JP4049219B2 - Acid rain-resistant flame-retardant polyolefin resin sheet that is capable of high-frequency fusion and has excellent fracture strength at the high-frequency fusion part, and method for producing the same - Google Patents

Description

The present invention particularly relates to an acid rain-resistant flame-retardant polyolefin-based resin sheet suitably used for buildings, structures and the like, and a method for producing the same. More specifically, the present invention is excellent in acid rain resistance, weather resistance, and flame retardancy, is capable of high-frequency fusion, and has a strong strength at its melt-bonded portion. Suitable for applications such as membrane materials for sheet warehouses, curing sheets for construction sites, and sound insulation sheets for construction sites, high-frequency fusion- resistant, acid rain-resistant flame-retardant polyolefins with excellent fracture strength at high-frequency fusion parts The present invention relates to a resin sheet and a manufacturing method thereof.

  Industrial material sheets such as tent membrane materials, sheet warehouse membrane materials, building site curing sheets, and building site sound insulation sheets, especially used as members of buildings and structures, are considered fireworks because they are considered as buildings and structures. It is required to have a flameproof performance prescribed by law. At present, sheet products in which a fiber woven fabric is surface-coated with a polyvinyl chloride resin occupy the mainstream as industrial material sheets used for these applications and having flameproof performance. However, recently, in applications other than buildings, such as food applications, household goods, toys, etc., suspicion of hormonal disruptors against phthalates contained as plasticizers in polyvinyl chloride resin products has been discussed. 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, the disposal of not only polyvinyl chloride resin products but also general baking of synthetic resin processed products is prohibited, and in the event of a fire, the generation of toxic combustion gases in these synthetic resin processed products in general is suppressed from the viewpoint of evacuation safety. Has become a social requirement. From such a social background, various measures for reducing polyvinyl chloride resin products as much as possible have been developed in disposable applications, and products using polyolefin resins such as polyethylene resins and polypropylene resins have begun to spread widely.

  As such social demands intensify, synthetic fiber woven fabric is the core for membrane materials suitable for buildings and structures, such as tents, sheet warehouses, building site curing sheets, and sound insulation sheets for building sites. As a material, a fiber fabric reinforcing sheet having a polyvinyl chloride resin layer formed on the surface thereof is used. These fiber fabric reinforcing sheets are canvas and tarpaulin 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 tarpaulins for construction use a flame retardant such as antimony trioxide and / or aluminum hydroxide on polyvinyl chloride resin. By adding a small amount of 5-20 parts by weight, a resin-coated sheet that conforms to the flameproof standard (Fire Prevention Law Construction Rules Article 4: JIS Standard L-1091) stipulated in the Fire Service Act is obtained. Is possible. However, when these constituent resins of canvas and tarpaulin are replaced with polyolefin resin, the polyolefin resin itself is flammable and further contains a flammable synthetic fabric, so that it is sufficiently flame retardant. There is a problem that cannot be easily obtained. Therefore, it is necessary to make these flame-retardant and improve their practicality.

In general, a commercially available flame retardant or a flame retardant resin is used to make a polyolefin resin flame retardant. For example, halogenated products such as organic chlorinated products and organic brominated products are particularly effective as flame retardants. For example, for electric wires and cables, insulating materials, and polyolefin resins as external coating materials such as organic chlorinated products and organic brominated products. Methods of blending halides to make flame retardant have been used for some time (Japanese Patent Laid-Open No. 51-132254 (Patent Document 1), Japanese Patent Laid-Open No. 56-136862 (Patent Document 2), 61-254646 (Patent Document 3), JP-A-62-2225541 (Patent Document 4)). Although it is possible to obtain a polyolefin-based resin composition that is certainly flame-retardant by these methods, such a flame-retardant resin has a disadvantage that it is inferior in weather resistance and easily discolored even for short-term outdoor use. Have. This poor weather resistance is not a problem for underground electric wires or black-colored products, but it is a major problem for outdoor use, especially for tents where color is important. Become. Further, these halides have a problem of causing NO _x gas discoloration.

  In recent years, as the demand for controlling toxic combustion gases from the viewpoint of safe evacuation in the event of a fire has increased, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, antimony trioxide, zinc borate, in particular, as flame retardants Metal oxides such as titanium dioxide are used (Japanese Patent Laid-Open No. 63-20348 (Patent Document 5), Japanese Patent Laid-Open No. 63-61055 (Patent Document 6), Japanese Patent Laid-Open No. 63-128038). (Patent Document 7), Japanese Patent Application Laid-Open No. 63-154760 (Patent Document 8), Japanese Patent Application Laid-Open No. 3-20342 (Patent Document 9), etc.). In the case of the method using these metal hydroxides and / or metal oxides, 100 to 300 parts by weight of metal hydroxide and / or metal oxide is used in order to impart sufficient flame retardancy to the polyolefin resin. Therefore, there are many products in which the ratio of these metal hydroxides and metal oxides contained in the polyolefin resin composition accounts for 50% or more. In general, in a composition containing such a large amount of flame retardant, the surface of the flame retardant particles is treated with a fatty acid compound or an unsaturated fatty acid compound in order to process it efficiently. Is improved and is uniformly dispersed in the resin. Furthermore, the use of flame retardant particles surface-treated with a coupling agent improves the affinity and adhesion between the flame retardant particles and the polyolefin resin in a large amount of flame retardant compounded system, and the resulting flame retardant resin molded product Techniques such as reducing the decrease in strength of the steel have been conventionally performed. Moreover, it is also possible to improve the water resistance of a flame-retardant resin molding by using a surface-treated flame retardant.

Recently, acid rain caused by nitrogen oxides (NO _x gas) and sulfur oxides (SO _x gas) caused by automobile exhaust gas in the atmosphere has become an environmental problem. . Although acid rain itself is not a strong acid, it has a troublesome property that an acidic component is concentrated as the rainwater dries, and thus becomes strongly acidic. Therefore, fundamental solutions such as death from trees, plants, crops, etc. due to acid rain, corrosion damage from concrete structures, steel structures, houses, etc., discoloration damage from rain-washed laundry, rain-wet clothes, etc. are reported. Is known as a difficult problem. By the way, it was obtained from a polyolefin resin composition containing a large amount of a metal compound such as aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, titanium dioxide in an environment where acid rain frequently occurs. When fiber composite sheets are used for long-term applications such as awning tents and tent houses, metal compounds contained as flame retardants in polyolefin resin compositions are gradually corroded by acid rain (strong acid that remains after being concentrated during drying). The problem of gradually deactivating the flame retardancy, and at the same time, the flame retardant particles are thinned by corrosion (the volume is reduced), resulting in a fine gap between the polyolefin resin and the particles. The problem is that the strength of the coating layer is significantly reduced, and the appearance of the sheet is whitened by acid rain. It is causing the problem. Although this problem can be improved to some extent at the initial level by the conventional flame retardant polyolefin resin composition using the surface-treated flame retardant, the weather resistance of the surface treatment when it is used outdoors for a long time. The water resistance is lost due to the deterioration, and as a result, there is a problem that the sheet is deteriorated and cannot be used in 1 to 2 years due to corrosion by acid rain (strong acid remaining after being concentrated when dried).

  In addition to these problems, the dielectric loss factor of the polyolefin-based resin is too low, so that there is an inconvenience that a high-frequency fusion machine used for sewing a polyvinyl chloride resin sheet cannot be used. In addition, even if these sheets are sewn using a special heat-sealing machine, a large amount of halogen-free flame retardant corresponding to the flameproof standard (Article 4 of the Fire Service Construction Rules: JIS Standard L-1091) In addition to the problem that the strength of the polyolefin-based resin film is remarkably low from the design stage, the adhesiveness with the synthetic fiber fabric is not sufficiently obtained, and therefore, there is a defect that thread breakage at the sewing joint is likely to occur. It was a thing. In addition, a compound in which these halogen-free flame retardants are blended with a polyolefin-based resin is a kneading machine such as a Banbury mixer or a kneader. In this case, it is difficult to quantitatively disperse the halogen-free flame retardant with respect to the polyolefin resin, and therefore, it is impossible to stably meet the flameproof standard stipulated in the Fire Service Law. there were.

Therefore, even if there is a flameproof sheet product obtained by adding flame retardant containing no halogen, it has sufficient resistance to acid rain, and as a result, maintains stable flame retardancy for a long time outdoors. No possible polyolefin resin canvas sheet or tarpaulin sheet has been developed yet. Also, a halogen-free polyolefin resin canvas sheet and tarpaulin sheet that are capable of high-frequency welder fusion, excellent joint strength, and excellent light resistance have not yet been developed.
JP 51-132254 A JP-A-56-136862 JP 61-254646 A Japanese Patent Laid-Open No. 62-225541 JP 63-20348 A JP 63-61055 A JP 63-128038 A JP 63-154760 A JP-A-3-20342

The present invention has resistance to acid rain that could not be achieved with the above conventional halogen-free flame retardant polyolefin resin sheet, flame resistance stable for a long period of time outdoors, and high frequency welder fusion. It is also excellent in strength and has high adhesive strength, suitable for use in industrial material sheets such as tents, sheet warehouses, building site curing sheets, and sound insulation sheets for construction sites . An object of the present invention is to provide an acid rain resistant flame retardant polyolefin resin sheet (hereinafter referred to as an acid rain resistant flame retardant polyolefin resin sheet) excellent in breaking strength .

The acid rain resistant flame retardant polyolefin resin sheet of the present invention (hereinafter referred to as acid rain resistant flame retardant polyolefin resin sheet) includes a base fabric including a fiber fabric and at least one surface of the base fabric. And a polyolefin-based resin coating layer that covers
The fiber fabric for base fabric is pretreated with a treating agent containing a silicon compound component composed of one or more selected from synthetic amorphous silica, colloidal silica and silane coupling agent,
The polyolefin resin coating layer is
(A) 100 parts by weight of a polyolefin-based resin blend (B) 20 to 200 parts by weight of a flame retardant particle main body, and at least one kind of surface coating layer formed on the surface thereof and containing a thermosetting resin Halogen-free flame retardant particles;
(D) 0.05 to 3.0 parts by weight of a light-resistant stabilizer;
Including
The polyolefin resin blend (A) is
(A) a linear low-density polyethylene resin obtained by copolymerizing ethylene and at least one α-olefin in the presence of a metallocene catalyst;
(B) an ethylene-based copolymer resin composed of at least one selected from an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer;
Including
The total amount of vinyl acetate and (meth) acrylic acid (ester) contained in the copolymer resin (b) is in the range of 5 to 30% by weight with respect to the total weight of the polyolefin resin blend (A). It is in,
It is characterized by this.
In the acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, the polyolefin resin coating layer covers the surface of the base fabric, and the back surface of the base fabric is a thermoplastic resin. Coated with a layer, the back surface thermoplastic resin layer,
(C) 100 parts by weight of a thermoplastic resin, (B) 20 to 200 parts by weight of a flame retardant particle body, and at least one surface coating layer formed on the surface thereof and containing a thermosetting resin Halogen-free flame retardant particles of
It is preferable to contain.
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the surface coating layer of the halogen-free flame retardant particles (B) is an epoxy resin, an unsaturated polyester resin, a phenol resin, a melamine resin, a urea resin, or a triazine. It is preferable that 1 or more types of thermosetting resin chosen from resin and diallyl phthalate resin is included, and the coating layer is 2 to 15 weight% with respect to the weight of the said halogen-free flame retardant particle | grains.
In the acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the halogen-free flame retardant particles (B) thermosetting resin for the surface coating layer, further metal alkoxide compound, organic silane compound, organic titanate compound, One or more additives selected from an alkylfluoro group-containing compound and a silicone-based compound are mixed, and the amount of the additive is 1 to 30% by weight based on the weight of the thermosetting resin. It is preferable.
In the acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, a light-resistant stabilizer (D) may further be contained in the surface coating layer of the halogen-free flame retardant particles (B).
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the light stabilizer is at least one selected from a benzotriazole compound, a benzophenone compound, a cyanoacrylate compound, a salicylate compound, and a hindered amine compound. It is preferable to contain.
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the flame retardant particle body of the halogen-free flame retardant particles (B) contains at least one of a phosphorus-containing compound, a nitrogen-containing compound, and an inorganic compound. It is preferable.
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the phosphorus-containing compound for the flame retardant particle body of the halogen-free flame retardant particles (B) is red phosphorus, (metal) phosphate, (metal) It is preferably selected from organic phosphates and ammonium polyphosphates.
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the halogen-containing flame retardant particle main body of the halogen-free flame retardant particles (B) is an (iso) cyanurate compound or (iso) cyanuric acid type. It is preferably selected from a compound, a guanidine compound, a urea compound, and a derivative compound thereof.
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the halogen-free flame retardant particle (B) inorganic compound for the flame retardant particle body is a metal oxide, a metal hydroxide, or a metal composite oxide. It is preferably selected from metal composite hydroxides.
In the acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, it is preferable that the fiber fabric for base fabric is composed of filament yarns and the porosity thereof is 5 to 40%.
In the acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, the treatment agent for the undertreatment of the fiber fabric for base fabric may further contain a thermoplastic resin in addition to the silicon compound component.
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the fiber fabric for base fabric is subjected to flame retardant treatment by kneading or doping a flame retardant during fiber formation, or by post-treatment after fiber formation. It is preferred that
In the acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, the metallocene catalyst for producing the linear low-density polyethylene resin contains an organic transition containing at least one of a cyclopentadienyl derivative and an indenyl derivative. It is preferable to contain a metal compound and an alkylaluminoxane.
In the acid rain resistant flame-retardant polyolefin resin sheet of the present invention having a back surface thermoplastic resin layer, the thermoplastic resin for back surface thermoplastic resin layer (C) is an ionomer resin, an acrylic resin, a vinyl acetate resin, It is preferable to include at least one selected from polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, polystyrene resins, saturated polyester resins, polyamide resins, and modified resins thereof.
In the acid rain resistant flame retardant polyolefin resin sheet of the present invention having a back surface thermoplastic resin layer, the thermoplastic resin for back surface thermoplastic resin (C) is an ionomer resin, an acrylic resin, a vinyl acetate resin, polyvinyl At least one selected from alcohol resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, polystyrene resins, saturated polyester resins, polyamide resins, and modified resins thereof, phenol resins, melamine It may contain a blend with at least one selected from a resin, a urea resin, an unsaturated polyester resin, an epoxy resin, a thermosetting polyurethane resin, and an allyl phthalate resin.

In order to produce the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the method for producing the acid rain resistant flame retardant polyolefin resin sheet of the present invention,
(1) Halogen-free flame retardant particles (B) having the flame retardant particle main body and a surface coating layer formed on the surface thereof and containing a thermosetting resin in the ethylene copolymer resin (b). ) At least one kind of (b) + (B) pellets containing at a high concentration,
(2) A resin compound for coating by mixing all kinds of the (b) + (B) pellets and the linear low-density polyethylene resin (a) and containing the light-resistant stabilizer (D). Prepare
(3) The resin compound is subjected to calendar molding or T-die extrusion molding to mold a polyolefin resin film,
(4) At least a base fabric composed of a fiber fabric prepared by pretreating the polyolefin resin film with a treating agent containing a silicon compound component composed of one or more selected from synthetic silica, colloidal silica, and a silane coupling agent. Laminate and stick on one side.
It is characterized by this.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, a step of laminating and sticking the polyolefin resin film on the surface of the base treatment base fabric, and further on the back surface of the base treatment base fabric And a step of forming a thermoplastic resin layer,
The back surface thermoplastic resin layer is
(C) 100 parts by weight of a thermoplastic resin; (B) 20 to 200 parts by weight of a flame retardant particle main body, and at least one halogen-free material having a surface coating layer formed on the surface thereof and containing a thermosetting resin. Containing flame retardant particles,
Including
In the step of forming the back surface thermoplastic resin layer,
(A ′) an aqueous resin solution comprising at least one selected from an aqueous emulsion and an aqueous dispersion of the thermoplastic resin (C), or (b ′) dissolving the thermoplastic resin (C) in an organic solvent. Obtained solution,
It is preferable that a coating liquid is prepared by containing the halogen-free flame retardant particles (B), and this coating liquid is applied to the back surface of the pretreated base fabric and dried.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the halogen-free flame retardant particles (B) differ in the composition of the flame retardant particle main body and / or the composition of the surface coating layer. Consisting of two or more
In the (b) + (B) pellet manufacturing process, all of the two or more halogen-free flame retardant particles (B) are mixed in the ethylene copolymer resin (b) to provide a single type. (B) + (B) pellets may be produced.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the halogen-free flame retardant particles (B) differ in the composition of the flame retardant particle main body and / or the composition of the surface coating layer. It consists of two or more types
In the (b) + (B) pellet manufacturing process, at least one of the two or more halogen-free flame retardant particles (B) and the ethylene copolymer resin (b) are mixed and at least 2 Producing seed (b) + (B) pellets;
In the coating resin compound preparation step, a coating resin compound is prepared by mixing all of the two or more types of (b) + (B) pellets and the linear low density polyethylene resin (a). May be.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the surface coating layer of the halogen-free flame retardant particles (B) is an epoxy resin, an unsaturated polyester resin, a phenol resin, a melamine resin, urea. 1 or more types of thermosetting resin chosen from resin, triazine resin, and diallyl phthalate resin are included, and the coverage is 2 to 15 weight% with respect to the weight of the said halogen-free flame retardant particle | grains. Is preferred.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the thermosetting resin for the surface coating layer of the halogen-free flame retardant particles (B), a metal alkoxide compound, an organic silane compound, an organic One or more additives selected from a titanate compound, an alkylfluoro group-containing compound and a silicone compound are mixed, and the mixing amount of the additive is 1 to 30 weights relative to the weight of the thermosetting resin. % Is preferred.
In the method for producing an acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, a light-resistant stabilizer (D) may be contained in the surface coating layer of the halogen-free flame retardant particles (B).
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the light stabilizer is selected from a benzotriazole compound, a benzophenone compound, a cyanoacrylate compound, a salicylate compound, and a hindered amine compound. It is preferable that 1 or more types are included.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the flame retardant particle body of the halogen-free flame retardant particles (B) is one of a phosphorus-containing compound, a nitrogen-containing compound, and an inorganic compound. It is preferable to include the above.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the phosphorus-containing compound for the flame retardant particle body of the halogen-free flame retardant particles (B) is red phosphorus, (metal) phosphate, It is preferably selected from (metal) organic phosphates and ammonium polyphosphate.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the nitrogen-containing compound for the flame retardant particle body of the halogen-free flame retardant particles (B) is an (iso) cyanurate compound, (iso) It is preferably selected from cyanuric acid compounds, guanidine compounds, urea compounds, and derivative compounds thereof.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the halogen-free flame retardant particle (B) inorganic compound for the flame retardant particle body is a metal oxide, a metal hydroxide, or a metal. It is preferably selected from complex oxides and metal complex hydroxides.
In the method for producing an acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, it is preferable that the fiber fabric for base fabric is composed of filament yarns and the porosity thereof is 5 to 40%.
In the method for producing an acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, the treatment agent for the undertreatment of the fiber fabric for base fabric further contains a thermoplastic resin in addition to the silicon compound component. Also good.
In the method for producing an acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, the fiber fabric for base fabric is difficult to knead or dope with a flame retardant at the time of fiber formation, or after-treatment after fiber formation. It is preferable that it is what has been subjected to a combustion treatment.
In the method for producing an acid rain-resistant flame retardant polyolefin resin sheet of the present invention, the metallocene catalyst for producing the linear low-density polyethylene resin comprises at least one of a cyclopentadienyl derivative and an indenyl derivative. It is preferable to contain the organic transition metal compound to contain and an alkylaluminoxane.
In the method for producing an acid rain-resistant flame-retardant polyolefin resin sheet of the present invention having a back surface thermoplastic resin layer, the thermoplastic resin for back surface thermoplastic resin layer (C) is an ionomer resin, an acrylic resin, or vinyl acetate. Containing at least one selected from a resin based on a resin, a polyvinyl alcohol resin, an ethylene-vinyl acetate copolymer resin, a polyurethane resin, a polystyrene resin, a saturated polyester resin, a polyamide resin, and a modified resin thereof Is preferred.
In the method for producing an acid rain-resistant flame-retardant polyolefin resin sheet of the present invention having a back surface thermoplastic resin layer, the thermoplastic resin for back surface thermoplastic resin (C) is an ionomer resin, an acrylic resin, or a vinyl acetate type. At least one selected from resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, polystyrene resins, saturated polyester resins, polyamide resins and modified resins thereof, and phenolic resins It may contain a blend with at least one selected from resins, melamine resins, urea resins, unsaturated polyester resins, epoxy resins, thermosetting polyurethane resins and allyl phthalate resins.

