² was prepared according to the same composition and procedure as in Reference Example 1 except that the following pretreatment (1) was performed.
<Pretreatment agent composition (1)>
Trademark: Nip seal E200, manufactured by Nippon Silica Industry Co., Ltd.
Synthetic amorphous silica, water content 6% by weight, average particle size 3 μm 10 parts by weight Trademark: Aquatex E-1800, manufactured by Chuo Rika Kogyo Co., Ltd.
Ethylene-vinyl acetate copolymer resin emulsion (solid content: 40% by weight) 50 parts by weight Diluent: 150 parts by weight of distilled water The polyester plain woven fabric is immersed in a bath of the above-mentioned pretreatment agent (1) and woven. The fabric was pulled up and simultaneously squeezed with a nip roll (wet adhesion mass 30 g / m ² ), and then dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester plain woven fabric obtained by the pretreatment was 58 g / m ² . (Synthetic amorphous silica: thermoplastic resin weight ratio = 10: 20)

Example 2
Polypropylene plain woven fabric of Reference Example 2 (377.8 dtex (340 denier) polypropylene multifilament: yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm: porosity 18%: mass 65 g / m ² ) In the same pretreatment liquid (1) as in Example 1, the woven fabric was pulled up and simultaneously squeezed with a nip roll (wet weight 30 g / m ² ), and then dried in a hot air oven at 100 ° C. for 2 minutes. did. The mass of the polypropylene plain woven fabric obtained by the pretreatment was 68 g / m ² (synthetic amorphous silica: thermoplastic resin weight ratio = 10: 20). A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 483 g / m ² was prepared in accordance with the same formulation and procedure as in Reference Example 2 except that the above pretreatment (1) was performed.

Example 3
Polyester plain woven fabric of Reference Example 3 (277.8 dtex (250 denier) polyester multifilament, yarn density warp 20 / 2.54 cm × 21 weft / 2.54 cm, porosity 17%, mass 55 g / m ² ) A polyolefin resin sheet having a thickness of 0.45 mm and a mass of 468 g / m ² was prepared in accordance with the same composition and procedure as in Reference Example 3 except that the following pretreatment liquid (2) was applied.
<Pretreatment agent composition (2)>
Trademarks: Snowtex C, manufactured by Nippon Silica Industry,
Silica anhydride content 20% by weight, average particle size 10-20 nm 100 parts by weight Trademark: KBM303, manufactured by Shin-Etsu Chemical Co., Ltd.,
Epoxy silane coupling agent (active ingredient 100% by weight) 3 parts by weight Diluent: distilled water 50 parts by weight A polyester plain weave woven fabric is immersed in the above-mentioned pretreatment agent (2) bath, and the woven fabric is pulled up and nip rolls. And then squeezed (wet adhesion mass 30 g / m ² ), and then dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester plain woven fabric obtained by the pretreatment was 58 g / m ² (silicic anhydride: silane coupling agent weight ratio = 20: 3).

Example 4
Polypropylene plain woven fabric of Reference Example 4 (377.8 dtex (340 denier) polypropylene multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 18%, mass 65 g / m ² ) It was immersed in the same pretreatment liquid (2) as in Example 3, the woven fabric was pulled up, and simultaneously squeezed with a nip roll (wet weight 30 g / m ² ), and then dried in a hot air oven at 100 ° C. for 2 minutes. . The mass of the polypropylene plain woven fabric obtained by the pretreatment was 68 g / m ² (silica anhydride: silane coupling agent weight ratio = 20: 3). A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 483 g / m ² was prepared in accordance with the same formulation and procedure as in Reference Example 4 except that the pretreatment (2) was performed.

Example 5
Polyester plain woven fabric of Reference Example 5 (555.6 dtex (500 denier) polyester multifilament, yarn density warp 20 / 2.54 cm × weft 21 / 2.54 cm, porosity 19%, mass 75 g / m ² , Teijin A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 488 g / m ² was prepared according to the same composition and procedure as in Reference Example 5 except that the following pretreatment (3) was applied to (Co.). did.
<Pretreatment agent composition (3)>
Trademark: Nip seal E200, manufactured by Nippon Silica Industry Co., Ltd.
Synthetic amorphous silica, water content 6% by weight, average particle size 3 μm 10 parts by weight Trademark: KBM303, Shin-Etsu Chemical Co., Ltd.,
Epoxy silane coupling agent (active ingredient 100% by weight) 3 parts by weight Diluent: 150 parts by weight distilled water At the same time as immersing the polyester plain weave fabric in the above-mentioned pretreatment agent (3) bath and pulling up the fabric The film was squeezed with a nip roll (wet mass of 30 g / m ² ), and then dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester plain woven fabric obtained by the pretreatment was 78 g / m ² . (Synthetic amorphous silica: silane coupling agent weight ratio = 10: 3)