The acid rain resistant flame retardant polyolefin resin sheet of the present invention is a laminated sheet in which a polyolefin resin coating layer is provided on at least one surface of a base fabric made of a fiber fabric, and the fiber fabric for base fabric is In addition, the polyolefin resin coating layer is pretreated by a treatment containing a silicon compound component composed of one or more selected from synthetic amorphous silica, colloidal silica and a silane coupling agent.
(A) 100 parts by weight of a polyolefin-based resin blend; (B) 20 to 200 parts by weight of a flame retardant particle body; and at least one halogen having a surface coating layer formed on the surface thereof and containing a thermosetting resin. Non-containing flame retardant particles,
(D) 0.05 to 3.0 parts by weight of a light-resistant stabilizer;
Including
The polyolefin resin blend (A) is:
(A) a linear low-density polyethylene resin obtained by copolymerizing ethylene and at least one α-olefin in the presence of a metallocene catalyst;
(B) an ethylene-based copolymer resin comprising at least one selected from an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer resin;
Including
The total amount of vinyl acetate and (meth) acrylic acid (ester) contained in the copolymer resin (b) is in the range of 5 to 30% by weight with respect to the total weight of the polyolefin resin blend (A). It is in.
The (meth) acrylic acid (ester) used in the present invention includes acrylic acid, methacrylic acid, acrylic acid ester, and methacrylic acid ester.

  The linear low density polyethylene resin (a) used in the polyolefin resin blend (A) of the polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention includes a metallocene catalyst. An ethylene-α-olefin copolymer resin obtained by copolymerizing ethylene in the presence with one or more α-olefins preferably having 3 to 18 carbon atoms. This ethylene-α-olefin copolymer resin (a) comprises an ethylene monomer, preferably an α-olefin monomer having 3 to 18 carbon atoms, in the presence of a metallocene-based homogeneous catalyst, a gas phase method, a slurry liquid phase. It can be obtained by polymerization by the method or the high pressure method. 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, heptadecene- 1 and octadecene-1 are used, and α-olefins having 4 to 10 carbon atoms are particularly preferable. Moreover, you may use ethylene-alpha-olefin copolymer resin obtained by using these alpha olefins 1 type (s) or 2 or more types and copolymerizing these with an ethylene monomer. These ethylene-α-olefin copolymer resins (a) can be used in combination with not only one type but also two or more types of ethylene-α-olefin copolymer resins. -It is preferable that the melt index of the single body of olefin copolymer resin and a blend body is 0.3-20 g / 10min. If the melt index is less than 0.3 g / 10 min, the kneadability and moldability with the halogen-free flame retardant particles (B) may be insufficient, and if it is higher than 20 g / 10 min. The resulting acid rain resistant flame retardant polyolefin resin sheet may not only have insufficient strength and heat resistance, but may also increase the tackiness and cause blocking.

  Examples of the metallocene catalyst that can be used for the polymerization of the ethylene-α-olefin copolymer resin (a) used in the present invention include cyclopentadienyl derivatives and organic transition metal compounds containing at least one of indenyl derivatives. It is preferable that the catalyst component includes at least one catalyst component and a co-catalyst including at least one alkylaminoxan. The transition metal of the organic transition metal compound containing a cyclopentadienyl derivative and / or an indenyl derivative is preferably selected from group IVB of the periodic table. For example, zirconium, titanium, and hafnium are preferable. 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. The former metallocene catalyst containing a cyclopentadienyl derivative has a high syndiotacticity, and the latter metallocene catalyst containing an indenyl derivative has a high isotacticity. By using these metallocene catalysts, ethylene-α -It can be obtained by controlling the stereoregularity of the olefin copolymer resin.

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

  The ethylene copolymer resin (b) that can be used in the polyolefin resin blend (A) for the polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention is an ethylene-vinyl acetate copolymer resin. And / or ethylene- (meth) acrylic acid (ester) copolymer resins, which are preferably copolymer resins produced by radical polymerization. Examples of the monomer capable of radical polymerization with the ethylene monomer include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, esterified products, acid anhydrides, and vinyl acetate. 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 ethylene copolymer resin used in the polyolefin resin blend (A) of the acid rain resistant flame retardant polyolefin resin sheet of the present invention is preferably ethylene having a vinyl acetate component content of 5 to 60% by weight. A vinyl acetate copolymer resin or an ethylene- (meth) acrylic acid (ester) copolymer resin having a (meth) acrylic acid (ester) component content of 5 to 60% by weight is used. In the blend of ethylene-vinyl acetate copolymer resin and (meth) acrylic acid (ester) copolymer resin, the total content of vinyl acetate component and (meth) acrylic acid (ester) component is 5 to 60 wt. % Is preferred. A melt index of these ethylene-based copolymer resins (b) of 0.3 to 20 g / 10 min can be suitably used in the present invention. If the melt index is less than 0.3 g / 10 min, the kneadability and moldability of the halogen-free flame retardant may be insufficient, and if it is higher than 20 g / 10 min, the resulting acid-resistant rain The flame retardant flame retardant polyolefin resin sheet may have insufficient strength and heat resistance, and may increase the tackiness and cause blocking.

  In the polyolefin resin blend (A) of the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the linear low density polyethylene resin (ethylene-α-olefin copolymer resin) (a) and the above In the blend (A) with the ethylene copolymer resin (b), the weight ratio of the components (a) and (b) is preferably 100: 10 to 100: 100. The weight ratio of the total amount of the vinyl acetate component and the (meth) acrylic acid (ester) component in the ethylene copolymer resin (b) is 5 to 5 with respect to the total weight of the polyolefin resin blend (a). 30% by weight. When the weight ratio is less than 100: 10, the resulting polyolefin resin sheet is not preferable because the high-frequency welder fusion property, flame retardancy, and flexibility are insufficient, and it is obtained when it exceeds 100: 100. The coating resin strength of the polyolefin-based resin sheet becomes insufficient, resulting in inconveniences such as being easily scratched. At the same time, the total content of the vinyl acetate component and the (meth) acrylic acid (ester) component contained in the polyolefin resin blend layer is preferably 5 to 30 parts by weight, and optimally 8 to 20 parts by weight. When the total content of the vinyl acetate component and the (meth) acrylic acid (ester) component is less than 5% by weight, the polyolefin resin film material obtained has insufficient high frequency welder fusion, flame retardancy, and flexibility. It is not preferable, and if it exceeds 30% by weight, the coating resin strength of the resulting polyolefin resin sheet is insufficient, and scratches are easily obtained, which is not preferable. Further, the heat resistant creep resistance is insufficient, which is not preferable.

The blend of the ethylene-α-olefin copolymer resin (a) and the ethylene copolymer resin (b) used for the polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention. (a) the density of component is preferably 0.913~0.938g / cm ^3, and more preferably in particular the range of 0.916~0.933g / cm ^3. When the density exceeds 0.938 g / cm ³ , the crystallinity of the resulting resin blend may increase and the texture may become hard, and the halogen-free flame retardant particles (B) may bloom on the surface of the polyolefin resin sheet. And the appearance may be clouded. If the density is less than 0.913 g / cm ³ , the bloom resistance will be good, but the film strength and heat resistance will be reduced, and sufficient wear strength may not be obtained, and high frequency welder fusion will be poor. May be enough.

  The polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention includes, in addition to the linear low density polyethylene resin (a), improved impact strength and improved resin wear strength. Therefore, about 5 to 10% by weight of isotactic polypropylene resin and / or syndiotactic polypropylene resin obtained by self-polymerization of propylene monomer in the presence of a metallocene catalyst may be added.

  The polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention may be colored with an organic pigment and / or an inorganic pigment. Conventionally known organic and inorganic pigments can be used and are not particularly limited.

  The particulate halogen-free flame retardant (B) contained in the polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention coats the particle body composed of the flame retardant and the surface thereof. It is preferable that any one or more of a phosphorus-containing compound, a nitrogen-containing compound, and an inorganic compound is used as the particle main body, and the particle main body is 100 parts by weight of the polyolefin resin blend (A). It is used by blending 20 to 200 parts by weight of the halogen-free flame retardant particles (B).

  Examples of the phosphorus-containing compound for the flame retardant particle body include red phosphorus, (metal) phosphate, (metal) organic phosphate, and ammonium polyphosphate. As red phosphorus, powdery red phosphorus having an average particle diameter of 5 to 25 μm, which is converted to red phosphorus by heating at 250 to 350 ° C. in an inert gas atmosphere, can be used. Further, as the red phosphorus used in the present invention, the surface coating is carried out by at least one selected from epoxy resins, unsaturated polyester resins, phenol resins, melamine resins, urea resins, triazine resins, and diallyl phthalate resins. It is preferable to use powdered red phosphorus particles having an average particle diameter of 5 to 25 μm.

Examples of the metal phosphate include metal salts such as phosphoric acid, phosphorous acid, and 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 that forms a salt with organic phosphoric acid include Na, K, Li, Ca, Ba, Mg, Al, and Zn. As the ammonium polyphosphate compound, a condensed phosphate compound which is 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 ammonium polyphosphate (NH ₄ PO ₃ ) _n , those having a polymerization degree n of 200 or more are preferably used. For applications where the degree of polymerization of ammonium polyphosphate is less than 200, ammonium polyphosphate becomes water-soluble, and elution into water results in loss of sustainability of the flame retardant effect. It becomes inappropriate. The condensed phosphorus compound that can be used in the flame retardant light-resistant polyolefin resin sheet of the present invention has a polymerization degree n of 600 to 1200, which is surface-coated with a nitrogen-containing thermoplastic resin such as a melamine resin, urea resin, or triazine resin. Ammonium polyphosphate can be preferably used.

  Examples of the nitrogen-containing compound used in the flame retardant particle body of the halogen-free flame retardant particles (B) include (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, urea compounds, and derivatives thereof. It is preferable that it is 1 or more types chosen from the compound. Specific examples of nitrogen-containing compounds include cyanurate derivatives such as trimethylcyanurate and triethylcyanurate, composites of these (iso) cyanurate derivatives and melamine compounds, and isocyanurate derivatives such as trimethylisocyanurate and triethylisocyanurate. , Melamine (cyanuric acid amide), guanamine, benzoguanamine, melamine sulfate, trimethylol melamine, cyanuric acid trimethyl ester, cyanuric acid triethyl ester, cyanuric acid monoamide, cyanuric acid diamide, and 1,3,5-triazine, 2,4, Cyanuric acid derivatives such as 6-trioxy-1,3,5-triazine, isocyanuric acid monoimide, isocyanuric acid diimide, isocyanuric acid triimide, trimethyldicyanamide, triethyl Isocyanuric acid derivatives such as dicyanamide, tricarbimide, and dicyanamide trimer (melon), and guanidine derivatives such as dicyandiamide, dicyandiamidicin, guanidine, guanidine sulfamate, guanidine phosphate, and diguanide, urea, thiourea, Examples include urea compounds such as dimethylolurea, diacetylurea, trimethylurea, N-benzoylurea, and guanylurea phosphate, and composites of these nitrogen-containing compounds. Moreover, the composite of these nitrogen-containing compounds and polyphosphoric acid, for example, the composite of polyphosphoric acid and melamine, the composite of the dimer of polyphosphoric acid and melamine, etc. are mentioned. As other nitrogen-containing compounds, heterocyclic compounds such as pyrroles, indoles, oxazoles, oxazines, thiazines and pyridazines can be used.

  Examples of the inorganic compound used as the particle main body of the halogen-free flame retardant particles (B) include metal oxides, metal hydroxides, metal composite oxides, and metal composite hydroxides. Specifically, these include metal oxides such as aluminum oxide, magnesium oxide, barium oxide, titanium oxide, zinc oxide, tin oxide, zirconium oxide, molybdenum oxide, antimony oxide, and zinc borate, zinc metaborate, barium metaborate. , Metal complex oxides such as aluminum borate, potassium titanate, and zirconium-antimony. Also, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, zirconium hydroxide, basic magnesium carbonate, and hydrates of dolomite, hydrotalcite, zinc hydroxystannate, tin oxide The particle size of the metal composite hydroxides such as borax and the inorganic compound particles varies depending on the type of the compound. For example, the average particle size is 20 μm or less, preferably 10 μm or less. In addition, these inorganic compounds may be used alone or in combination of two or more.

  The surface coating layer of these halogen-free flame retardant particles (B) contains one or more selected from thermosetting resins, and is 2 to 15% by weight with respect to the halogen-free flame retardant, and the optimum amount is 3 It is formed with a coverage of 10% by weight. When the coverage of the halogen-free flame retardant is less than 2% by weight, the resulting sheet may have insufficient water resistance and acid rain corrosion resistance, and when the coverage exceeds 15% by weight, In the surface coating treatment step of the non-containing flame retardant, the flame retardant particles may aggregate to deteriorate the dispersibility and processability in the polyolefin resin, and may reduce the mechanical strength of the obtained sheet.

  Examples of the thermosetting resin that can be used for the surface coating layer include epoxy resins, unsaturated polyester resins, phenol resins, melamine resins, urea resins, triazine resins, and diallyl phthalate resins. Examples of the epoxy resin include glycidyl ether type epoxy resins obtained by polycondensation of phenols or alcohols with epichlorohydrin (ECH), for example, bisphenol A type epoxy resins obtained by polycondensation of bisphenol A and ECH. In particular, a polyfunctional glycidyl ether type epoxy resin using phenol novolak as a phenol derivative can be preferably used because it produces a three-dimensional stitch structure. In addition, glycidyl ester type epoxy resins obtained by polycondensation of carboxylic acids and ECH, glycidyl amine type epoxy resins obtained by polycondensation of amines or cyanuric acids or hydantoins with ECH, and alicyclic An epoxy resin etc. are mentioned. In addition, these epoxy resins include polyamines, modified polyamines, acid anhydrides, isocyanates, polymercaptans, organic acid and other polyaddition type curing agents, tertiary amines, imidazoles, Lewis acids, Bronsted acid salts and other catalyst type curing agents. The resin can be further cured by using a condensation type curing agent such as a resol type phenol resin, a methylol group-containing urea resin, or a methylol group-containing melamine resin.

  Examples of the unsaturated polyester resin include those obtained by polycondensation of a dibasic acid containing an unsaturated dibasic acid and a dihydric alcohol and having unsaturated bonds crosslinked with a vinyl monomer. Unsaturated dibasic acids include maleic anhydride, fumaric acid, itaconic acid, etc., and dibasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, adipic acid, sebacic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride Examples thereof include acid and het anhydride. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, triethylene glycol and the like. Examples of the vinyl monomer for crosslinking include styrene, vinyl toluene, diallyl phthalate, triallyl cyanurate, and methyl methacrylate. In addition, a vinyl ester resin can also be used as the unsaturated polyester resin.

  As the phenolic resin, phenol or a novolac resin obtained by condensation in the presence of an acidic catalyst of a phenol derivative and formaldehyde with a crosslinking agent such as hexamethylenetetramine, or a phenol or Examples thereof include those obtained by curing a resol-type resin obtained by condensation of a phenol derivative and formaldehyde in the presence of a basic catalyst by an acid catalyst or heating. Phenol derivatives include (o-, m-, p-) cresol, (2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-) xylenol, resorcinol The characteristics of the phenol resin obtained by using in combination with phenol can be controlled.

  As the melamine resin, melamine or a methylolated melamine obtained by addition of a melamine derivative and formaldehyde is condensed. As a urea resin, methylolated urea obtained by addition of urea or a urea derivative and formaldehyde is condensed. Examples of the triazine resin include guanamine or those obtained by condensing methylolated guanamine obtained by addition of a guanamine derivative and formaldehyde. In addition, a product obtained by adding two or more melamine, urea, guanamine, and derivatives thereof to form a cocondensation resin in methylolation may be used.

  As the diallyl phthalate, diallyl orthophthalate, which is an adduct of allyl chloride and phthalic anhydride, or a prepolymer obtained by radical polymerization of diallyl isophthalate, which is an adduct of allyl chloride and isophthalic acid, is thermally cured. Or those cured by ultraviolet rays.

  Further, the surface coating layer of the halogen-free flame retardant particles (B) used in the present invention is one kind selected from a metal alkoxide compound, an organic silane compound, an organic titanate compound, an alkylfluoro group-containing compound, and a silicone compound. The above additive compounds are preferably contained. These additive compounds are preferably contained in an amount of 1 to 30% by weight based on the thermosetting resin. When the additive compound is uniformly dispersed in the surface coating layer, the content relative to the thermosetting resin is preferably 1 to 10% by weight, and the halogen-free flame retardant particles (B) Surface treated with the above additive compound, surface treated with the thermosetting resin, or surface treated with the thermosetting resin on the surface of the halogen-free flame retardant particles (B) In the case where the surface is further treated with an additive compound, the content of the additive compound with respect to the thermosetting resin is preferably 10 to 30% by weight.

As the metal alkoxide compound, the hydroxyl group of the metal hydroxide of M (OH) _n was substituted with an alkoxy group (OR: —OCH ₃ , —OC ₂ H ₅ , —OC ₃ H ₇ , —OC ₄ H _9, etc.). It is an organometallic compound M (OR) _n , which includes Ba, Y, Cu, Zr, Nb, Ta, In, Sn, Fe, Si, Ga, Sr, W, Mn, Co, Zn, Ni, Al, La, Ti, etc. These are specifically diethoxybarium, di-i-propoxybarium, di-n-butoxybarium, triethoxyaluminum, tri-i-propoxyaluminum, tri-n-butoxy. Aluminum, tetraethoxy silicon, tetra-i-propoxy silicon, tetra-n-butoxy silicon, etc. These metal alkoxides are known sol-gel methods, Others, is hydrolyzed by the hydrolysis precipitation method can be used by polycondensation.

Examples of the organosilane compound include silane coupling agents having two or more different reactive groups in the molecule represented by the general formula: XR-Si (Y) ₃ , for example, X = amino group, vinyl group, Examples thereof include an epoxy group, a chloro group, a mercapto group (R = alkyl chain), Y = methoxy group, ethoxy group and the like. These hydrolysates and cohydrolyzed compounds with alkoxysilane compounds can also be used. Specific examples of the organic silane compound include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycol. Sidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-amino Propyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, perfluorooctylethyltriethoxysilane And the like. These organosilane compounds can be used at a concentration of 1 to 5% by weight and hydrolyzed. Further, modified dimethylpolysiloxane can be used as the organosilane compound.

  Examples of the organic titanate compound include titanium alkoxide compounds such as tetraethoxy titanium, tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetra-i-propoxy titanium polymer, tetra-n-butoxy titanium polymer, tri-n- Titanium acylate compounds such as butoxytitanium stearate, isopropoxytitanium tristearate, titanium chelate compounds such as di-i-propoxytitanium bisacetylacetonate, di-i-propoxytitanium bisethylacetoacetate, Isopropoxy titanium / triisostearate, isopropoxy titanium / dimethacrylate / isostearate, isopropoxy titanium / trisdioctyl phosphate, bisdioctyl phosphate / ethylene glycolate Tan, titanium coupling agent such as di -n- butoxy bis triethanolaminato titanium and the like. The organic titanate compound is used at a concentration of 1 to 3% by weight and can be used after being hydrolyzed.

Among the alkylfluoro group-containing compounds, the fluorine-based compound is a compound having a perfluoroalkyl group (C _n F _{2n + 1} ) having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms, and a hydrophilic group. The surface tension in the aqueous solution is preferably 10 to 15 dyn / cm. Examples of such a fluorine compound include fluoroalkyl (C ₄ -C ₁₀ ) carboxylic acid, N-perfluorooctanesulfonyl glutamate disodium, 3- [fluoroalkyl (C ₆ -C ₁₁ ) oxy] -1- alkyl (C ₃ -C ₄₎ sulfonate, sodium 3- [ω- fluoroalkanoyl (C ₆ ~C ₈₎ -N- ethylamino] -1-sodium sulfonate, N- [3- (perfluorooctane sulfonate Amido) propyl] -N, N-dimethyl-N-carboxymethylene ammonium betaine, fluoroalkyl (C ₁₁ -C ₂₀ ) carboxylic acid, perfluoroalkyl (C ₇ -C ₁₃ ) carboxylic acid, perfluorooctanesulfonic acid diethanolamide , perfluoroalkyl (C ₄ ~C ₁₂₎ sulfonate (Li, K, Na) N- propyl-N-(2-hydroxyethyl) perfluorooctane sulfonamide, perfluoroalkyl (C ₆ -C ₁₀₎ sulfonamide propyl trimethyl ammonium salts, perfluoroalkyl (C ₆ ~C ₁₀₎ -N- ethylsulfonyl Examples include glycine salt (K), bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, and monoperfluoroalkyl (C ₆ -C ₁₆ ) ethyl phosphate. These fluorine compounds may be emulsified. The fluorine-based compound used for the surface coating layer of the halogen-free flame retardant particles (B) is preferably heat-treated at 150 to 180 ° C. after being preliminarily dried at around 100 ° C. The orientation of the perfluoro group is aligned.

  Examples of the silicone compound include methylchlorosilane, methylpolysiloxane, methylphenylpolysiloxane, dimethylpolysiloxane, methylhydropolysiloxane, alkyl-modified polysiloxanes, fluorine-modified polysiloxanes, polyether-modified polysiloxanes, and alcohol-modified compounds. Examples thereof include polysiloxanes, amino-modified polysiloxanes, epoxy-modified polysiloxanes, phenol-modified polysiloxanes, carboxy-modified polysiloxanes, and mercapto-modified polysiloxanes. Among these silicone compounds, examples of the modified polysiloxane include those in which the modified site is a side chain modified product, those in which both ends are modified, and those in which one end is modified. In particular, methylhydrodiene polysiloxane or a combination of methylhydrodiene polysiloxane and hydroxyl-terminated dimethylpolysiloxane can be preferably used. Further, a metal salt of an organic acid such as 2-ethylhexylic acid or acetic acid may be used as a catalyst for promoting siloxane (Si—O—Si) cross-linking between methylhydrodiene polysiloxane molecules, and the halogen-free flame retardant An aminoplast resin can be used in combination in order to improve the adhesion to the resin. The silicone compound treated with the halogen-free flame retardant is preferably subjected to heat treatment at 150 to 180 ° C. after preliminary drying at around 100 ° C. in order to promote siloxane crosslinking.

  As the thermosetting resin used for the surface treatment coating of the halogen-free flame retardant particles (B) such as the phosphorus-containing compound, the nitrogen-containing compound, and the inorganic compound, the thermosetting resin, that is, an epoxy resin, Any one selected from unsaturated polyester resin, phenol resin, melamine resin, urea resin, triazine resin, and diallyl phthalate resin may be used. Especially, when melamine resin, urea resin, or triazine resin is used, surface coating treatment is easy. This is preferable. As the phosphorus-containing compound, ammonium polyphosphate and melamine polyphosphate are particularly preferable, and those obtained by surface-coating these particles with a thermosetting resin such as melamine resin, urea resin, and triazine resin can be particularly preferably used.

  Further, as the nitrogen-containing compound, (iso) cyanuric acid derivatives, (iso) cyanurate derivatives and the like are particularly preferable, and those obtained by surface coating with thermosetting resins such as melamine resin, urea resin, and triazine resin can be preferably used. These surface coating layers preferably contain an additive compound such as an alkylfluoro group-containing compound or a silicone compound, and these surface coating layers preferably further contain a light-resistant stabilizer.

  In the polyolefin-based resin coating layer, the halogen-based flame retardant particles (B) having a surface coating layer are blended at a weight ratio of 20 to 200 parts by weight with respect to 100 parts by weight of the polyolefin-based resin blend (A). At this time, in order to prevent aggregation of the flame retardant particles (B) and to improve dispersibility in the resin, these halogen-free flame retardant particles (B) include oleic acid, lauric acid, Surface modification treatment with higher fatty acids such as myristylic acid, palmitic acid, stearic acid, and behenic acid, and metal salts of these higher fatty acids may be further performed.

  In addition, when the particle main body of the halogen-free flame retardant particles is composed of an inorganic compound, it contains a metal alkoxide compound, an organic silane compound, an organic titanate compound, an alkyl fluoro group, which is used in combination with a thermosetting resin for forming a surface coating layer. Among additive compounds such as compounds and silicone compounds, it is particularly preferable to use metal alkoxide compounds, organic silane compounds, and organic titanate compounds. One or more additive compounds selected from the metal alkoxide compound, the organic silane compound, and the organic titanate compound may be uniformly dispersed in the thermosetting resin to form a surface coating layer. The surface of the inorganic compound particles may be treated with one or more additive compounds selected from a metal alkoxide compound, an organic silane compound, and an organic titanate compound, and surface coating with a thermosetting resin may be performed thereon. As the inorganic compound, it is particularly preferable to use aluminum hydroxide, magnesium hydroxide or the like, and these surface coating layers may further contain a light-resistant stabilizer.

  The method of forming the surface coating layer of the halogen-free flame retardant particles (B) used in the present invention is based on the properties and form of the particle main body of the halogen-free flame retardant particles (B) used and the thermosetting resin used. Accordingly, it can be appropriately selected from known methods such as a gas phase method, a liquid phase method, a microcapsule method, an autoclave method, a spray method, and a mechanochemical method. For the surface coating of the particle main body of the halogen-free flame retardant particles (B), a method in which the particle main body for halogen-free flame retardant particles (B) is dispersed and brought into contact with a thermosetting resin solution is simple and suitable. . At this time, as the thermosetting resin solution, a solution dissolved in an organic solvent, an emulsion, a solution in which a thermosetting resin precursor is dissolved in an organic solvent, or an aqueous solution of a thermosetting resin precursor, Any of these may be used. Also, at this time, one or more additions selected from compounds such as metal alkoxide compounds, organic silane compounds, organic titanate compounds, alkylfluoro group-containing compounds, and silicone compounds, particularly metal alkoxide compounds, organic silane compounds, and organic titanate compounds. It can be used by containing a compound and a light stabilizer.

  In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the light-resistant stabilizer (D) is added to the polyolefin resin coating layer in an amount of 0.05 to 3.3 with respect to 100 parts by weight of the polyolefin resin blend (A). Contains 0 part by weight. Examples of the light-resistant stabilizer (D) added to the polyolefin resin blend (A) include benzotriazole compounds, benzophenone compounds, cyanoacrylate compounds, salicylate compounds, and hindered amine compounds. Examples of the benzotriazole compound include 2- (2′-hydroxy-3′-tert-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-3 ′, 5′-di). tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole, 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) be Zotriazole, 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- And a condensate of 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′-dihydroxybenzophenone. 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and the like. Examples of the cyanoacrylate compound include ethyl-2-cyano-3,3-diphenyl acrylate and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate. Examples of salicylate compounds include phenyl salicylate, 4-t-butyl-phenyl salicylate, 4-t-octyl-phenyl salicylate, and bisphenol A-disalicylate.

  Examples of the hindered amine compounds include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, and bis (2-decanoic acid) ( 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- Condensate of tetramethyl-1-piperidineethanol, N, N ′, N ″, N ′ ″-tetrakis [4,6-bis [butyl (N-methyl-2,2,6,6, -te Lamethylpiperidin-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) 1,3-benzenedicarboxamide-N, N′-bis (2,2,6,6, -tetramethyl-4-piperazinyl), poly [[6- (1,1,3,3-tetra Methylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6- Tetramethyl-4-piperidyl) imino]], dibutylamine-1,3,5-triazine-N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl-1,6-hexamethylene Examples thereof include polycondensates of diamine-N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine.

  As the light-resistant stabilizer (D) added to the polyolefin resin blend (A), two or more kinds selected from the above compounds can be used in combination. In particular, those compounds having a melting point of 150 ° C. or lower are preferable because they have good dispersibility when kneaded with the polyolefin resin blend (A). Further, as the hindered amine compound, the N-position hydrogen of the piperidyl group is a methyl group. Those substituted with an alkyl group such as methoxy, and those substituted with an alkoxy group such as a methoxy group are particularly preferred because they are more stable. The addition amount of the light-resistant stabilizer (D) is 0.05 to 3.0 parts by weight with respect to 100 parts by weight of the polyolefin resin blend (A). If the addition amount is less than 0.05, light resistance cannot be obtained satisfactorily, and if it is added in an amount exceeding 3.0 parts by weight, the light resistance is sufficient, but the addition amount is increased. A suitable improvement in light resistance cannot be obtained, and conversely, it may cause a trouble of blooming of the light resistance stabilizer.

  Moreover, the said light-resistant stabilizer (D) may be contained in the surface coating layer of the said halogen-free flame retardant particle (B). In this case, the light-resistant stabilizer (D) is one or more kinds selected from the thermosetting resin, the metal alkoxide compound, the organic silane compound, the organic titanate compound, the alkylfluoro group-containing compound, and the silicone compound. It is preferable that it is 0.05-3.0 weight% with respect to the surface coating layer which consists of a compound, and is 0.1-1.5 weight% of compounding quantities as an optimal amount. When the blending amount of the light stabilizer is less than 0.05%, the thermosetting resin contained in the surface treatment coating layer of the halogen-free flame retardant is photodegraded, nitrogen oxides contained in the rain, and Due to corrosion by sulfur oxides, a problem of gradually deactivating flame retardancy occurs, and at the same time, the flame retardant particles are thinned by corrosion (volume reduction), thereby reducing the strength of the obtained sheet. Moreover, when the compounding quantity of the said light-resistant stabilizer exceeds 3.0%, not only will a light-resistant stabilizer bloom from a thermosetting resin, but the flame retardance of the sheet | seat obtained will be reduced.

  The film for forming a polyolefin-based resin coating layer of the acid rain-resistant flame-retardant polyolefin-based resin sheet of the present invention can be formed by a conventionally known molding method, for example, a T-die extrusion method, an inflation method, a calendar method, or the like. it can. A compound for forming a polyolefin-based resin coating layer, for example, by a calendar molding method after melt-kneading with a Banbury mixer or kneader, or after melt-kneading using a twin-screw kneader, etc., with a single-screw extruder, twin-screw extruder, etc. After melt-kneading granulation, it may 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 acid rain resistant flame retardant polyolefin resin sheet of the present invention is a polyolefin resin in which one or more halogen-free flame retardant particles (B) are collectively contained at a high concentration. The pellets granulated from the blend (A) or the pellets obtained by granulating the polyolefin resin blend (A) containing two or more kinds of flame retardant particles (B) separately in high concentrations are prepared in advance. In addition, this may be blended as part of a compound composition resin for forming a polyolefin resin coating layer and melt kneaded with a Banbury mixer, kneader, etc., and this kneaded product may be formed into a film by a calendar method. The method is preferable because the halogen-free flame retardant can be quantitatively dispersed efficiently. In the conventional batch kneading method, these halogen-free flame retardant particles sometimes settle and agglomerate in a kneader such as a Banbury mixer or a kneader, and therefore remain in the polyolefin resin blend (A). It is insufficient to quantitatively disperse the halogen-free flame retardant particles (B), resulting in non-compliance with the flame proof standards (Article 4 of the Fire Service Act: JIS Standard L-1091) established in the Fire Service Act. Sometimes. In addition to the halogen-free flame retardant particles (B), these granulated pellets may be melt-kneaded and granulated with colorants such as organic pigments and inorganic pigments, and light stabilizers.

  The film for a polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention can be produced by a processing technique such as a T-die extrusion method, an inflation method, a calendar method, etc., using the above compound. However, the use of the calendar method for the production of films colored with organic pigments, inorganic pigments, etc., or for processing with many color change operations, is simple with less compounding. The film for a polyolefin resin coating layer of the acid rain resistant flame retardant polyolefin resin sheet of the present invention is preferably molded into a film in a temperature range of 100 to 200 ° C. by a calendering method. In order to improve the film appearance, it is preferable to add a phosphate ester-based, aliphatic amide-based or montanic acid-based lubricant. The thickness of the polyolefin resin coating layer film obtained by the calendering method is preferably 80 to 500 μm, and more preferably 130 to 300 μm. If the thickness is less than this range, molding is difficult, and when laminated to the base fabric, the film breaks off at the intersection of the base fabric fiber fabric, impairing waterproofness, and durability of the sheet May decrease. Although there is no restriction | limiting in the thickness of the acid rain-resistant flame-retardant polyolefin resin sheet of this invention, it can laminate on a base fabric using 1-4 sheets of 80-500 micrometers polyolefin resin coating layer films. preferable. In particular, it is preferable that two films for a polyolefin-based resin coating layer having a thickness of 130 to 300 μm are laminated and adhered to both surfaces of the base fabric.