Example 6
Polyester plain woven fabric of Reference Example 6 (833.3 dtex (750 denier) polyester multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 22%, mass 95 g / m ² ) In the same pretreatment liquid (3) as in Example 5, the woven fabric was pulled up and simultaneously squeezed with a nip roll (wet mass of 30 g / m ² ), and then dried in a hot air oven at 100 ° C. for 2 minutes. did. The mass of the polyester plain woven fabric obtained by the pretreatment was 98 g / m ² (synthetic amorphous silica: silane coupling agent weight ratio = 10: 3). A polyolefin resin sheet having a thickness of 0.50 mm and a mass of 538 g / m ² was prepared according to the same composition and procedure as in Reference Example 6 except that the pretreatment (3) was performed.

Example 7
Polyester plain woven fabric of Reference Example 7 (555.6 dtex (500 denier) polyester multifilament, yarn density warp 20 / 2.54 cm × weft 21 / 2.54 cm, porosity 19%, mass 75 g / m ² , Teijin A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 488 g / m ² was prepared according to the same composition and procedure as in Reference Example 7 except that the following pretreatment (4) was applied to (Co.). did.
<Pretreatment agent composition (4)>
Trademarks: Nip seal E200, Nippon Silica Industry Co., Ltd.
Synthetic amorphous silica, water content 6% by weight, average particle size 3 μm 10 parts by weight Trademark: KBM303, Shin-Etsu Chemical Co., Ltd.,
Epoxy silane coupling agent (active ingredient 100% by weight) 3 parts by weight Trademark: Aquatex E-1800, Chuo Rika Kogyo Co., Ltd.,
Ethylene-vinyl acetate copolymer resin emulsion (solid content: 40% by weight) 50 parts by weight Diluent: 150 parts by weight of distilled water A polyester plain weave woven fabric is immersed in a bath of the above-mentioned pretreatment agent (4) to prepare a woven fabric. At the same time as pulling up, it was squeezed with a nip roll (wet mass of 30 g / m ² ) and then dried in a hot air oven at 100 ° C. for 2 minutes. The mass of the polyester plain woven fabric obtained by the pretreatment was 78 g / m ² . (Synthetic amorphous silica: silane coupling agent: thermoplastic resin weight ratio = 10: 3: 20)

Example 8
Polyester plain woven fabric of Reference Example 8 (833.3 dtex (750 denier) polyester multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 22%, mass 95 g / m ² ) In the same pretreatment liquid (4) as in Example 7, the woven fabric was pulled up and simultaneously squeezed with a nip roll (wet mass of 30 g / m ² ), and then dried in a hot air oven at 100 ° C. for 2 minutes. did. The mass of the polyester plain woven fabric obtained by the pretreatment was 98 g / m ² (synthetic amorphous silica: silane coupling agent: thermoplastic resin weight ratio = 10: 3: 20). A polyolefin resin sheet having a thickness of 0.50 mm and a mass of 538 g / m ² was prepared in accordance with the same formulation and procedure as in Reference Example 8 except that the pretreatment (4) was performed.

  The test results of Examples 1 to 8 are shown in Table 2.

Effects of Examples 1 to 8 The polyolefin resin sheets of Examples 1 to 8 all have flameproofness that complies with the Fire Service Act, and are fusion-bonded by a conventional high-frequency welder dedicated to polyvinyl chloride resin. (Anode current value was 0.8 A, fusion time 5 seconds, cooling time 5 seconds, weld bar temperature 40-50 ° C.). Moreover, these sheets were stably improved to the extent that the shear fracture of the joint part was destroyed by subjecting the fiber fabric to a pretreatment containing a silicon compound. In particular, the pretreatment containing these silicon compounds is the joining of the polyolefin resin sheets of Reference Examples 1 to 8 without the problem of texture hardening and the problem of reduction in tear strength, which was a problem of the conventional adhesive treatment. This was a treatment that could improve the partial thread breakage failure. Furthermore, when the heat-resistant creep resistance test was evaluated, all of the polyolefin resin sheets of Examples 1 to 8 passed the heat-resistant creep test of 60 ° C. × 25 kgf load × 24 hours. The polyolefin resin sheets of Examples 1 to 8 were also excellent in light resistance, and the color change ΔE value in the accelerated test for 500 hours by the sunshine carbon weather meter was all 3 or less. In addition, the film residual strength retention after 500 hours of accelerated light resistance is 90% or more, and all these sheets have a soft texture and are not inferior to the texture of the sheet made of soft polyvinyl chloride resin. Therefore, the polyolefin resin sheets of Examples 1 to 8 were determined to be suitable for outdoor use. In particular, the polyolefin resin sheets of Examples 1 to 8 are excellent in processability during production, and the kneadability of halogen-substituted organic compounds, inorganic compounds, and phosphorus-containing compounds is efficient and Since it was carried out accurately, there was no variation in the flame resistance of the obtained sheet, and the flame resistance was reliable.

Comparative Example 1
A polyolefin resin sheet was produced in the same manner as in Reference Example 1. However, linear low density polyethylene resin (1) obtained by polymerization in the presence of the metallocene catalyst of Reference Example 1 (trademark, Kernel KF360, MFR2.0, density 0.898, manufactured by Nippon Polychem Co., Ltd.) 60 parts by weight of a linear low density polyethylene resin polymerized in the presence of a Ziegler-Natta catalyst (Trademark: Sumikasen α / FZ203-0, MFR 2.0, density 0.932, manufactured by Sumitomo Chemical Co., Ltd.) 10 parts by weight of ethylene-vinyl acetate copolymer resin (1) (Trademark: Evertate K2010, MFR3.0, VA content 25% by weight, manufactured by Sumitomo Chemical Co., Ltd.) In addition, light stabilizer (A-1) (Trademark Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, manufactured by Kyodo Yakuhin Co., Ltd.) Was changed from 0.5 parts by weight to 1.5 parts by weight, and light stabilizer (A-2) (trademark: Tinuvin 765, bis (1,2,2,6,6-pentamethyl-4-piperidyl) ) Sebacate, manufactured by Ciba Specialty Chemicals Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight, and light stabilizer (B-1) (trademark: KS-1010A-1, Dioctyl) The amount of tin malate polymer, manufactured by Kyodo Yakuhin Co., Ltd. was changed from 1.0 part by weight to 1.5 parts by weight. Further, in Comparative Example 1, the above compounding compound was kneaded for 5 minutes with a test roll (Nishimura Seisakusho Co., Ltd .: two 6 inch diameter rolls) set to 150 ° C. by batch charging (the compounding material that could not be kneaded in 5 minutes was from the compounding system). Excluded). Next, from this compound, a polyolefin resin coating layer film having a thickness of 0.17 mm, containing 2.5% by weight of a vinyl acetate component, and having a LOI value of 28.8 was obtained by calender rolling. A polyester plain woven fabric (277.8 dtex (250 denier) polyester multifilament: yarn density warp 20 / 2.54 cm × 21 weft / 2.54 cm: porosity 17%: mass 55 g / m ²⁾ was laminated on both surfaces of a thickness of 0.45 mm, to prepare a polyolefin-based resin sheet weight 465 g / m ^2.

Comparative Example 2
A polyolefin resin sheet was prepared in the same manner as in Reference Example 2. However, linear low density polyethylene resin (2) polymerized in the presence of the metallocene catalyst of Reference Example 2 (trademark: Evolu SP2020, MFR1.7, density 0.917, manufactured by Mitsui Chemicals, Inc.) 50 parts by weight Was changed to 90 parts by weight, and ethylene-vinyl acetate copolymer resin (2) (trademark: Everflex P1905, MFR2.5, VA content 19% by weight, manufactured by Mitsui DuPont Polychemical Co., Ltd.) 50 parts by weight The light-resistant stabilizer (A-1) (trademark: Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, manufactured by Kyodo Yakuhin Co., Ltd.) Was changed from 0.5 parts by weight to 1.5 parts by weight, and light stabilizer (A-2) (trademark: Tinuvin 765, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate, manufactured by Ciba Specialty Chemicals Co., Ltd. was changed from 0.5 parts by weight to 1.5 parts by weight, and light-resistant stabilizer (B-1) (trademark: KS-1010A-1, dioctyltin) The blending amount of malate polymer, manufactured by Kyodo Yakuhin Co., Ltd. was changed from 1.0 part by weight to 1.5 parts by weight. Further, in Comparative Example 2, the above compounding compound was added all at once, and kneaded for 5 minutes with a test roll set at 150 ° C. (Nishimura Seisakusho Co., Ltd .: two 6-inch diameter rolls). Excluded). Next, a film for polyolefin resin coating layer having a thickness of 0.17 mm, containing 2% by weight of a vinyl acetate component, and having a LOI value of 29.2 was obtained from this compound by calendar rolling. In accordance with the same procedure as in Reference Example 2, this film was subjected to a polypropylene plain woven fabric (377.8 dtex (340 denier) polypropylene multifilament: yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 18%, A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 480 g / m ² laminated on both surfaces having a mass of 65 g / m ² ) was obtained.