  The fiber fabric that can be used for the base fabric of the acid rain-resistant flame-retardant polyolefin resin sheet of the present invention may be either a woven fabric or a knitted fabric, and examples of the woven fabric include plain weave, twill weave and satin weave. Particularly, when a plain woven fabric is used, the warp / wet property balance of the polyolefin resin sheet obtained is excellent. The warp and weft yarns of the fiber fabric may be woven with any of synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers, or mixed fibers composed of two or more of these, but considering 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 can be 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 for the base fabric of the high-frequency fusible polyolefin resin sheet of the present invention, plain weaving with multifilament fiber yarns composed of polyester fiber, nylon fiber, polypropylene fiber, vinylon fiber, and mixed fibers thereof is used. A woven fabric is preferred. As these fiber fabrics, it is also possible to use fiber fabrics that have been flame-retarded as necessary and fabrics woven with fibers that have been flame-retarded in advance. As the fiber fabric subjected to flame retardant treatment, depending on the type of fiber, phosphate ester compound flame retardant, ammonium polyphosphate compound flame retardant, (iso) cyanuric acid derivative compound flame retardant, cyanamide compound flame retardant, Difficult to contain one or more selected from urea compound flame retardant and sulfur compound flame retardant using water or organic solvent, or emulsion and latex as dispersion medium, and dispersing or dissolving flame retardant Examples include those obtained by impregnating the above-mentioned fiber fabric with a flame retardant, drying and heat treatment. In addition, as the fiber flame-retarded in advance, one or more kinds selected from the above flame retardants are blended at the stage of spinning the yarn from a thermoplastic resin such as polyethylene resin, polypropylene resin, polyester resin, polyamide resin. Flame retardant fiber obtained by melt spinning, or polyester obtained by polycondensation by replacing part of the raw material monomer with phosphate ester-containing monomer or halogen-containing monomer in the stage of synthesizing thermoplastic resin Examples thereof include flame retardant fibers melt-spun from resin, polyamide resin, and the like.

  As the multifilament yarn used in the fiber fabric for base fabric of the acid rain-resistant flame-retardant polyolefin resin sheet of the present invention, a multifilament yarn of 125 to 2000 denier, particularly 250 to 1000 denier can be used. . If the multifilament yarn is less than 125 denier, the tear strength of the obtained sheet is inferior, and if it exceeds 2000 denier, the breaking strength and tearing strength are improved, but as the yarn diameter increases, the sheet becomes thicker, Unevenness caused by the weaving intersections of the fiber fabric is increased, resulting in poor smoothness. Moreover, it is preferable that the fiber fabric used for the 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 a woven fabric obtained by driving 8 to 38 multifilament yarns of 125 to 2000 denier per inch of warp / weft yarn, for example, 500 denier multifilament In the case of filament yarn, a plain woven fabric obtained by driving 14-24 yarns per inch, and in the case of 1000 denier multifilament yarn, a plain woven fabric obtained by driving 12-22 yarns per inch can be exemplified. .

  Further, those fiber fabrics preferably have a porosity (missing) of 5 to 40%. If the porosity is less than 5%, the yarn density may be excessive and the resulting sheet may have insufficient flexibility, and for two polyolefin resin coating layers to be adhered to the front and back surfaces of the fiber fabric. This is not preferable because the bridge-bonding property between films may be lowered and the dynamic durability may be deteriorated. Also, if the porosity exceeds 40%, the flexibility and the bridge fusing property of the film are improved, but the content of the fiber yarns in the weft direction becomes too small, resulting in insufficient dimensional stability of the obtained sheet. In some cases, the tear strength of the sheet is lowered and the utility is deteriorated. The porosity can be obtained as a value obtained by subtracting 100 from the area of the fiber yarn in the unit area of the fiber fabric as a percentage. It is preferable that the porosity is obtained by using a unit area of 10 cm in the longitudinal direction and 10 cm in the weft direction.

Moreover, the fiber fabric used for the base fabric of the acid rain-resistant flame retardant polyolefin resin sheet of the present invention is pretreated with a silicon compound-containing composition. The silicon compound-containing composition is selected from a composition comprising at least one selected from synthetic amorphous silica, colloidal silica, and silane coupling agent, and synthetic amorphous silica, colloidal silica, and silane coupling agent. Moreover, the composition of 1 or more types and a thermoplastic resin is mentioned. Among these silicon compounds, synthetic amorphous silica includes 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, silicon sodium and mineral acid with a low hydroxyl group content It is obtained by a wet method in which silica, sodium silicate, mineral acid, and salts are reacted in an aqueous solution obtained by the airgel method, in which silica gel is generated from the silica gel and the organosol in which the water in the silica gel is replaced with an organic solvent such as alcohol is dried. Silica etc. which can be used can be used. These silica particles preferably have an average particle size of about 1 to 20 μm. In the preparation of the fiber fabric, the fiber fabric is immersed in a silica aqueous solution having a SiO ₂ concentration of 10 to 30% by weight in which synthetic amorphous silica is uniformly dispersed in water, and the fiber fabric is pulled up from the bath and simultaneously passed through a nip roll. It is possible to remove excess silica aqueous solution and dry the water. 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 synthetic amorphous silica and a silane coupling agent in combination.

Examples of the colloidal silica include an aqueous dispersion medium colloidal silica sol (SiO ₂ ) having a BET average particle diameter of 10 to 50 nm obtained by cation exchange of a sodium silicate solution, or a BET average using an organic solvent as a dispersion medium. Colloidal silica sol (SiO ₂ ) having a particle diameter 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, and to remove moisture or organic matter. It can be carried out by drying the system 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 a colloidal silica and a silane coupling agent in combination.

The silane coupling agent is a compound having two or more different reactive groups in the molecule represented by the general formula: XR-Si (Y) ₃ , for example, X = amino group, vinyl group, epoxy group , Chloro group, mercapto group and the like (R = alkyl chain), Y = methoxy group, ethoxy group and the like. 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- Examples include aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, and γ-mercaptopropyltrimethoxysilane. It is preferred to use a coupling agent. The silane coupling agent is preferably used at a concentration of 1 to 5% by weight and 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 together, and the adhesion rate to the fiber fabric is not particularly limited, but the adhesion rate is preferably 3 to 10% by weight.

  As the thermoplastic resin used together with the silicon compound, an aqueous dispersion such as an emulsion of a thermoplastic resin or a dispersion, or a form solubilized in an organic solvent can be used, and an ionomer resin or an acrylic resin can be used. Resins, vinyl acetate resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, polystyrene resins, saturated polyester resins, polyamide resins, and modified resins thereof can be used. Particularly preferred are ethylene copolymer resins and acrylic copolymer resins modified with glycidyl methacrylate, dimethylaminoethyl methacrylate, itaconic anhydride, maleic anhydride, N-methylmaleimide and the like. If necessary, blend with thermosetting resins such as phenol resins, melamine resins, urea resins, unsaturated polyester resins, epoxy resins, thermosetting polyurethane resins, allyl phthalate resins. You can also. The fiber fabric is pretreated by immersing the fiber fabric in an aqueous treatment bath in which the silicon compound is mixed in these thermoplastic resin emulsions or dispersions, pulling up from the bath and simultaneously passing through a nip roll to remove excess silicon. It can be carried out by removing the compound-containing composition 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, It is preferable that it is about thermoplastic resin: silicon compound (synthetic amorphous silica) / 10-50: 90-50 weight%.

  A film formed from a composition containing a polyolefin resin blend (A) containing 3 to 25% by weight of the synthetic amorphous silica is applied to a base fabric comprising a fiber fabric pretreated with these silicon compound-containing compositions. It is preferable to laminate and, in the present invention, the silicon compound-containing composition further comprising the thermoplastic resin: silicon compound / 10 to 50:90 to 50% by weight contains at least a silane coupling agent, and It is preferable that a film layer made of a polyolefin resin blend (A) -containing composition containing 3 to 25% by weight of the synthetic amorphous silica is laminated.

  In the acid rain resistant flame retardant polyolefin resin sheet of the present invention, the fiber fabric is pretreated with a silicon compound-containing composition, and the base fabric is a flame retardant fiber fabric pretreated with a silicon compound-containing composition. The laminated form of the polyolefin resin coating film is particularly preferably a polyolefin resin coating film laminated on both sides of these fiber fabrics, but may be a laminated form on only one side depending on the application. . Moreover, as a lamination method, an adhesive layer may be provided between the polyolefin-based resin coating film and the above-mentioned base treatment base fabric, or they may be laminated without an adhesive layer. In particular, when a form in which the polyolefin resin coating film is laminated only on one side of the base fabric is required, the base fabric to be used is preferably flame-retardant. As a method for laminating the polyolefin resin coating film, a calendar topping method or a T-die extrusion laminating method in which the polyolefin resin coating film is heat-laminated to the base fabric at the same time as the molding process of the polyolefin resin coating film, or a calendar method, After a polyolefin resin coating film is produced by a single molding process using a T-die extrusion method or an inflation method, the polyolefin resin coating film is thermocompression bonded onto the base fabric surface using a laminator. Examples include a method of stacking. In the production of the flame retardant light-resistant polyolefin resin sheet of the present invention, a production method by thermocompression bonding of a polyolefin resin coating film molded by a calender method and a pretreated base fabric is efficient and economical. It is preferable. At this time, the two polyolefin resin coating films on the front and the back of the fiber fabric for base fabric are hot-melt bridged through the voids in the fiber fabric for the base fabric. For this reason, good adhesion and durability can be obtained without the need for special adhesive application and extra steps.

Alternatively, a polyolefin resin coating film may be laminated on the surface of the base treatment base fabric, and the back surface of the base treatment base fabric may be covered with a thermoplastic resin layer. This thermoplastic resin layer
(C) 100 parts by weight of a thermoplastic resin, (B) 20 to 200 parts by weight of a flame retardant particle body, a surface coating layer formed on the surface thereof , and including a thermoplastic resin and a light-resistant stabilizer (D). At least one halogen-free flame retardant particle having
In order to form the thermoplastic resin layer,
(A ′) an aqueous resin liquid comprising at least one selected from an aqueous emulsion and an aqueous dispersion of the thermoplastic resin (C),
Or
(B ′) a solution obtained by dissolving the thermoplastic resin (C) in an organic solvent,
The coating solution (coating solution) is prepared by containing the halogen-free flame retardant particles (B) and the light-resistant stabilizer (D), and this coating solution is applied to the back surface of the pretreated base fabric. And dry. These thermoplastic resins include ionomer resins, acrylic resins, vinyl acetate resins, polyvinyl alcohol resins, ethylene-vinyl acetate copolymer resins, polyurethane resins, polystyrene resins, saturated polyester resins, polyamide resins. Those containing at least one of resins and modified resins thereof can be used. If necessary, at least one of a thermoplastic resin such as phenolic resin, melamine resin, urea resin, unsaturated polyester resin, epoxy resin, thermosetting polyurethane resin, and allyl phthalate resin may be added to one or more of the above thermoplastic resins. It is also possible to use a blend of various thermosetting resins.

  The acid rain resistant flame retardant polyolefin resin sheet of the present invention can be easily joined by fusion using a high frequency welder. As the high-frequency welder bonding method, specifically, two or more polyolefin resin sheets of the present invention or a part of other polyolefin resin molded products that can be heat-sealed with the polyolefin resin sheet of the present invention. 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 to the joining portion. The overlapped portions are thermally fused and bonded and sealed by molecular frictional heat of the thermoplastic resin generated in the portions pressurized and applied by the weld bar. 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 that oscillates at a 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. High-frequency welder fusion machines such as YC-7000FT and YF-7000 from Yamamoto Vinita Co., Ltd., KM-5000TA and KA-7000TE from Seiden 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 and comparative examples, test methods such as evaluation of flame resistance, evaluation of light resistance, evaluation of workability, evaluation of high-frequency welder adhesion, evaluation of joint strength, etc. of the polyolefin resin sheet of the present invention are as follows. It is as follows.

(I) Flame-proof evaluation of polyolefin resin sheet The test was conducted in accordance with Article 4 of the Fire Service Act Construction Rules (JIS L-1091: A-2 Method Category 3: 2 minutes heating) and evaluated according to the following criteria.
○: Carbonized area 40 cm ² or less, after flame time 5 seconds or less,
The residual dust time is 20 seconds or less and the carbonization distance is 20 cm or less.
×: One or more items of carbonization area, afterflame time, residual time, and carbonization distance exceed the standard numerical values.
(II) Evaluation of acid resistance of polyolefin resin sheet Polyolefin resin compound was melted and kneaded uniformly with two rolls set at 140 ° C for 5 minutes, and then a press machine manufactured by Toyo Seiki Seisakusho Co., Ltd. Automatic lab press: 15 tons), temperature 150 ° C × compression pressure 100 kgf / cm ² × (heating compression time 3 min + water-cooled compression time 2 min), smooth surface 1.0 mm thickness × 150 mm × 150 mm size A polyolefin resin press sheet was obtained. From this press sheet, a No. 3 type test piece specified in JIS K-6301 was collected from the press sheet, and in a mixed aqueous solution of a 1 N (N) concentration nitric acid aqueous solution and a 0.1 N (N) concentration sulfuric acid aqueous solution. After being soaked at 20 ° C. for 24 hours, it was naturally dried at room temperature and left as it was for 6 days. This immersion-drying was taken as one cycle, and 5 cycles were tested, and the critical oxygen index (JIS K-7231) and residual strength (JIS K-6301) of the test piece were measured.
○: It has a critical oxygen index retention of 80% or more and a residual strength retention of 80% or more.
(Triangle | delta): It has a limit oxygen index retention of 80% or more, or a residual strength retention of 80% or more.
X: Both the critical oxygen index retention rate and the residual strength retention rate are less than 80%.

(III) Evaluation of light resistance of polyolefin resin sheet The test sample was subjected to a light resistance acceleration test (JIS L-0842) using a sunshine carbon weather meter for 1000 hours, and the surface of the test sample was measured based on the sample before the acceleration. The degree of color fading was digitized by measuring the color difference ΔE (JIS Z-8729), and the light resistance 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.
ΔE = 8˜: × = discoloration is conspicuous and has a problem in practicality.
Further, the sample after 1000 hours of the light resistance acceleration test was subjected to the acid resistance test of the above test (II), and its critical oxygen index (JIS K-7231) and residual strength (JIS K-6301) were measured.
○: It has a critical oxygen index retention of 80% or more and a residual strength retention of 80% or more.
(Triangle | delta): It has a limit oxygen index retention of 80% or more, or a residual strength retention of 80% or more.
X: Both the critical oxygen index retention rate and the residual strength retention rate are less than 80%.

(IV) 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 4 cm x 30 cm weld bar (tooth shape: convex portions are 4 cm wide linearly shaped with a uniform spacing 9) High frequency welder fusion machine (Yamamoto Vinita) (equipment: 25.4mm, convex height: 0.5mm: concave part is 4cm wide, 9 linear straight forming / 25.4mm, concave part depth 0.5mm) Co., Ltd. YF-7000 type: output 7 KW). A sample of 3 cm width × 30 cm including a 4 cm overlap bonded portion was collected from the bonded body, a shear test (JIS L-1096) of the 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

(V) Evaluation of joint strength A specimen with a test piece width of 3 cm and a test piece length of 30 cm including a stacking width of 4 cm was collected from the welder fusion sheet of (IV), and a tensile tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.). : Strograph V10 type) until the specimen was broken.
○: Destructed except at the joint.
Δ: Some thread breakage was broken at the joint.
X: Yarn breakage at the joint was broken.

(VI) Evaluation of workability 100 g of polyolefin resin compound was put into two 6-inch diameter rolls (test rolls) set at 140 ° C. with a gap between rolls set to 1 mm, and the compounds were kneaded for 5 minutes. Next, the limiting oxygen index defined in JIS K-7231 was measured using a 1 mm thick sheet obtained by kneading.
○: Kneading was easy and completed within 5 minutes. The obtained compound had an oxygen index within ± 2% of the designed value.
Δ: Complete mixing was difficult within 5 minutes, and powder spilled under the roll. The obtained compound had an oxygen index of ± 2 to 5% of the designed value.
X: Complete kneading was difficult within 5 minutes, and powder spilled under the roll. The obtained compound had an oxygen index of ± 5% or more of the designed value.