Comparative Example 3
A polyolefin resin sheet was produced in the same manner as in Reference Example 3. However, linear low density polyethylene resin (1) produced by polymerization in the presence of the metallocene catalyst of Reference Example 3 (trademark: Kernel KF360, MFR2.0, density 0.898, manufactured by Nippon Polychem Co., Ltd.) 60 parts by weight of a linear low-density polyethylene resin produced by polymerization in the presence of a Ziegler-Natta catalyst (trademark: Sumikasen α · FZ203-0, MFR 2.0, density 0.932, Sumitomo Chemical Co., Ltd.) ) Made by changing to 10 parts by weight, and ethylene-vinyl acetate copolymer resin (1) (trademark: Evertate K2010, MFR3.0, VA content 25% by weight, manufactured by Sumitomo Chemical Co., Ltd.) 40 parts by weight Was changed to 90 parts by weight, and the light stabilizer (A-1) (trademark Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, Manufactured by Kyodo Yakuhin Co., Ltd.), light stabilizer (A-3) (trademark: Tinuvin 114, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, manufactured by Ciba Specialty Chemicals Co., Ltd.), light stabilizer (B-1) (trademark: KS-1010A-1, dioctyltin malate polymer) All of the three combinations of Kyodo Yakuhin Co., Ltd. were omitted. In Comparative Example 3, the above blended compound was kneaded for 5 minutes with a test roll set at 150 ° C. by batch loading (blended materials that could not be kneaded in 5 minutes were excluded from the blending system). Next, a film for polyolefin-based resin coating layer having a thickness of 0.17 mm, containing 22% by weight of a vinyl acetate component, and having a LOI value of 32.3 was obtained from this compound by calendar rolling. This film was made into a polyester plain woven fabric (277.8 dtex (250 denier) polyester multifilament: yarn density warp 20 yarns / 2.54 cm × weft yarn 21 yarns / 2.54 cm: porosity 17% according to the same procedure as in Reference Example 1. : it was laminated on both sides of the mass 55g / m ^2), to obtain a thickness 0.45 mm, mass 465 g / m ² polyolefin resin sheet.

Comparative Example 4
Use of linear low density polyethylene resin (2) produced by polymerization in the presence of a metallocene catalyst of Reference Example 4 (trademark: Evolu SP2020, MFR1.7, density 0.917, manufactured by Mitsui Chemicals, Inc.) The amount was changed from 50 parts by weight to 10 parts by weight, and ethylene-vinyl acetate copolymer resin (2) (Trademark: Evaflex P1905, MFR2.5, VA content 19% by weight, manufactured by Mitsui DuPont Polychemical Co., Ltd.) In addition, the light-use stabilizer (A-1) (trademark: Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, co-chemicals was changed from 50 parts by weight to 90 parts by weight. Product), light stabilizer (A-3) (trademark: Tinuvin 114, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1- The Tilethyl) -4-hydroxyphenyl] methyl] butyl malonate, manufactured by Ciba Specialty Chemicals Co., Ltd.), light stabilizer (B-1) (trademark: KS-1010A-1, dioctyltin malate polymer, joint chemical) All of the three types of blends) were omitted. In Comparative Example 4, the above compounding compound was kneaded for 5 minutes with a test roll set at 150 ° C. by batch charging (the compounding material that could not be kneaded in 5 minutes was excluded from the compounding system). Next, from this compound, a polyolefin resin blend film having a thickness of 0.17 mm, containing 18% by weight of a vinyl acetate component, and having a LOI value of 32.7 was produced by calender rolling. This film was made into a polypropylene plain woven fabric (377.8 dtex (340 denier) polypropylene multifilament: yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm: porosity 18 according to the same procedure as in Reference Example 2. %: Mass 65 g / m ² ), a polyolefin resin sheet having a thickness of 0.46 mm and a mass of 480 g / m ² was obtained.

Comparative Example 5
A polyolefin resin sheet was produced in the same manner as in Reference Example 5. However, linear low density polyethylene resin (1) produced by polymerization in the presence of the metallocene catalyst of Reference Example 5 (Trademark: Kernel KF360, MFR2.0, density 0.898, manufactured by Nippon Polychem Co., Ltd.) 50 parts by weight of a linear low-density polyethylene resin produced by polymerization in the presence of a Ziegler-Natta catalyst (trademark: Sumikasen α · FZ203-0, MFR 2.0, density 0.932, Sumitomo Chemical Co., Ltd.) )) 50 parts by weight, and in the composition of the polyolefin resin blend, the light-resistant stabilizer (A-1) (trademark Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole , Manufactured by Kyodo Yakuhin Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight, and the light-resistant stabilizer (A-2) (trademarks: 2,2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by Ciba Specialty Chemicals Co., Ltd., light stabilizer (B-2) (Trademark: Alkamizer I, synthetic hydrotalcite, Kyowa Chemical Industry) 2 types of compound) were abbreviate | omitted. In Comparative Example 5, the above blended compound was kneaded for 5 minutes with a test roll set at 150 ° C. by batch charging (blended materials that could not be kneaded in 5 minutes were excluded from the blend system). Next, from this compound, a polyolefin resin blend film having a thickness of 0.17 mm, containing 11% by weight of a vinyl acetate component, and having a LOI value of 27.0 was obtained by calendar rolling. This film was made into a polyester plain woven fabric (555.6 dtex (500 denier) polyester multifilament, yarn density warp 20 / 2.54 cm × 21 weft / 2.54 cm, porosity 19% according to the same procedure as in Reference Example 5. It was laminated on both sides of the mass 75 g / m ^2), to obtain a thickness 0.45 mm, mass 485 g / m ² polyolefin resin sheet.

Comparative Example 6
A polyolefin resin sheet was produced in the same manner as in Reference Example 6. However, linear low density polyethylene resin (1) produced by polymerization in the presence of the metallocene catalyst of Reference Example 6 (trademark: Kernel KF360, MFR2.0, density 0.898, manufactured by Nippon Polychem Co., Ltd.) 50 parts by weight of a linear low-density polyethylene resin produced by polymerization in the presence of a Ziegler-Natta catalyst (trademark: Sumikasen α · FZ203-0, MFR 2.0, density 0.932, Sumitomo Chemical Co., Ltd.) )) Changed to 50 parts by weight, and in the composition of the polyolefin resin blend, light stabilizer (A-1) (trademark Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, The blending amount of Kyodo Yakuhin Co., Ltd. was changed from 0.5 parts by weight to 1.5 parts by weight, and the light resistance stabilizer (A-2) (trademark: Tinuvin 765, bis (1,2, 2,6,6-pentamethyl-4-piperidyl) sebacate, manufactured by Ciba Specialty Chemicals Co., Ltd., light stabilizer (B-2) (Trademark: Alkamizer I, synthetic hydrotalcite, Kyowa Chemical Industry Co., Ltd.) ))) Was omitted. In Comparative Example 6, the above blended compound was kneaded for 5 minutes with a test roll set at 150 ° C. by batch loading (blended materials that could not be kneaded in 5 minutes were excluded from the blend system). Next, a film for polyolefin resin coating layer having a thickness of 0.20 mm, containing 11% by weight of a vinyl acetate component, and having a LOI value of 29.8 was obtained from this compound by calendar rolling. According to the same procedure as in Reference Example 6, this film was made into a polyester plain woven fabric (833.3 dtex (750 denier) polyester multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 22 %, Mass 95 g / m ² ), a polyolefin resin sheet having a thickness of 0.50 mm and a mass of 535 g / m ² was obtained.

Comparative Example 7
A polyolefin resin sheet was prepared in the same manner as in Reference Example 7. However, linear low density polyethylene resin (1) produced by polymerization in the presence of the metallocene catalyst of Reference Example 7 (trademark: Kernel KF360, MFR2.0, density 0.898, manufactured by Nippon Polychem Co., Ltd.) 50 parts by weight of a linear low-density polyethylene resin produced by polymerization in the presence of a Ziegler-Natta catalyst (trademark: Sumikasen α · FZ203-0, MFR 2.0, density 0.932, Sumitomo Chemical Co., Ltd.) )) 50 parts by weight, and in the composition of the polyolefin resin blend, the light-resistant stabilizer (A-1) (trademark Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole , Manufactured by Kyodo Yakuhin Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight, and the light stabilizer (A-3) (trademark: Tinuvin 114, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, manufactured by Ciba Specialty Chemicals ) And light stabilizer (B-2) (trademark: Alkamizer I, synthetic hydrotalcite, Kyowa Chemical Industry Co., Ltd.) were omitted. In Comparative Example 7, the compounding compound was kneaded for 5 minutes with a test roll set at 150 ° C. by batch charging (the compounding material that could not be kneaded in 5 minutes was excluded from the compounding system). Next, a film for polyolefin resin coating layer having a thickness of 0.17 mm, containing 11 wt% of vinyl acetate component, and having a LOI value of 32.9 was obtained from this compound by calendar rolling. According to the same procedure as in Reference Example 7, this film was subjected to a polyester plain weave fabric (555.6 dtex (500 denier) polyester multifilament, yarn density warp 20 threads / 2.54 cm × 21 weft threads / 2.54 cm, porosity 19 %, was laminated on both sides of the mass 75 g / m ^2), to obtain a thickness 0.46 mm, mass 485 g / m ² polyolefin resin sheet.