(VII) Evaluation of Bloom (Bleed) Property of Sheet A 10 cm × 10 cm size sample was taken from the sheet of (VI), left in a refrigerator at 0 ° C. for 24 hours, and then a gear set at 40 ° C. It was left in the oven for 24 hours. With this as one cycle, the environmental temperature change of 0 ° C. → 40 ° C. → 0 ° → 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)

[Comparative Example 1]
30 parts by weight of linear low density polyethylene resin (a-1) polymerized in the presence of a metallocene catalyst (Trademark: Kernel KF360: MFR2.0: Density 0.898: Nippon Polychem Co., Ltd.), ethylene-acetic acid With respect to 70 parts by weight of a polyolefin resin blend comprising 40 parts by weight of a vinyl copolymer resin (b-1) (trademark: Evertate K2010: MFR3.0: VA content 25% by weight: Sumitomo Chemical Co., Ltd.) A compound was prepared by blending 100 parts by weight of inorganic compound particles (B-1) subjected to surface coating.
This compound contains inorganic compound particles (B-1) at a concentration of 58.8% by weight using a twin-screw extruder (Thermo Plastics Industries Co., Ltd .: TPP-20F: hot cut pelletizing device). 3.5 mm square cubic pellets were granulated.
Next, linear low density polyethylene resin (a-1) (trademark: kernel) polymerized in the presence of a metallocene catalyst with respect to 170 parts by weight of the obtained pellets containing inorganic compound (1-a). 30 parts by weight of KF360: MFR2.0: density 0.898: Nippon Polychem Co., Ltd.) and light stabilizer (D-1) (trademark: Biosorb 510: 2- (2′-hydroxy-4′-octoxyphenyl) ) Benzotriazole: Kyodo Yakuhin Co., Ltd.) 0.5 parts by weight, light stabilizer (D-2) (Trademark: Tinuvin 765: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate : Ciba Specialty Chemicals Co., Ltd.) 0.5 parts by weight, phosphate ester lubricant (trademark: LTP-2: Kawaken Fine Chemicals Co., Ltd.) 1.0 part by weight, and [(organic Family face Colored pellets: Trademark: HCM1617 Blue: Cyanine blue (α) content 20 wt%: 1 part by weight of Dainichi Seika Kogyo Co., Ltd. + Inorganic pigment Colored pellets: Trademark: HCM2060 White: Titanium dioxide (R) 60 wt% : Dainichi Seika Kogyo Co., Ltd.] 2 parts by weight] A compound containing 3 parts by weight was prepared.
This compound was kneaded for 5 minutes with a test roll set at 150 ° C. (Nishimura Seisakusho Co., Ltd .: 2 rolls of 6 inch diameter), and then the roll interval of the test rolls was adjusted to 0.17 mm, and the thickness was reduced to 0 by calendar rolling A polyolefin resin coating layer film having a LOI value of 28.4 containing 10% by weight of a vinyl acetate component of .17 mm was prepared.
Next, the obtained film was placed on both sides of a polyester plain woven fabric (250 denier polyester multifilament: yarn density warp 20 / 2.54 cm × weft 21 / 2.54 cm: porosity 20%: mass 55 g / m ² ). A polyolefin resin sheet having a thickness of 0.45 mm and a mass of 485 g / m ² was obtained by bonding with a laminator having a heat roll and a pressure roll pair set at 140 ° C. and an infrared heater.

<Inorganic compound particles with surface coating layer (B-1)>
i) A total of 500 parts of 400 parts by weight of distilled water and 100 parts by weight of methanol is added to an organic silane compound (trademark: SH6040: γ-glycidoxypropyl-trimethoxysilane: molecular weight 236: effective amount 100%: Toray Dow After adding 3 parts by weight of Corning Silicone Co., Ltd. and stirring for 30 minutes, the inorganic compound particle body (1) (Trademark: Magsees N-3: Magnesium hydroxide: Average particle size 1.2 μm: Kamishima Chemical Industries) 100 parts by weight was added, and the mixture was further stirred for 30 minutes, filtered and dried at 120 ° C. for 2 hours to obtain 100.6 g of inorganic compound particles (B-1 ′).

  ii) Next, 500 parts by weight of distilled water was mixed with melamine resin (trademark: Polyfix LF11: modified melamine: solid content 55% by weight: 20 parts by weight of Showa Polymer Co., Ltd.), and light stabilizer (trademark: Sunlife LPS- 700: Benzotriazole-based UV absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) 0.5 part by weight was added and stirred, and the inorganic compound particles (B-1 ′) obtained in the step i) ) 100.6 g was added and stirred for 10 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.58 g of inorganic compound particles (B-1) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body was 4.38%, and the content of the organosilane compound with respect to the melamine resin was 13.1% by weight. Further, the content of the light stabilizer in the surface coating layer was 1.27% by weight.

[Comparative Example 2]
20 parts by weight of a linear low-density polyethylene resin (a-2) polymerized in the presence of a metallocene catalyst (trademark: Evolue SP2020: MFR1.7: density 0.917: Mitsui Chemicals, Inc.), ethylene-acetic acid Vinyl copolymer resin (b-2) (Trademark: EVAFLEX P1905: MFR2.5: VA content 19% by weight: Mitsui DuPont Polychemical Co., Ltd.) 50 parts by weight of polyolefin resin blend consisting of 50 parts by weight The compound which mix | blended 100 weight part of inorganic type compounds (B-2) which gave the following surface coating was prepared. This compound was granulated into 3.5 mm square cubic pellets containing the inorganic compound (B-2) at a concentration of 58.8% by weight using a twin-screw extruder (same as Comparative Example 1). Next, a linear low density polyethylene resin (a-2) (trademark: Evolue SP2020) polymerized in the presence of a metallocene catalyst with respect to 170 parts by weight of the obtained pellets containing the inorganic compound (B-2). : MFR1.7: Density 0.917: Mitsui Chemicals, Inc.) 30 parts by weight and light-resistant stabilizer (D-1) (trademark: Biosorb 510: 2- (2′-hydroxy-4′-octoxyphenyl) 0.5 parts by weight of benzotriazole: Kyodo Yakuhin Co., Ltd., and light stabilizer (D-2) (trademark: Tinuvin 765: bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate: Ciba Specialty Chemicals Co., Ltd. 0.5 parts by weight, phosphate ester lubricant (trademark: LTP-2: Kawaken Fine Chemicals Co., Ltd.) 1.0 part by weight, and [(organic pigments Mosquito Pellets: Trademark: HCM1617 Blue: Cyanine Blue (α) content 20% by weight: 1 part by weight of Daiichi Seika Kogyo Co., Ltd. + Inorganic pigment Colored pellets: Trademark: HCM2060 White: Titanium dioxide (R) 60% by weight: Daiichi Seika Kogyo Co., Ltd.] 2 parts by weight] 3 parts by weight were blended to prepare a compound. This compound was kneaded for 5 minutes with a test roll set at 150 ° C. (same as Comparative Example 1), the roll interval of the test roll was adjusted to 0.17 mm, and a vinyl acetate component having a thickness of 0.17 mm was formed by calendar rolling. A polyolefin resin coating film having a LOI value of 29.3 and containing 10% by weight was obtained. Next, the obtained film was applied to both sides of a polypropylene plain woven fabric (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 ). A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 490 g / m ² was obtained by thermocompression bonding with a laminator having an infrared heater set at 140 ° C.

<Inorganic compound particles with surface coating layer (B-2)>
i) To a total of 500 parts by weight of 400 parts by weight of methanol and 100 parts by weight of distilled water, a metal alkoxide compound (trademark: tetra-n-butoxysilicon: effective amount 100%: Sumitomo Cement Co., Ltd. 5 parts by weight was added. After stirring for 30 minutes, 100 parts by weight of inorganic compound particle body (2) (trademark: B-315: aluminum hydroxide: average particle size 15 μm: Alcoa Kasei Co., Ltd.) was added, and the mixture was further stirred for 30 minutes. And dried at 120 ° C. for 2 hours to obtain 100.6 g of inorganic compound particles (B-2 ′).

  ii) Next, in 500 parts by weight of distilled water, a benzoguanamine resin (trademark: Polyfix PG-251: modified benzoguanamine: solid content 54% by weight: 20 parts by weight of Showa Polymer Co., Ltd.) and a light-resistant stabilizer (trademark: Sun Life) LPS-700: benzotriazole-based UV absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) 0.5 parts by weight was added and stirred, and the inorganic compound particles (B-2) obtained in step i) above were stirred. ') 100.6g was added and it stirred for 10 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.52 g of an inorganic compound (B-2) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body (2) was 4.32%, and the content of the metal alkoxide compound with respect to the benzoguanamine resin was 13.3% by weight. Further, the content of the light stabilizer relative to the surface coating layer was 1.29% by weight.

[Comparative Example 3]
70 wt. Of polyolefin resin blend comprising 30 wt. Parts of linear low density polyethylene resin (a-1) polymerized in the presence of a metallocene catalyst and 40 wt. Parts of ethylene-vinyl acetate copolymer resin (b-1). The compound which mix | blended 50 weight part of inorganic compound (B-3) particle | grains which gave the following surface coating and 30 weight part of nitrogen containing compound particles which gave the following surface coating with respect to the part was prepared. Using this compound, a 3.5 mm square cubic shape containing a total amount of the inorganic compound (B-3) and the nitrogen-containing compound in a concentration of 53.3% by weight using a twin-screw extruder (same as Comparative Example 1). The pellets were granulated. Next, with respect to 150 parts by weight of the obtained granulated pellets, 30 parts by weight of a linear low density polyethylene resin (1) polymerized in the presence of a metallocene catalyst and 0.5 parts by weight of a light stabilizer (D-1) Part, light-resistant stabilizer (D-3) (trademark: Tinuvin 114: bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl)] -4-hydroxyphenyl] methyl] butyl malonate: 0.5 parts by weight of Ciba Specialty Chemicals), 1.0 part by weight of a phosphate ester lubricant (same as Comparative Example 1), and a coloring pigment (Pigment colored pellets: the same as Comparative Example 1) and a compound containing 3 parts by weight were prepared. This compound was kneaded with a test roll (same as Comparative Example 1) for 5 minutes, then the roll interval of the test roll was adjusted to 0.17 mm, and a 0.17 mm thick vinyl acetate component was contained by calendar rolling to contain 10% by weight. A polyolefin resin blend film having a LOI value of 32.6 was obtained. Next, the obtained film was bonded to both sides of the same polyester plain woven fabric (250 denier polyester multifilament) as in Example 1 with a laminator in the same manner as in Example 1, and the thickness was 0.46 mm and the mass was 485 g / m ² . A polyolefin resin sheet was obtained.

<Inorganic compound with surface coating layer (B-3)>
i) To 500 parts by weight of isopropyl alcohol, 5 parts by weight of an organic titanate compound (trademark: B-1: tetra-n-butoxytitanium (TBT): molecular weight 340: effective amount 100%: Nippon Soda Co., Ltd.) After stirring for 30 minutes, inorganic compound particle body (1) (Trademark: Magsees N-3: Magnesium hydroxide: average particle size 1.2 μm: 100 parts by weight of Kamishima Chemical Co., Ltd.) was added, and stirring was continued for 30 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 100.6 g of inorganic compound particles (B-3 ′).

  ii) Next, in 500 parts by weight of distilled water, urea resin (trademark: Polyfix LF20: highly condensed urea: solid content 55% by weight: 20 parts by weight of Showa Polymer Co., Ltd.) and light-resistant stabilizer (trademark: Sunlife LPS) -700: Benzotriazole-based ultraviolet absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) 0.5 parts by weight was added and stirred, and the inorganic compound particles (B-3 ′) obtained in the above step i) ) 100.6 g was added and stirred for 10 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.52 g of inorganic compound particles (B-3) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body was 4.32%, and the content of the organic titanate compound with respect to the urea resin was 15.3% by weight. Further, the content of the light stabilizer in the surface coating layer was 1.27% by weight.

<Surface coating of nitrogen-containing compound particles>
500 parts by weight of distilled water, 20 parts by weight of an epoxy resin (trademark: Denacast EM-101: modified bisphenol A type epoxy emulsion: epoxy equivalent 520: solid content concentration 50% by weight: Nagase Kasei Co., Ltd.) and triethanol as a catalyst 0.5 parts by weight of an amine and 0.5 parts by weight of a light-resistant stabilizer (trademark: Sunlife LPS-700: benzotriazole ultraviolet absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) After stirring for 5 minutes, 100 parts by weight of a nitrogen-containing compound particle main body (trademark: MC-610: melamine cyanurate: average particle diameter of 1 to 5 μm: Nissan Chemical Co., Ltd.) was added and further stirred for 30 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.78 g of a nitrogen-containing compound having a surface coating layer. The coverage of the surface coating layer with respect to the nitrogen-containing compound was 4.56%, and the content of the light-resistant stabilizer in the surface coating layer was 1.47% by weight.

[Comparative Example 4]
70 weight parts of polyolefin resin blend comprising 20 parts by weight of linear low density polyethylene resin (a-2) polymerized in the presence of a metallocene catalyst and 50 parts by weight of ethylene-vinyl acetate copolymer resin (b-2) The compound which mix | blended 30 weight part of inorganic compound particles (B-4) which gave the following surface coating and phosphorus containing compound particle which gave the following surface coating with respect to the part was prepared. Using this compound, a 3.5 mm square cubic pellet containing inorganic compound particles (B-4) and phosphorus-containing compound particles at a concentration of 53.3% by weight using a twin-screw extruder (same as Comparative Example 1) Granulated. Next, 30 parts by weight of a linear low density polyethylene resin (a-2) polymerized in the presence of a metallocene catalyst and 150 parts by weight of the obtained granulated pellets and 0. 5 parts by weight and a light-resistant stabilizer (D-3) (trademark: Tinuvin 114: bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethyl) Ethyl) -4-hydroxyphenyl] methyl] butyl malonate: Ciba Specialty Chemicals Co., Ltd. 0.5 parts by weight, phosphate ester lubricant (same as Comparative Example 1) 1.0 part by weight, coloring A compound containing 3 parts by weight of pigment (pigment colored pellets: the same as in Comparative Example 1) was prepared. This compound was kneaded with a test roll (same as Comparative Example 1) for 5 minutes, then the roll interval of the test roll was adjusted to 0.17 mm, and a 0.17 mm thick vinyl acetate component was contained by calendar rolling to contain 10% by weight. A polyolefin resin coating film having a LOI value of 33.5 was obtained. Next, the obtained film was bonded to both sides of the same polypropylene plain woven fabric (340 denier polypropylene multifilament) as in Comparative Example 2 by thermocompression bonding with a laminator in the same manner as in Example 2, and the thickness was 0.47 mm and the mass was 512 g. A polyolefin resin sheet of / m ² was obtained.

<Inorganic compound with surface coating layer (B-4)>
i) In total 500 parts of 400 parts by weight of distilled water and 100 parts by weight of methanol, an organosilane compound (trademark: SH6040: γ-glycidoxypropyl trimethoxysilane: molecular weight 236: effective amount 100%: Toray Dow After adding 3 parts by weight of Corning Silicone Co., Ltd. and stirring for 30 minutes, inorganic compound particle body (2) (Trademark: B-315: Aluminum hydroxide: Average particle size 15 μm: Alcoa Kasei Co., Ltd.) 100 parts by weight was added, and the mixture was further stirred for 30 minutes, filtered and dried at 120 ° C. for 2 hours to obtain 100.6 g of an inorganic compound (B-4 ′).

  ii) Next, in 500 parts by weight of distilled water, 20 parts by weight of phenol resin (trademark: Tamanol 720: resol type phenol resin aqueous solution: solid content 45% by weight: Arakawa Chemical Co., Ltd.) and light-resistant stabilizer (trademark: Sun Life) LPS-700: benzotriazole-based UV absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) 0.5 parts by weight was added and stirred, and the inorganic compound particles (B-4) obtained in step i) above were stirred. ') 100.6g was added and it stirred for 10 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.46 g of inorganic compound particles (B-4) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body was 4.27%, and the content of the organosilane compound with respect to the phenol resin was 15.5% by weight. The content of the light stabilizer relative to the surface coating layer was 1.34% by weight.

<Surface coating of phosphorus-containing compound particles>
To 500 parts by weight of distilled water, 20 parts by weight of a benzoguanamine resin (trademark: Polyfix PG-251: modified benzoguanamine: solid content 54% by weight: Showa High Polymer Co., Ltd.) and a light-resistant stabilizer (trademark: Sunlife LPS-700) : Benzotriazole-based ultraviolet absorber: Solid content 30% by weight: Nikka Chemical Co., Ltd. 0.5 part by weight and after stirring for 5 minutes, phosphorus-containing compound particle body (trademark: Exorit AP422: Polylin Ammonium acid (NH ₄ PO ₃ ) _n , n = 1000: phosphorus content 31 to 32% by weight: average particle size distribution of 40 μm or less: Clariant Japan Co., Ltd. (100 parts by weight) was added, and the mixture was further stirred for 30 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.65 g of phosphorus-containing compound particles having a surface coating layer. The coverage of the surface coating layer with respect to the phosphorus-containing compound particle main body was 4.44%, and the content of the light-resistant stabilizer in the surface coating layer was 1.29% by weight.

[Comparative Example 5]
70 wt. Of polyolefin resin blend comprising 50 wt. Parts of linear low density polyethylene resin (a-1) polymerized in the presence of a metallocene catalyst and 20 wt. Parts of ethylene-vinyl acetate copolymer resin (b-1). 30 parts by weight of nitrogen-containing compound particles (trademark: MC-610: melamine cyanurate: average particle diameter: 1 to 5 μm: Nissan Chemical Co., Ltd.) with the following surface coating and phosphorus with the following surface coating: A compound containing 30 parts by weight of contained compound particles was prepared. This compound was granulated into 3.5 mm square cubic pellets containing a nitrogen-containing compound and a phosphorus-containing compound at a concentration of 46.1% by weight using a twin-screw extruder (same as Comparative Example 1). Next, with respect to 130 parts by weight of the obtained granulated pellets, ethylene-methyl methacrylate copolymer resin (trademark: ACRIFTH WH206: MFR2.0: MMA content 20% by weight: Sumitomo Chemical Co., Ltd.) 30 weights and , 0.5 parts by weight of a light-resistant stabilizer (D-1), 0.5 parts by weight of a light-resistant stabilizer (D-2), 1.0 part by weight of a phosphate ester lubricant (same as Comparative Example 1), A compound containing 3 parts by weight of (pigment colored pellets: the same as in Comparative Example 1) as a colored pigment was prepared. After kneading this compound with a test roll (same as Comparative Example 1) for 5 minutes, the roll interval of the test roll was adjusted to 0.17 mm, and a 0.17 mm thick vinyl acetate component and a methyl methacrylate component were adjusted by calendar rolling. A film for polyolefin resin coating layer containing 11% by weight in total and having a LOI value of 32.2 was obtained. Next, the obtained film was applied to both sides of a polyester plain woven fabric (500 denier polyester multifilament: 20 yarn density warps / 2.54 cm × 21 wefts / 2.54 cm: porosity 19%: mass 75 g / m ² ). A polyolefin resin sheet having a thickness of 0.48 mm and a mass of 515 g / m ² was obtained by laminating with a laminator having a heat roll set to 140 ° C. and a pressure-bonding roll pair.
<Surface coating of nitrogen-containing compound particle body> …… Same as Comparative Example 3 <Surface coating of phosphorus-containing compound particle body> …… Same as Comparative Example 4

[Comparative Example 6]
30 parts by weight of the nitrogen-containing compound particles with the surface coating of Comparative Example 5 were changed to 50 parts by weight of the inorganic compound particles (B-5) with the following surface coating, and the compound was tested in the same manner as in Comparative Example 5. After kneading for 5 minutes in (same as Comparative Example 1), the roll interval of the test rolls was adjusted to 0.20 mm, and the total of the vinyl acetate component and methyl methacrylate component having a thickness of 0.20 mm by calendar rolling was 11% by weight. A polyolefin-based resin coating film having a LOI value of 32.1 was obtained. Next, the obtained film was applied to both sides of a polyester plain woven fabric (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 0.52 mm and a mass of 545 g / m ² was obtained by laminating with a laminator having a heat roll set at 140 ° C. and a pressure-bonding roll pair.