Comparative Example 8
A polyolefin resin sheet was prepared in the same manner as in Reference Example 8. However, the linear low density polyethylene resin (1) produced by polymerization in the presence of the metallocene catalyst of Reference Example 8 (Trademark: Kernel KF360, MFR2.0, density 0.898, manufactured by Nippon Polychem Co., Ltd.) 50 parts by weight of a linear low-density polyethylene resin produced by polymerization in the presence of a Ziegler-Natta catalyst (trademark: Sumikasen α · FZ203-0, MFR 2.0, density 0.932, Sumitomo Chemical Co., Ltd.) )) 50 parts by weight, and in the composition of the polyolefin resin blend, the light-resistant stabilizer (A-1) (trademark Biosorb 510, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole , Manufactured by Kyodo Yakuhin Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight, and the light stabilizer (A-3) (trademark: Tinuvin 114, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, manufactured by Ciba Specialty Chemicals ) And light stabilizer (B-2) (trademark: Alkamizer I, synthetic hydrotalcite, Kyowa Chemical Industry Co., Ltd.) were omitted. In Comparative Example 8, the compounding compound was kneaded for 5 minutes with a test roll set at 150 ° C. by batch charging (the compounding material that could not be kneaded in 5 minutes was excluded from the compounding system). Next, from this compound, a polyolefin resin blend film having a thickness of 0.20 mm, containing 11% by weight of a vinyl acetate component, and having a LOI value of 28.6 was obtained by calendar rolling. This film was subjected to the same procedure as in Reference Example 8 using a polyester plain woven fabric (833.3 dtex (750 denier) polyester multifilament, yarn density warp 19 yarns / 2.54 cm × weft yarn 20 yarns / 2.54 cm, porosity 22 %, Mass 95 g / m ² ), a polyolefin resin sheet having a thickness of 0.50 mm and a mass of 535 g / m ² was obtained.

  The test results of Comparative Examples 1 to 8 are shown in Table 3.

Results of Comparative Examples 1 to 8 In Comparative Example 1, the linear low density polyethylene resin polymerized in the presence of the metallocene catalyst used in the polyolefin resin blend composition was used in the presence of a Ziegler-Natta catalyst (ZN catalyst). The polymer was replaced with a linear low-density polyethylene resin polymerized in step 1, and the blending ratio was increased to 90% by weight, so that high-frequency welder fusion was insufficient. In Comparative Example 2, since the blending ratio of the linear low density polyethylene resin polymerized in the presence of the metallocene catalyst was increased to 90% by weight, the high frequency welder fusion was insufficient. Moreover, in Comparative Example 1 and Comparative Example 2, since the blending amount of the light-resistant stabilizers (A-1), (A-2), and (B-1) was increased, the light resistance was applied to the surface of the sheet on the third day from the production. The stabilizer was blooming. (Also confirmed by Test VII.) In Comparative Examples 3 and 4, the blending ratio of the ethylene-vinyl acetate copolymer resin was increased to 90% by weight, resulting in poor wear resistance. In particular, in Comparative Examples 3 to 8 in which all of the light stabilizers (A-1), (A-2), and (B-1) were omitted, the light resistance was poor, and the sunshine carbon arc acceleration test was performed in 500 hours. The surface of the sheet turned brown. This discoloration was 8.4 to 11.5 in ΔE value, which was much inferior to the ΔE values 1.7 to 2.6 in Reference Examples 1 to 8 and Examples 1 to 8. At the same time, the strength retention of the film was reduced to 64 to 77%. (The strength retention in Examples 1 to 16 was 92 to 96%.)

  In Comparative Examples 5 to 8, the polyethylene component of Examples 5 to 8 was replaced with a linear low density polyethylene resin polymerized in the presence of a Ziegler-Natta catalyst (ZN catalyst). The occurrence of troubles in which halogen-substituted organic compounds, inorganic compounds, phosphorus-containing compounds, etc. bloom was confirmed. In Comparative Examples 1 to 8, since the sheet manufacturing method, particularly the kneading method of the polyolefin resin, the halogen-substituted organic compound, the inorganic compound, and the phosphorus-containing compound, was performed as a batch kneading, the kneading efficiency was extremely poor, Compounds such as halogen-substituted organic compounds, inorganic compounds, and phosphorus-containing compounds cannot be completely kneaded into the resin within 5 minutes of the kneading setting time, and a large amount of these compounds are under the roll of the test roll. It was in a spilled state. Therefore, the flameproof test of the sheets of Comparative Examples 1 to 8 which did not contain the prescribed amount of the halogen-substituted organic compound, the inorganic compound, and the phosphorus-containing compound was unstable and partially unsuitable. For confirmation, these compounds spilled under the roll were collected and the test roll kneading was continued again. However, these compounds still spilled under the roll. By repeating this operation, these compounds could eventually be kneaded into the resin, but during the repetition of this operation, these compounds were scattered, resulting in a large loss.