<Inorganic compound particles with surface coating layer (B-5)>
i) To a total of 500 parts by weight of 400 parts by weight of methanol and 100 parts by weight of distilled water, a metal alkoxide compound (trademark: tetra-n-butoxysilicon: effective amount 100%: Sumitomo Cement Co., Ltd. 5 parts by weight was added. After stirring for 30 minutes, 100 parts by weight of inorganic compound particle body (1) (Trademark: Magsees N-3: Magnesium hydroxide: average particle size 1.2 μm: Kamijima Chemical Co., Ltd.) is added for another 30 minutes. The mixture was filtered and dried at 120 ° C. for 2 hours to obtain 100.6 g of inorganic compound particles (B-5 ′).
ii) Next, 500 parts by weight of methyl ethyl ketone, 10 parts by weight of diallyl phthalate resin (trademark: Isodap: polymer of isophthalic acid diallyl ester: Osaka Soda Co., Ltd.) and light stabilizer (A-1) (trademark: Biosorb 510) : 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole: Kyodo Yakuhin Co., Ltd.) was added with 0.15 part by weight and stirred, and the inorganic compound particles (B -5 ′) 100.6 g was added and stirred for 10 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.55 g of an inorganic compound (B-5) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body was 4.35%, and the content of the metal alkoxide compound with respect to the diallyl phthalate resin was 15.2% by weight. The content of the light stabilizer relative to the surface coating layer was 1.29% by weight.
<Surface coating of phosphorus-containing compound particle body> …… Same as Comparative Example 4

[Comparative Example 7]
The composition of the halogen-free flame retardant of Comparative Example 5 was made up of 20 parts by weight of nitrogen-containing compound particles with surface coating, 20 parts by weight of phosphorus-containing compound particles with surface coating, and inorganic compound particles with the following surface coating ( B-6) The amount was changed to 30 parts by weight. Moreover, it was the same as that of the comparative example 5 except having changed 0.5 weight part of light-resistant stabilizer (D-2) of the comparative example 5 into 0.5 weight part of light-resistant stabilizer (D-3). After kneading this compound with a test roll (same as Comparative Example 1) for 5 minutes, the roll interval of the test roll was adjusted to 0.17 mm, and a 0.17 mm thick vinyl acetate component and a methyl methacrylate component were adjusted by calendar rolling. A film for polyolefin resin coating layer containing 11% by weight in total and having a LOI value of 34.3 was obtained. Next, the obtained film was bonded to both sides of the same polyester plain woven fabric (500 denier polyester multifilament) as in Comparative Example 5 with a laminator having a heat roll and a pressure roll pair set at 140 ° C., and a thickness of 0.48 mm. A polyolefin-based resin sheet having a mass of 515 g / m ² was obtained.

<Inorganic compound particles with surface coating layer (B-6)>
i) To 500 parts by weight of isopropyl alcohol, 5 parts by weight of an organic titanate compound (trademark: B-1: tetra-n-butoxytitanium (TBT): molecular weight 340: effective amount 100%: Nippon Soda Co., Ltd.) After stirring for 30 minutes, 100 parts by weight of inorganic compound particle body (1) (Trademark: Magsees N-3: Magnesium hydroxide: average particle size 1.2 μm: Kamijima Chemical Co., Ltd.) is added, and further for 30 minutes. Stir. This was filtered and dried at 120 ° C. for 2 hours to obtain 100.6 g of inorganic compound particles (B-6 ′).

ii) Epoxy resin (trademark: Denacast EM-101: Modified bisphenol A type epoxy emulsion: Epoxy equivalent 520: Solid concentration 50% by weight: Nagase Kasei Co., Ltd.) 20 parts by weight with 500 parts by weight of distilled water, 0.5 parts by weight of triethanolamine and 0.5 parts by weight of a light-resistant stabilizer (trademark: Sunlife LPS-700: benzotriazole UV absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) After stirring for 5 minutes, 100.6 g of the inorganic compound particles (B-6 ′) obtained in the step i) were added, and the mixture was further stirred for 30 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.50 g of inorganic compound particles (B-6) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body was 4.30%, and the content of the organic titanate compound with respect to the epoxy resin was 15.4% by weight. Further, the content of the light stabilizer relative to the surface coating layer was 1.33% by weight.
<Surface coating of nitrogen-containing compound particle body> …… Same as Comparative Example 3 <Surface coating of phosphorus-containing compound particle body> …… Same as Comparative Example 4

[Comparative Example 8]
The composition of the halogen-free flame retardant of Comparative Example 6 was composed of 20 parts by weight of a phosphorus-containing compound with surface coating, 40 parts by weight of inorganic compound particles (B-1) with surface coating, and an inorganic system with surface coating. The compound particle (B-2) was changed to 40 parts by weight. Moreover, it was the same as that of the comparative example 6 except having changed 0.5 weight part of the light-resistant stabilizer (D-2) of the comparative example 6 into 0.5 weight part of the light-resistant stabilizer (D-3). After kneading this compound with a test roll (same as Comparative Example 1) for 5 minutes, the roll interval of the test roll was adjusted to 0.20 mm, and a 0.20 mm thick vinyl acetate component and a methyl methacrylate component were formed by calendar rolling. A polyolefin resin blend film having a LOI value of 31.7 containing 11% by weight in total was obtained. Next, the obtained film was bonded to both sides of the same polyester plain woven fabric (750 denier polyester multifilament) as in Comparative Example 6 with a laminator having a heat roll and a pressure roll pair set at 140 ° C., and a thickness of 0.52 mm. A polyolefin resin sheet having a mass of 545 g / m ² was obtained.
<Surface coating of inorganic compound particle body (1): (B-1)> ... same as Comparative Example 1 <Surface coating of inorganic compound particle body (2): (B-2)> ... Same as Comparative Example 2 <Surface coating of phosphorus-containing compound particle body> ... Same as Comparative Example 4

[Example 1]
The processing method of the inorganic compound particle (B-1) with a surface coating layer of the comparative example 1 was changed into the following process.
To a total of 500 parts of 400 parts by weight of distilled water and 100 parts by weight of methanol, 20 parts by weight of melamine resin (trademark: Polyfix LFl1: modified melamine: solid content 55% by weight: Showa Polymer Co., Ltd.) and organosilane Compound (trade name: SH6040: γ-glycidoxypropyl trimethoxysilane: molecular weight 236: effective amount 100%: Toray Dow Corning Silicone Co., Ltd.) 3 parts by weight, light-resistant stabilizer (trademark: Sunlife LPS-700 : Benzotriazole ultraviolet absorber: Solid content 30 wt%: Nikka Chemical Co., Ltd. 0.5 part by weight, stirred for 30 minutes, then inorganic compound particle body (trademark: Magsees N-3: 100 parts by weight of magnesium hydroxide: average particle size 1.2 μm: Kamishima Chemical Co., Ltd.) was added, and the mixture was further stirred for 30 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.66 g of an inorganic compound (B-1) having a surface coating layer. The coverage of the surface coating layer on the inorganic compound particle main body was 4.45%.

Further, the following plain treatment was applied to the polyester plain woven fabric of Comparative Example 1 (250 denier polyester multifilament: 20 yarn density warps / 2.54 cm × 21 weft yarns / 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 488 g / m ² was obtained according to the same formulation and procedure as in Example 1 except that the treatment with the agent (1) was performed.
<Composition of pretreatment agent (1)>
Trademark: 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: 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 cloth is immersed in the above-mentioned pretreatment agent (1) bath to prepare a woven cloth. Simultaneously with the pulling up, it was 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 / 10: 20)

[Example 2]
The processing step (B-2) of the inorganic compound particles with a surface coating layer in Comparative Example 2 was changed to the following step.
To a total of 500 parts of 400 parts by weight of distilled water and 100 parts by weight of methanol, 20 parts by weight of benzoguanamine resin (trademark: Polyfix PG-251: modified benzoguanamine: solid content 54% by weight: Showa Polymer Co., Ltd.) Stabilizer (trademark: Sunlife LPS-700: benzotriazole-based UV absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) 0.5 part by weight, and metal alkoxide compound (trademark: tetra-n-butoxysilicon) : Effective amount 100%: Sumitomo Cement Co., Ltd. 5 parts by weight was added and stirred for 30 minutes, and then the inorganic compound particle body (trademark: B-315: aluminum hydroxide: average particle size 15 μm: Alcoa Chemical ( 100 parts by weight) was added and stirred for another 30 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.6 g of an inorganic compound (B-2) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body was 4.4%.

Further, a polypropylene plain woven fabric of Comparative Example 2 (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 agent (1) as 9 and the woven 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 polypropylene plain woven fabric obtained by the pretreatment was 68 g / m ² . (Synthetic Amorphous Silica: Thermoplastic Resin / 10: 20) A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 493 g / m ² was obtained according to the same composition and procedure as in Comparative Example 2 except for the above.

Example 3
The processing step (B-3) of the inorganic compound particles with a surface coating layer of Comparative Example 3 was changed to the following step.
To 500 parts by weight of isopropyl alcohol, 5 parts by weight of an organic titanate compound (trademark: B-1: tetra-n-butoxytitanium (TBT): molecular weight 340: effective amount 100%: Nippon Soda Co., Ltd.) is added. After stirring for minutes, 100 parts by weight of inorganic compound particle body (1) (trademark: Magsees N-3: magnesium hydroxide: average particle size 1.2 μm: Kamijima Chemical Co., Ltd.) was added, and the mixture was further stirred for 30 minutes. . Next, 20 parts by weight of urea resin (trademark: Polyfix LF20: highly condensed urea: solid content 55% by weight: Showa High Polymer Co., Ltd.) and a light-resistant stabilizer (trademark: Sunlife LPS-700: benzotriazole ultraviolet light) Absorber: solid content 30% by weight: Nikka Chemical Co., Ltd. 0.5 part by weight was added and stirred for 10 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.47 g of inorganic compound particles (B-3 ′) having a surface coating layer. The coverage of the surface coating layer on the inorganic compound particle main body was 4.28%.

The surface coating treatment of nitrogen-containing compound particles (trademark: MC-610: melamine cyanurate: average particle diameter of 1 to 5 μm: Nissan Chemical Co., Ltd.) was the same as in Comparative Example 3.
Further, the following plain treatment was performed on the polyester plain woven fabric of Comparative Example 3 (250 denier polyester multifilament: 20 yarn density warps / 2.54 cm × 21 weft yarns / 2.54 cm: porosity 17%: mass 55 g / m ² ). A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 488 g / m ² was obtained according to the same formulation and procedure as in Example 3 except that the treatment with the agent (2) was performed.
<Composition of pretreatment agent (2)>
Trademark: Snowtex C: Nippon Silica Industry Co., Ltd .:
Silica anhydride content 20% by weight: average particle size 10-20 nm 100 parts by weight Trademark: KBM303: Shin-Etsu Chemical Co., Ltd .:
Epoxy silane coupling agent (active ingredient 100% by weight) 3 parts by weight Diluent: 50 parts by weight distilled water A polyester plain woven fabric is immersed in the bath of the above-mentioned pretreatment agent (2) and the woven fabric is pulled up and nip rolls (Wet adhesion mass 30 g / m ² ), followed by drying 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 . (Silic anhydride: silane coupling agent / 20: 3)

Example 4
The surface coating (B-4) treatment step of the inorganic compound (2) of Comparative Example 4 was changed to the following step.
A total of 500 parts of 400 parts by weight of distilled water and 100 parts by weight of methanol, 20 parts by weight of phenol resin (trademark: Tamanol 720: resol type phenol resin aqueous solution: solid content 45% by weight: Arakawa Chemical Co., Ltd.), light resistance Stabilizer (Trademark: Sunlife LPS-700: Benzotriazole UV absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.) 0.5 part by weight, organosilane compound (trademark: SH6040: γ-glycidoxy Propyl trimethoxysilane: Molecular weight 236: Effective amount 100%: Toray Dow Corning Silicone Co., Ltd. 3 parts by weight was added and stirred for 30 minutes, and then the inorganic compound particle body (2) (trademark: B- 315: Aluminum hydroxide: Average particle size 15 μm: Alcoa Kasei Co., Ltd.) 100 parts by weight were added, and the mixture was further stirred for 30 minutes. Was dried for 2 hours to obtain 105.1 g of inorganic compound particles (B-4), and the coverage of the surface coating layer on the inorganic compound particle main body was 4.85% Phosphorus-containing compound (trademark: Exorit) The surface coating treatment of AP422: ammonium polyphosphate (NH ₄ PO ₃ ) _n , n = 1000: phosphorus content 31 to 32% by weight: Clariant Japan Co., Ltd. is the same as Comparative Example 4.

Further, a polypropylene plain woven fabric of Comparative Example 4 (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 agent (2) as 3 and the woven 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 polypropylene plain woven fabric obtained by the pretreatment was 68 g / m ² . (Silic anhydride: silane coupling agent / 20: 3) A polyolefin resin sheet having a thickness of 0.47 mm and a mass of 516 g / m ² was obtained in accordance with the same formulation and procedure as in Comparative Example 4 except for the above.

Example 5
Polyester plain woven fabric of Comparative Example 5 (500 denier polyester multifilament: yarn density warp 20 yarns / 2.54 cm × weft yarn 21 yarns / 2.54 cm: porosity 19%: mass 75 g / m ² : Teijin Ltd.) A polyolefin resin sheet having a thickness of 0.48 mm and a mass of 518 g / m ² was obtained according to the same formulation and procedure as in Comparative Example 5 except that the treatment with the following pretreatment agent (3) was performed.
<Composition of pretreatment agent (3)>
Trademark: 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-based silane coupling agent (active ingredient 100% by weight) 3 parts by weight Diluent: 150 parts by weight of distilled water A polyester plain weave fabric is immersed in a bath of the above-mentioned pretreatment agent (3), and the woven fabric is pulled up and nip roll (Wet adhesion mass 30 g / m ² ), followed by drying 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 / 10: 3)

Example 6
The treatment process of the inorganic compound particles with surface coating layer (B-5) in Comparative Example 6 was changed to the following process.
To 500 parts by weight of methyl ethyl ketone, 10 parts by weight of diallyl phthalate resin (trademark: Isodap: polymer of isophthalic acid diallyl ester: Osaka Soda Co., Ltd.) and metal alkoxide compound (trademark: tetra-n-butoxysilicon: effective amount 100%) : Sumitomo Cement Co., Ltd.) 5 parts by weight, light stabilizer (A-1) (trademark: Biosorb 510: 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole: Kyodo Yakuhin Co., Ltd.) After adding 0.15 part by weight and stirring for 30 minutes, inorganic compound particle body (1) (trademark: Magsees N-3: magnesium hydroxide: average particle diameter 1.2 μm: Kamishima Chemical Co., Ltd.) 100 weights Was added and stirred for another 30 minutes. This was filtered and dried at 120 ° C. for 2 hours to obtain 104.50 g of inorganic compound particles (B-5) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body (1) was 4.30%.
The surface coating of the phosphorus-containing compound (trademark: Exorit AP422: ammonium polyphosphate (NH ₄ PO ₃ ) _n , n = 1000: phosphorus content 31 to 32% by weight: Clariant: Japan Co., Ltd.) is the same as in Comparative Example 4. is there.

Further, the polyester plain woven fabric of Comparative Example 6 (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 :) It was immersed in the same pretreatment agent (3) as in Example 5, the woven 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 98 g / m ² . (Synthetic Amorphous Silica: Silane Coupling Agent / 10: 3) A polyolefin resin sheet having a thickness of 0.52 mm and a mass of 548 g / m ² was obtained in accordance with the same composition and procedure as in Comparative Example 6 except for this.

Example 7
The processing step (B-6) of the inorganic compound particles with a surface coating layer in Comparative Example 7 was changed to the following step.
500 parts by weight of isopropyl alcohol, 0.5 parts by weight of a light-resistant stabilizer (trademark: Sunlife LPS-700: benzotriazole UV absorber: solid content 30% by weight: Nikka Chemical Co., Ltd.), organic titanate compound (trademark) : B-1: Tetra-n-butoxytitanium (TBT): Molecular weight 340: Effective amount 100%: Nippon Soda Co., Ltd. (5 parts by weight) was added and stirred for 30 minutes, followed by epoxy resin (trademark: Denacast EM) -101: modified bisphenol A type epoxy emulsion: epoxy equivalent 520: solid content concentration 50% by weight: Nagase Kasei Co., Ltd.) 20 parts by weight, triethanolamine 0.5 parts by weight as a catalyst, and inorganic compound particles ( Trademark: Magsees N-3: Magnesium hydroxide: Average particle size 1.2 μm: Kamijima Chemical Co., Ltd.) 100 parts by weight were added. And the mixture was stirred for 30 minutes. This was filtered and dried at 120 ° C. for 2 minutes to obtain 104.27 g of inorganic compound particles (B-6) having a surface coating layer. The coverage of the surface coating layer with respect to the inorganic compound particle main body (1) was 4.14%. The surface coating of the nitrogen-containing compound is the same as in Comparative Example 3, and the surface coating of the phosphorus-containing compound is the same as in Comparative Example 4.