  According to the present invention, a polyolefin resin sheet having excellent light resistance and excellent flame retardancy and capable of high frequency fusion, and a polyolefin type excellent in fracture strength and heat resistance creep resistance of a high frequency fusion part A resin sheet can be easily provided. The polyolefin resin sheet obtained by the method and the production method of the present invention is a conventional soft polyvinyl chloride resin product such as a tent film material, a sheet warehouse film material, a building site curing sheet, and a building sound insulation sheet. It is a flame retardant sheet that can be suitably used for the used applications and is extremely useful as a new sheet for industrial materials that can be used outdoors for a long period of time.

Claims (21)

Formed on both surfaces of a base fabric comprising a fiber fabric pretreated with a composition containing at least one silicon compound selected from synthetic amorphous silica, colloidal silica, and a silane coupling agent; A polyolefin resin coating layer, wherein the polyolefin resin coating layer is (1) 100 parts by weight of a polyolefin resin blend,
(2) 5 to 100 parts by weight of a flame retardant containing at least one halogen-substituted organic compound, and (3) 0.005 to 3.5 parts by weight of a light-resistant stabilizer,
The polyolefin resin blend is
(A) a main component comprising a linear low-density polyethylene resin obtained by copolymerizing ethylene and an α-olefin in the presence of a metallocene catalyst, and (b) an ethylene-vinyl acetate copolymer resin and A blend component comprising at least one selected from ethylene- (meth) acrylic acid (ester) copolymer resins, and copolymerized vinyl acetate and (meth) acrylic acid (ester) contained in the blend component ) Is 5 to 30% by weight based on the weight of the polyolefin-based resin blend,
The light resistance stabilizer is at least one selected from a benzotriazole compound, a benzophenone compound, a cyanoacrylate compound, a salicylate compound, and a hindered amine compound, and an organic tin compound. A flame retardant, characterized by being a mixture comprising: a zinc-based metal composite compound, a metal soap, an epoxidized oil and fat, a hydrotalcite, and a light stabilizer component (B) comprising at least one selected from zeolite Light-resistant polyolefin resin sheet.   The flame retardant contains at least one inorganic compound in addition to the at least one halogen-substituted organic compound, and the total weight of the halogen-substituted organic compound and the inorganic compound is: The flame-retardant light-resistant polyolefin-based resin sheet according to claim 1, wherein the amount is 5 to 100 parts by weight with respect to 100 parts by weight of the polyolefin-based resin blend.   The flame retardant according to claim 1 or 2, wherein the polyolefin resin coating layer further comprises 5 to 50 parts by weight of at least one phosphorus-containing compound with respect to 100 parts by weight of the polyolefin resin blend. Light-resistant polyolefin resin sheet.   The flame retardant light-resistant polyolefin resin sheet according to claim 1, wherein the halogen-substituted organic compound for flame retardant is selected from a bromine-substituted organic compound, a brominated polymer compound, and a chlorinated polymer compound. .   The flame retardant light-resistant polyolefin resin sheet according to claim 2, wherein the inorganic compound for a flame retardant is selected from metal oxides, metal hydroxides, metal composite oxides, and metal composite hydroxides. .   The flame-retardant light-resistant polyolefin according to claim 3, wherein the phosphorus-containing compound is selected from red phosphorus, inorganic phosphate, organic phosphate, phosphate ester, ammonium polyphosphate, and a phosphorus-nitrogen-containing composite. Resin sheet.   The flame retardant according to claim 1, wherein the hindered amine compound used in the light stabilizer component (A) has a piperidyl group, and the N position thereof is selected from an alkyl group or an alkoxy group. Light-resistant polyolefin resin sheet.   The flame retardant light-resistant polyolefin resin sheet according to any one of claims 1 to 7, wherein the fiber fabric for base fabric is made of filament yarn and has a porosity of 5 to 40%.   The flame-retardant light-resistant polyolefin resin according to any one of claims 1 to 8, wherein the metallocene catalyst comprises an organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative and an alkylaluminoxane. Sheet.   