Polyester plain woven fabric of Comparative Example 7 (500 denier polyester multifilament: yarn density warp 20 / 2.54 cm × weft 21 / 2.54 cm: porosity 19%: mass 75 g / m ² : Teijin Ltd. A polyolefin resin sheet having a thickness of 0.48 mm and a mass of 518 g / m ² was obtained in accordance with the same formulation and procedure as in Comparative Example 7, except that the following treatment with the following pretreatment agent (4) was applied to the above.
<Composition of pretreatment agent (4)>
Trademark: 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% by weight
Diluent: 150 parts by weight of distilled water The polyester plain woven fabric is dipped in the bath of the above-mentioned pretreatment agent (4), and the woven fabric is pulled up and simultaneously squeezed with a nip roll (wet adhesion mass 30 g / m ² ) and then 100 ° C. Drying was performed in a hot stove 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 / 10: 3: 20)

Example 8
The treatment method (B-1) of the inorganic compound particles with the surface coating layer of Comparative Example 8 is the same as in Example 1, and (B-2) of the inorganic compound particles with the surface coating layer is the same as in Example 2. changed. The surface coating of the phosphorus-containing compound was the same as in Comparative Example 4. Further, it was carried out on the polyester plain woven fabric of Comparative Example 8 (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 :). It was immersed in the same pretreatment agent (4) as in Example 7, the woven 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 98 g / m ² . (Synthetic Amorphous Silica: Silane Coupling Agent: Thermoplastic Resin / 10: 3: 20) Except for this, a polyolefin system having a thickness of 0.52 mm and a mass of 548 g / m ² according to the same composition and procedure as in Comparative Example 8 A resin sheet was obtained.

[Effects of Comparative Examples 1 to 8 and Examples 1 to 8]
Table 1 shows the structure and performance of the polyolefin resin sheets of Comparative Examples 1 to 8.
Table 2 shows the configurations and performances of the polyolefin resin sheets of Examples 1 to 8.
Table 3 shows the compositions of the halogen-free flame retardant particles used in the polyolefin resin sheets of Comparative Examples 1 to 8 and Examples 1 to 8.

The films for polyolefin resin coating layers used in the polyolefin resin sheets of Examples 1 to 8 all have a high oxygen index by using halogen-free flame retardant particles whose surface is coated with a specific thermosetting resin. And immersed in a mixed aqueous solution of a 1 N (N) concentration nitric acid aqueous solution and a 0.1 N (N) concentration sulfuric acid aqueous solution at 20 ° C. for 24 hours, and then naturally dried at room temperature. In a harsh test in which the acid is concentrated inside the resin of the sheet after being left in the state for 6 days, it exhibits excellent acid resistance, such as a critical oxygen index retention of 90% or more and a residual strength retention of 90% or more. I had it.
Moreover, when the same acid resistance test was implemented with the polyolefin-type resin sheet of Example 1- Example 8, it has favorable acid resistance similarly to a film, and also has the flame-proof property which can be adapted to the Fire Service Act. It was a thing. Furthermore, the film of the polyolefin resin layer used for the polyolefin resin sheet of Example 1 to Example 8 was subjected to a 1000 hour weather resistance acceleration test with a carbon arc sunshine weather meter, and the color difference of its appearance was measured. All ΔE was 2.0 or less. Moreover, as a result of conducting an acid resistance test of the film which accelerated the weather resistance for 1000 hours, (Test II) was excellent even after the weather resistance test, such as showing a critical oxygen index retention of 80% or more and a residual strength retention of 85% or more. It also has flame resistance and acid resistance.
As for the high-frequency welder property, it was possible to easily perform fusion bonding with a conventional high-frequency welder dedicated to polyvinyl chloride resin. (Anode current value is 0.8 A, fusion time is 5 seconds, cooling time is 5 seconds, weld bar temperature is 40 to 50 ° C.) In addition, the shear failure state of the joints of Comparative Examples 1 to 8 includes thread breakage failure Was included.
Moreover, in the polyolefin-type resin sheet which gave the pretreatment which contains the silicon compound to the textile fabric base fabric of Example 1- Example 8, it improved stably so that the main body destroyed in the shear fracture test of a junction part. In particular, the pretreatment containing these silicon compounds does not have the problem of texture hardening and the problem of reduction in tear strength, which are problems of the conventional adhesive treatment, and the polyolefin resin sheets of Comparative Examples 1 to 8 This was an effective fiber woven fabric base preparation that could improve the thread breakage failure of the joint.
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. In addition, the sheets of Examples 1 to 8 are all soft in texture, are not inferior to the texture of soft polyvinyl chloride resin sheets, and are excellent in weather resistance and acid resistance. It was judged that the resin sheet can be used even in an environment where there is a lot of acid rain.
In particular, the polyolefin resin sheets of Examples 1 to 8 are excellent in processability at the time of production, and high concentrations of non-halogen-containing flame retardants such as nitrogen-containing compounds, phosphorus-containing compounds, and inorganic compounds in advance. By performing the preliminary granulation, the kneadability into the polyolefin resin was easy and efficient. In addition, since the kneading can be carried out extremely accurately, there is no variation in the flame resistance of the obtained sheet, and the flame resistance is reliable.

[Comparative Example 9]
In the presence of the Ziegler-Natta catalyst, 60 parts by weight of the linear low-density polyethylene resin (a-1) (trademark: Kernel KF360: Nippon Polychem Co., Ltd.) polymerized in the presence of the metallocene catalyst of Comparative Example 1 was used. Polymerized linear low density polyethylene resin (Trademark: Sumikasen α · FZ2203-0: MFR2.0: Density 0.932: Sumitomo Chemical Co., Ltd.) 90 parts by weight, and ethylene-vinyl acetate copolymer 40 parts by weight of the blended resin (b-1) (Trademark: Evertate K2010: VA content 25% by weight: Sumitomo Chemical Co., Ltd.) was changed to 10 parts by weight. Furthermore, the blending amount of the weathering stabilizer (D-1) (trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight, and the light stabilizer (D-1) ( Trademark: Tinuvin 765: Ciba Specialty Chemicals Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight. Except for the change in the composition, the composition was the same as in Comparative Example 1, but the surface coating treatment of the inorganic compound particle body (1) (trademark: Magsees N-3: magnesium hydroxide: Kamijima Chemical Co., Ltd.) was omitted. did. Further, in this comparative example 9, 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 from the system). Next, a polyolefin resin coating layer film having a LOI value of 29.4 containing 2.5% by weight of a vinyl acetate component having a thickness of 0.17 mm was obtained from this compound by calendar rolling. Other than this, a polyester plain woven fabric (250 denier polyester multifilament: yarn density warp 20 yarns / 2.54 cm × weft yarn 21 yarns / 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 485 g / m ² was obtained.

[Comparative Example 10]
The blending amount of 50 parts by weight of the linear low density polyethylene resin (a-2) polymerized in the presence of the metallocene catalyst of Comparative Example 2 (trademark: Evolue SP2020: Mitsui Chemicals) was changed to 90 parts by weight. In addition, the blending amount of 50 parts by weight of the ethylene-vinyl acetate copolymer resin (b-2) (trademark: EVAFLEX P1905: VA content 19% by weight: Mitsui DuPont Polychemical Co., Ltd.) was changed to 10 parts by weight. . Further, the light stabilizer (D-2) (trademark) was changed from 0.5 parts by weight to 1.5 parts by weight of light stabilizer (D-1) (trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd.). : Tinuvin 765: Ciba Specialty Chemicals Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight. The composition was the same as in Comparative Example 2 except for the change in the composition, but the surface coating treatment of the inorganic compound particle main body (2) (trademark: B-315: aluminum hydroxide: Alcoa Kasei Co., Ltd.) was omitted. Further, in this comparative example 10, the above compounding compound was mixed at a time and kneaded for 5 minutes with a test roll (Nishimura Seisakusho Co., Ltd .: 2 rolls of 6 inches diameter) set to 150 ° C. Excluded from the system). Next, a polyolefin resin coating layer film having a LOI value of 30.3 containing 2% by weight of a vinyl acetate component having a thickness of 0.17 mm was obtained from this compound by calendar rolling. Other than this, according to the same procedure as in Comparative Example 2, a polypropylene plain woven fabric (340 denier polypropylene multifilament: 19 yarn density warps / 2.54 cm × 20 weft yarns / 2.54 cm: porosity 18%: mass 65 g / m ² ), A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 488 g / m ² was obtained.

[Comparative Example 11]
In the presence of the Ziegler-Natta catalyst, 60 parts by weight of the linear low-density polyethylene resin (a-1) (trademark: Kernel KF360: Nippon Polychem Co., Ltd.) polymerized in the presence of the metallocene catalyst of Comparative Example 3 was used. Polymerized linear low density polyethylene resin (Trademark: Sumikacene α · FZ203-0: MFR2.0: Density 0.932: Sumitomo Chemical Co., Ltd.) 10 parts by weight, and ethylene-vinyl acetate copolymer The blending amount of 40 parts by weight of coalesced resin (b-1) (trademark: Evertate K2010: VA content 25% by weight: Sumitomo Chemical Co., Ltd.) was changed to 90 parts by weight. Further, the light stabilizer (D-1) (trademark: Biosorb 510: Kyodo Pharmaceutical Co., Ltd.) and light stabilizer (D-3) (trademark: Tinuvin 114: Ciba Specialty Chemicals Co., Ltd.) All formulations were omitted. Except for the above composition change, the composition was the same as in Comparative Example 3, but the surface coating treatment of the inorganic compound particle main body (1) (trademark: Magsees N-3: magnesium hydroxide: Kamijima Chemical Co., Ltd.) and nitrogen The surface coating treatment of the containing compound particle main body (trademark: MC-610: melamine cyanurate: Nissan Chemical Co., Ltd.) was omitted. Moreover, in this comparative example 11, the said compounding compound was knead | mixed for 5 minutes with the test roll set to 150 degreeC by batch injection (the compounding material which cannot be kneaded in 5 minutes was excluded from the compounding system). Next, a polyolefin resin coating film having a LOI value of 31.4 containing 22% by weight of a vinyl acetate component having a thickness of 0.17 mm was obtained from the compound by calendar rolling. Other than this, according to the same procedure as in Comparative Example 1, a polyester plain woven fabric (250 denier polyester multifilament: yarn density warp 20 yarns / 2.54 cm × weft yarn 21 yarns / 2.54 cm: porosity 17%: mass 55 g / m ² ), A polyolefin resin sheet having a thickness of 0.46 mm and a mass of 484 g / m ² was obtained.

[Comparative Example 12]
The blending amount of 50 parts by weight of the linear low density polyethylene resin (a-2) polymerized in the presence of the metallocene catalyst of Comparative Example 4 (trademark: Evolue SP2020: Mitsui Chemicals) was changed to 10 parts by weight. In addition, the blending amount of 50 parts by weight of the ethylene-vinyl acetate copolymer resin (b-2) (trademark: EVAFLEX P1905: VA content 19% by weight: Mitsui DuPont Polychemical Co., Ltd.) was changed to 90 parts by weight. . Furthermore, all the combinations of light stabilizer (D-1) (trademark: Biosorb 510: Kyodo Pharmaceutical Co., Ltd.) and light stabilizer (D-3) (trademark: Tinuvin 114: Ciba Specialty Chemicals Co., Ltd.) Omitted. Except for the above composition change, the composition was the same as in Comparative Example 4, but the surface coating treatment of the inorganic compound particle body (2) (trademark: B-315: aluminum hydroxide: Alcoa Kasei Co., Ltd.) and the phosphorus-containing compound The surface coating treatment of the particle main body (trademark: Exorit AP422: ammonium polyphosphate (NH ₄ PO ₃ ) _n , n = 1000: phosphorus content 31 to 32% by weight: Clariant Japan Co., Ltd.) was omitted. Moreover, in this comparative example 12, the said compounding compound was kneaded for 5 minutes with the test roll set to 150 degreeC by batch injection (the compounding material which cannot be kneaded in 5 minutes was excluded from the compounding system). Next, from this compound, a polyolefin resin coating layer film having a LOI value of 31.7 containing 18% by weight of a vinyl acetate component having a thickness of 0.17 mm by calender rolling was obtained. Other than this, according to the same procedure as in Comparative Example 2, a polypropylene plain woven fabric (340 denier polypropylene multifilament: 19 yarn density warps / 2.54 cm × 20 weft yarns / 2.54 cm: porosity 18%: mass 65 g / m ² ), A polyolefin resin sheet having a thickness of 0.47 mm and a mass of 514 g / m ² was obtained.

[Comparative Example 13]
Polymerization of 50 parts by weight of linear low density polyethylene resin (a-1) (trademark: Kernel KF360: Nippon Polychem Co., Ltd.) polymerized in the presence of the metallocene catalyst of Comparative Example 5 in the presence of a Ziegler-Natta catalyst The linear low-density polyethylene resin (trademark: Sumikacene α · FZ203-0: MFR 2.0: density 0.932: Sumitomo Chemical Co., Ltd.) was changed to 50 parts by weight. In addition, the composition of the film for polyolefin resin coating layer was changed from 0.5 parts by weight to 1.5 parts by weight of the light stabilizer (D-1) (trademark: Biosorb 510: Kyodo Kagaku Co., Ltd.). , And light stabilizer (D-2) (trademark: Tinuvin 765: Ciba Specialty Chemicals Co., Ltd.) were all omitted. Except for the above composition change, the composition was the same as in Comparative Example 5, but the nitrogen-containing compound particle main body (trademark: MC-610: melamine cyanurate: Nissan Chemical Co., Ltd.) and the phosphorus-containing compound particle main body (trademark: Exorit AP422) : Ammonium polyphosphate (NH ₄ PO ₃ ) _n , n = 1000: Phosphorus content 31 to 32% by weight: Clariant Japan Co., Ltd.) was omitted. Further, in Comparative Example 13, 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 coating layer film having a LOI value of 33.5 containing 11 wt% of a vinyl acetate component having a thickness of 0.17 mm by calendar rolling was obtained. Other than this, 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 0.48 mm and a mass of 513 g / m ² was obtained.

[Comparative Example 14]
Polymerization of 50 parts by weight of linear low density polyethylene resin (a-1) (trademark: Kernel KF360: Nippon Polychem Co., Ltd.) polymerized in the presence of the metallocene catalyst of Comparative Example 6 in the presence of a Ziegler-Natta catalyst The linear low-density polyethylene resin (trademark: Sumikacene α · FZ203-0: MFR 2.0: density 0.932: Sumitomo Chemical Co., Ltd.) was changed to 50 parts by weight. Moreover, in the composition of the film for polyolefin resin coating layer, the blending amount of the light stabilizer (D-1) (trademark: Biosorb 510: Kyodo Kagaku Co., Ltd.) was changed from 0.5 parts by weight to 1.5 parts by weight, All formulations of the light stabilizer (D-2) (Trademark: Tinuvin 765: Ciba Specialty Chemicals Co., Ltd.) were omitted. Except for the above composition change, the composition was the same as in Comparative Example 6, but the surface coating treatment of the inorganic compound particle body (1) (Trademark: Magsees N-3: Magnesium hydroxide: Kamijima Chemical Co., Ltd.) (1- c) and surface coating treatment of phosphorus-containing compound particle body (trademark: Exolit AP422: ammonium polyphosphate (NH ₄ PO ₃ ) _n , n = 1000: phosphorus content 31 to 32% by weight: Clariant Japan Co., Ltd.) Was omitted. Moreover, in this comparative example 14, the said compounding compound was kneaded for 5 minutes with the test roll set to 150 degreeC by batch injection (the compounding material which cannot be kneaded in 5 minutes was excluded from the compounding system). Next, from this compound, a polyolefin resin coating layer film having a LOI value of 32.7 containing 11% by weight of a vinyl acetate component having a thickness of 0.20 mm was obtained by calendar rolling. Other than this, according to the same procedure as in Comparative Example 6, a polyester plain woven fabric (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 0.52 mm and a mass of 542 g / m ² was obtained.

[Comparative Example 15]
50 parts by weight of a linear low density polyethylene resin (a-1) polymerized in the presence of the metallocene catalyst of Comparative Example 7 (trademark: Kernel KF360: Nippon Polychem Co., Ltd.) in the presence of a Ziegler-Natta catalyst The amount was changed to 50 parts by weight of a polymerized linear low-density polyethylene resin (trademark: Sumikacene α · FZ203-0: MFR 2.0: density 0.932: Sumitomo Chemical Co., Ltd.). In addition, the composition of the film for polyolefin resin coating layer was changed from 0.5 parts by weight to 1.5 parts by weight of the light stabilizer (D-1) (trademark: Biosorb 510: Kyodo Kagaku Co., Ltd.). , And light stabilizer (D-3) (trademark: Tinuvin 114: Ciba Specialty Chemicals Co., Ltd.) were all omitted. Except for the above composition change, the composition was the same as in Comparative Example 7, but the surface coating treatment of inorganic compound particle body (1) (trademark: Magsees N-3: magnesium hydroxide: Kamijima Chemical Co., Ltd.) and phosphorus Containing compound particle body (trademark: Exorit AP422: ammonium polyphosphate (NH ₄ PO ₃ ) _n , n = 1000: phosphorus content 31 to 32% by weight: Clariant Japan Co., Ltd.) and nitrogen-containing compound particle body (trademark) : MC-610: Melamine cyanurate: Nissan Chemical Co., Ltd.) surface coating treatment was omitted. Moreover, in this comparative example 15, the said compounding compound was kneaded for 5 minutes with the test roll set to 150 degreeC by lump-sum charging (the compounding material which cannot be kneaded in 5 minutes was excluded from the compounding system). Next, from this compound, a polyolefin resin coating layer film having a LOI value of 33.8 containing 11 wt% of a vinyl acetate component having a thickness of 0.17 mm by calendar rolling was obtained. Other than this, a polyester plain woven fabric (500 denier polyester multifilament: 20 yarn density warps / 2.54 cm × 21 weft yarns / 2.54 cm: porosity 19%: mass 75 g / m ²⁾ ), A polyolefin resin sheet having a thickness of 0.48 mm and a mass of 515 g / m ² was obtained.