The following steps: (A) (a) a main component composed of a linear low density polyethylene resin obtained by copolymerizing ethylene and α-olefin in the presence of a metallocene catalyst, and (b) ethylene-vinyl acetate copolymer A polyolefin resin blend pellet containing at least one blend component selected from a polymer resin and an ethylene- (meth) acrylic acid (ester) copolymer, and copolymerized in the blend component The total content of vinyl acetate and (meth) acrylic acid (ester) is 5 to 30% by weight based on the weight of the polyolefin resin blend, and (B) the polyolefin resin blend and its A flame retardant containing at least one halogen-substituted organic compound with a content exceeding 5 parts by weight per 100 parts by weight, (C) Apart from the flame retardant containing pellets, a light-resistant stabilizer with a blending amount exceeding 0.05 parts by weight per 100 parts by weight of the polyolefin resin blend is blended. In this case, the light-resistant stabilizer-containing pellet is prepared from at least one selected from the group consisting of benzotriazole-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, salicylate-based compounds, and hindered amine-based compounds. A light-resistant stabilizer component (A), and an organic tin-based compound, a zinc-based metal composite compound, a metal soap, an epoxidized oil and fat, a hydrotalcite, and a zeolite. And (D) the flame retardant-containing pellets and the light-resistant stabilizer-containing pellets. The amount of the flame retardant added is 5 to 100 parts by weight, and the amount of the light stabilizer is 0.005 to 3.5 parts by weight based on 100 parts by weight of the total weight of the polyolefin resin blend. 1E or more selected from synthetic amorphous silica, colloidal silica, and a silane coupling agent. (E) A film is prepared from the compound. (F) The film is prepared from the compound. A method for producing a flame-retardant, light-resistant polyolefin resin sheet comprising laminating and bonding on both surfaces of a base fabric comprising a fiber fabric pretreated with a composition containing a silicon compound.   In the compound preparation step (D), at least one pellet selected from a polyolefin resin blend, an ethylene-vinyl acetate copolymer resin, and ethylene- (meth) acrylic acid (ester) is further blended. 10. The production method according to 10.   In the flame retardant-containing pellet preparation step (B), the halogen-substituted organic compound-containing flame retardant contains an inorganic compound in addition to the halogen-substituted organic compound, and the halogen-substituted organic compound The total weight of the inorganic compound exceeds 5 parts by weight with respect to 100 parts by weight of the polyolefin resin blend in the flame retardant-containing pellet, and in the compound preparation step (D), the polyolefin resin blend The manufacturing method of Claim 10 or 11 adjusted so that it may be 5-100 weight part with respect to the total weight of 100 weight part.   In the adjustment step (B) of the flame retardant-containing pellet, (1) a halogenated substituted organic compound-containing pellet containing the polyolefin resin blend and the halogen-substituted organic compound, and (2) the polyolefin resin. A mixture of a blend and at least one inorganic compound-containing pellet is prepared, provided that the total weight of the halogen-substituted organic compound and the inorganic compound includes the flame retardant More than 5 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin blend in the pellet, and 5 to 100 parts by weight with respect to 100 parts by weight of the total weight of the polyolefin resin in the compound. The manufacturing method according to claim 10 or 11, which is adjusted.   In the compound preparation step (D), a phosphorus-containing compound-containing pellet in which the polyolefin-based resin blend contains a phosphorus-containing compound in an amount exceeding 5 parts by weight with respect to 100 parts by weight thereof is further obtained. The manufacturing method of Claim 10 or 11 adjusted so that content of the phosphorus containing compound in a compound may be 5-50 weight part with respect to 100 weight part of total weight of a polyolefin-type resin blend.   In the flame retardant-containing pellet preparation step (B), in addition to the flame retardant, the polyolefin-based resin blend further contains a phosphorus-containing compound. It is adjusted so that it may exceed 5 weight part with respect to 100 weight part of resin-based resin blends, and may be 5-10 weight part with respect to 100 weight parts of the total weight of the polyolefin resin blend in the compound. 11. The production method according to 11.   The production method according to claim 10, wherein the halogen-substituted organic compound for the flame retardant is selected from a bromine-substituted organic compound, a brominated polymer compound, and a chlorinated polymer compound.   The manufacturing method according to claim 12 or 13, wherein the inorganic compound for a flame retardant is selected from a metal oxide, a metal hydroxide, a metal composite oxide, and a metal composite hydroxide.   The manufacturing method according to claim 14 or 15, wherein the phosphorus-containing compound is selected from red phosphorus, inorganic phosphate, organic phosphate, phosphate ester, ammonium polyphosphate, and a phosphorus-nitrogen-containing composite.   The production method according to claim 10, wherein the hindered amine compound used in the light stabilizer component (A) has a piperidyl group, and the N-position thereof is selected from an alkyl group or an alkoxy group. .   The manufacturing method according to any one of claims 10 to 19, wherein the fiber fabric for base fabric is made of filament yarn and has a porosity of 5 to 40%.   The manufacturing method according to any one of claims 10 to 20, wherein the metallocene-based catalyst includes an organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative and an alkylaluminoxane.