[Comparative Example 16]
50 parts by weight of a linear low density polyethylene resin (a-1) polymerized in the presence of the metallocene catalyst of Comparative Example 8 (trademark: Kernel KF360: Nippon Polychem Co., Ltd.) in the presence of a Ziegler-Natta catalyst The amount was changed to 50 parts by weight of a polymerized linear low-density polyethylene resin (trademark: Sumikacene α · FZ203-0: MFR 2.0: density 0.932: Sumitomo Chemical Co., Ltd.). In addition, the composition of the film for polyolefin resin coating layer was changed from 0.5 parts by weight to 1.5 parts by weight of the light stabilizer (D-1) (trademark: Biosorb 510: Kyodo Kagaku Co., Ltd.). The light stabilizer (D-3) (trademark: Tinuvin 114: Ciba Specialty Chemicals Co., Ltd.) was all omitted. Except for the above composition change, the composition was the same as in Comparative Example 7, but the surface coating treatment of inorganic compound particle body (1) (trademark: Magsees N-3: magnesium hydroxide: Kamijima Chemical Co., Ltd.) and inorganic -Based compound particle body (2) (Trademark: B-315: Aluminum hydroxide: Alcoa Kasei Co., Ltd. surface coating treatment and phosphorus-containing compound particle body (Trademark: Exolit AP422: Ammonium polyphosphate (NH ₄ PO ₃ ) _n ) N = 1000: Phosphorus content 31-32% by weight: Clariant Japan Co., Ltd.) In addition, in Comparative Example 14, the above compounded compound was fed at once with a test roll set at 150 ° C. Kneading was carried out for 5 minutes (mixed materials that could not be kneaded in 5 minutes were excluded from the blending system). A polyolefin resin coating film having a LOI value of 28.6 containing 11% by weight of a vinyl acetate component of 0 mm was obtained, and a polyester plain woven fabric (750 denier polyester multifilament: 750 denier polyester multifilament: The above film was laminated on both sides of a yarn density of 19 warps / 2.54 cm × 20 wefts / 2.54 cm: porosity 22%: mass 95 g / m ² ), thickness 0.52 mm, mass 547 g / m ^2. A polyolefin resin sheet was obtained.

Table 4 shows configurations and performances of the polyolefin resin sheets of Comparative Examples 9 to 16.
Table 5 shows the composition of the halogen-free flame retardant particles used in the polyolefin resin sheets of Comparative Examples 9 to 16.

[Comparative Example 9] to [Comparative Example 16]
In Comparative Example 9 and Comparative Example 10, since the blending ratio of the linear low-density polyethylene resin (a) was 90% by weight, the high-frequency welder meltability was insufficient and the fracture strength of the joint was insufficient. there were. In Comparative Example 9 and Comparative Example 10, the light stabilizers (D-1) and (D-2) were added in an increased amount. Therefore, on the third day from the production, these light stabilizers were bloomed on the surface of the sheet. )Was. In Comparative Example 11 and Comparative Example 12, since the blending ratio of the ethylene-vinyl acetate copolymer resin (b) was increased to 90% by weight, the high-frequency welder fusion was sufficient but the wear resistance was poor, and The fracture strength of the joint was also insufficient. Moreover, although the flame-proof property of the film of the polyolefin resin sheet of Comparative Example 9 to Comparative Example 16 initially had a flame-proof performance compatible with the Fire Service Law, as a result of the acid resistance test, 1 N (N) After being immersed in a mixed aqueous solution of a nitric acid solution having a concentration of 0.1N and a sulfuric acid solution having a concentration of 0.1 N (N) for 24 hours at 20 ° C., it is naturally dried at room temperature and left in that state for 6 days. In a severe test for concentrating the acid, the critical oxygen index decreased by 15 to 25%, and the residual strength decreased by 30 to 50%.
Moreover, the film of the polyolefin-type resin layer which does not contain the light-resistant stabilizer of Comparative Example 11- Comparative Example 16 was subjected to a 1000-hour weathering accelerated test with a carbon arc type sunshine weather meter, and the acid resistance test was conducted. The retention rate was only 16-21%. As the resin deteriorates, the acidic solution penetrates into the polyolefin resin film, causing the halogen-free flame retardant to corrode and lower the critical oxygen index value. Then, these flame retardant polyolefin resin sheets of Comparative Examples 9 to 16 were not at a level that could be used at all. In Comparative Examples 9 to 16, since the sheet manufacturing method, particularly the kneading method of the polyolefin resin and the halogen-free flame retardant (inorganic compound, nitrogen-containing compound, phosphorus-containing compound) was batch kneading, the kneading efficiency was extremely high. In addition, the halogen-free flame retardant could not be completely kneaded into the resin within 5 minutes of the kneading setting time, and a large amount of these halogen-free flame retardant spilled under the roll of the test roll. Met. Therefore, the flame-proof test of the sheets of Comparative Examples 9 to 16, which cannot contain the specified amount of the halogen-free flame retardant, 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 halogen-free flame retardants could eventually be kneaded into the resin, but during the repetition of this operation, these halogen-free flame retardants scattered and caused a large loss. became. The results are as shown in Tables 4 and 5.

  According to the present invention, a polyolefin resin sheet having excellent light resistance and acid resistance and capable of high frequency fusion, and a flame retardant polyolefin type excellent in fracture strength and heat creep resistance of a high frequency fusion part A resin sheet can be obtained easily. Accordingly, the polyolefin resin sheet obtained by the method and the production method of the present invention is used for outdoor exposure to acid rain, such as a membrane material for a tent, a membrane material for a sheet warehouse, a curing sheet for a building site, and a sound insulation sheet for a building site. In addition, it is extremely useful as an acid rain-resistant flame retardant sheet for industrial materials, which can maintain flameproof performance for a long period of time outdoors and has excellent melt adhesive strength.

Claims (34)

A base fabric including a fiber fabric, and a polyolefin-based resin coating layer covering at least one surface of the base fabric,
The fiber fabric for base fabric is pretreated with a treating agent containing a silicon compound component composed of one or more selected from synthetic amorphous silica, colloidal silica and silane coupling agent,
The polyolefin resin coating layer is
(A) 100 parts by weight of a polyolefin-based resin blend (B) 20 to 200 parts by weight of a flame retardant particle body, and at least one kind of surface coating layer formed on the surface thereof and containing a thermosetting resin Halogen-free flame retardant particles, and
(D) 0.05 to 3.0 parts by weight of a light-resistant stabilizer,
The polyolefin resin blend (A) is
(A) a linear low-density polyethylene resin obtained by copolymerizing ethylene and at least one α-olefin in the presence of a metallocene catalyst;
(B) an ethylene-based copolymer resin comprising at least one selected from an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer resin;
Including
The total weight of vinyl acetate and (meth) acrylic acid (ester) contained in the ethylene copolymer resin (b) is 5 to 30% by weight with respect to the total weight of the polyolefin resin blend (A). Is in range,
An acid rain-resistant flame-retardant polyolefin resin sheet that is capable of high-frequency fusion and has excellent breaking strength at the high-frequency fusion part . The polyolefin-based resin coating layer covers the surface of the pretreated base fabric, and further, the back surface of the pretreated base fabric is covered with a thermoplastic resin layer, and the back surface thermoplastic resin layer is
(C) 100 parts by weight of a thermoplastic resin, (B) 20 to 200 parts by weight of a flame retardant particle body, and at least one kind of surface coating layer formed on the surface thereof and containing a thermosetting resin. Halogen-free flame retardant particles;
including,
The acid rain-resistant flame-retardant polyolefin resin sheet that is capable of high-frequency fusion bonding according to claim 1 and has excellent breaking strength at the high-frequency fusion bonding portion . The surface coating layer of the halogen-free flame retardant particles (B) is at least one thermosetting selected from an epoxy resin, an unsaturated polyester resin, a phenol resin, a melamine resin, a urea resin, a triazine resin, and a diallyl phthalate resin. The high-frequency fusion-bondable part according to claim 1, wherein the high-frequency fusion-bonding part is capable of high-frequency fusion, and contains 2% to 15% by weight of the non-halogen containing flame retardant particles. Acid rain resistant flame retardant polyolefin resin sheet with excellent breaking strength . One or more kinds selected from a metal alkoxide compound, an organic silane compound, an organic titanate compound, an alkylfluoro group-containing compound, and a silicone compound in addition to the thermosetting resin for the surface coating layer of the halogen-free flame retardant particles (B). it is mixed additives, mixing amount of the additive relative to the weight of the thermosetting resin, according to any one of claims 1 to 3, 1 to 30 wt% high-frequency welding An acid rain-resistant flame-retardant polyolefin resin sheet that is possible and has excellent fracture strength at high-frequency welds . The light-resistant stabilizer (D) is further contained in the surface coating layer of the halogen-free flame retardant particles (B), and the high-frequency fusion is possible according to any one of claims 1 to 4. Acid rain resistant flame retardant polyolefin resin sheet with excellent fracture strength at high frequency welds . 6. The high-frequency fusion according to claim 5, wherein the light stabilizer includes at least one selected from a benzotriazole compound, a benzophenone compound, a cyanoacrylate compound, a salicylate compound, and a hindered amine compound. Acid rain resistant flame retardant polyolefin resin sheet with excellent fracture strength at high frequency welds . The high-frequency melting according to any one of claims 1 to 6, wherein the flame retardant particle main body of the halogen-free flame retardant particles (B) contains one or more of a phosphorus-containing compound, a nitrogen-containing compound, and an inorganic compound. Acid rain resistant flame retardant polyolefin resin sheet that can be worn and has excellent breaking strength at high-frequency welds . The phosphorus-containing compound for flame retardant particle main body of the halogen-free flame retardant particles (B) is selected from red phosphorus, (metal) phosphate, (metal) organic phosphate, and ammonium polyphosphate. An acid rain-resistant flame-retardant polyolefin resin sheet that is capable of high-frequency fusing as described above and has excellent breaking strength at the high-frequency fusing portion . The halogen-containing flame retardant particle main body nitrogen-containing compound of the halogen-free flame retardant particles (B) is an (iso) cyanurate compound, an (iso) cyanuric acid compound, a guanidine compound, a urea compound, and a derivative compound thereof. The acid rain-resistant flame-retardant polyolefin resin sheet which is selected and capable of being fused by high frequency according to claim 7 and excellent in breaking strength of the high-frequency fused portion . The inorganic compound for flame retardant particle body of the halogen-free flame retardant particles (B) is selected from metal oxides, metal hydroxides, metal composite oxides, metal composite hydroxides. Acid rain resistant flame retardant polyolefin resin sheet that is capable of high frequency fusion and has excellent fracture strength at high frequency fusion zones. The high-frequency meltable part according to claim 1 or 2, wherein the fiber fabric for base fabric is made of filament yarn and has a porosity of 5 to 40%, and is excellent in fracture strength of the high-frequency fused part. the acid rain resistance flame-retardant polyolefin-based resin sheet. The treatment agent for undertreatment of the fiber fabric for base fabric further includes a thermoplastic resin in addition to the silicon compound component, and is capable of high-frequency fusion bonding according to any one of claims 1, 2, and 11. An acid rain-resistant flame-retardant polyolefin resin sheet with excellent fracture strength at high-frequency welds . 13. The base fabric according to any one of claims 1, 2, 11, and 12, wherein the fiber fabric for base fabric is subjected to a flame retardant treatment by kneading or doping a flame retardant during fiber formation, or by post-processing after fiber formation. An acid rain-resistant flame-retardant polyolefin resin sheet that is capable of high-frequency fusion as described in item 1 and has excellent fracture strength at the high-frequency fusion part . The metallocene catalyst for producing the linear low-density polyethylene-based resin includes an organic transition metal compound containing at least one of a cyclopentadienyl derivative and an indenyl derivative, and an alkylaluminoxane. An acid rain-resistant flame-retardant polyolefin resin sheet that is capable of high-frequency fusing as described above and has excellent breaking strength at the high-frequency fusing portion . The thermoplastic resin (C) for the back surface thermoplastic resin layer is an ionomer resin, an acrylic resin, a vinyl acetate resin, a polyvinyl alcohol resin, an ethylene-vinyl acetate copolymer resin, a polyurethane resin, a polystyrene resin, The acid-resistant rain that is capable of high-frequency fusing according to claim 2 and has excellent fracture strength at a high-frequency fusing portion, comprising at least one selected from saturated polyester resins, polyamide resins, and modified resins thereof. Flame retardant polyolefin resin sheet. The thermoplastic resin (C) for the back surface thermoplastic resin is an ionomer resin, an acrylic resin, a vinyl acetate resin, a polyvinyl alcohol resin, an ethylene-vinyl acetate copolymer resin, a polyurethane resin, a polystyrene resin, or a saturated resin. At least one selected from polyester resins, polyamide resins, and modified resins thereof, phenol resins, melamine resins, urea resins, unsaturated polyester resins, epoxy resins, thermosetting polyurethane resins And an acid rain-resistant flame-retardant polyolefin system that is capable of high-frequency fusing and has excellent fracture strength at the high-frequency fusing portion, comprising a blend with at least one selected from allyl phthalate resins Resin sheet. In order to produce the acid rain resistant flame retardant polyolefin resin sheet according to claim 1,
(1) Halogen-free flame retardant particles (B) having the flame retardant particle main body and a surface coating layer formed on the surface thereof and containing a thermosetting resin in the ethylene copolymer resin (b). ) At least one kind of (b) + (B) pellets containing at a high concentration,
(2) A resin compound for coating by mixing all kinds of the (b) + (B) pellets and the linear low-density polyethylene resin (a) and containing the light-resistant stabilizer (D). Prepare
(3) The coating resin compound is subjected to calendar molding or T-die extrusion molding to mold a polyolefin resin film,
(4) A group comprising a fiber fabric prepared by pretreating the polyolefin resin film with a treating agent containing a silicon compound component composed of one or more selected from synthetic amorphous silica, colloidal silica, and a silane coupling agent. Laminate and stick to at least one surface of the cloth,
A method for producing an acid rain-resistant flame-retardant polyolefin-based resin sheet that is capable of high-frequency fusion and has excellent fracture strength at a high-frequency fusion part . A step of laminating and sticking the polyolefin-based resin film on the surface of the base treatment base fabric, and a step of forming a thermoplastic resin layer on the back surface of the base fabric,
The back surface thermoplastic resin layer is
(C) 100 parts by weight of a thermoplastic resin;
(B) 20 to 200 parts by weight of a flame retardant particle main body, and at least one halogen-free flame retardant particle having a surface coating layer formed on the surface thereof and containing a thermosetting resin;
Including
In the step of forming the back surface thermoplastic resin layer,
(A ′) an aqueous resin solution comprising at least one selected from an aqueous emulsion and an aqueous dispersion of the thermoplastic resin (C), or
(B ′) a solution obtained by dissolving the thermoplastic resin (C) in an organic solvent,
In, the halogen-free flame retardant particles (B) coating solution prepared by incorporating the coating on the back surface of the lower processing base fabric, drying, a possible high frequency welding according to claim 17 And a method for producing an acid rain-resistant flame-retardant polyolefin resin sheet having excellent fracture strength at high-frequency welds . The halogen-free flame retardant particles (B) consist of two or more different in the composition of the flame retardant particle main body and / or the composition of the surface coating layer,
In the (b) + (B) pellet manufacturing process, all of the two or more halogen-free flame retardant particles (B) are mixed in the ethylene copolymer resin (b) to provide a single type. (B) + (B) pellets of
The method for producing an acid rain-resistant flame-retardant polyolefin resin sheet according to claim 17 or 18 , which is capable of high-frequency fusion and has excellent fracture strength at the high-frequency fusion part . The halogen-free flame retardant particles (B) are composed of two or more different in the composition of the flame retardant particle main body and / or the composition of the surface coating layer,
In the (b) + (B) pellet manufacturing process, at least one of the two or more halogen-free flame retardant particles (B) and the ethylene copolymer resin (b) are mixed and at least 2 Producing seed (b) + (B) pellets;
In the coating resin compound preparation step, a coating resin compound is prepared by mixing all of the two or more types of (b) + (B) pellets and the linear low density polyethylene resin (a). The method for producing an acid rain-resistant flame-retardant polyolefin resin sheet according to claim 17 or 18 , which is capable of high-frequency fusing and has excellent fracture strength at a high-frequency fusing portion . The surface coating layer of the halogen-free flame retardant particles (B) is at least one thermosetting selected from an epoxy resin, an unsaturated polyester resin, a phenol resin, a melamine resin, a urea resin, a triazine resin, and a diallyl phthalate resin The high frequency fusion bonding according to any one of claims 17 to 20, wherein the high-frequency fusion resin is capable of containing 2% to 15% by weight based on the weight of the halogen-free flame retardant particles. And a method for producing an acid rain-resistant flame-retardant polyolefin resin sheet having an excellent fracture strength at a high-frequency fused portion . One or more kinds selected from a metal alkoxide compound, an organic silane compound, an organic titanate compound, an alkylfluoro group-containing compound, and a silicone compound in addition to the thermosetting resin for the surface coating layer of the halogen-free flame retardant particles (B). it is mixed additives, mixing amount of the additive relative to the weight of the thermosetting resin, according to any one of claims 17 to 21 1 to 30 wt% high-frequency welding A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet , which is possible and has excellent fracture strength at high-frequency welds . The light-resistant stabilizer (D) is contained in the surface coating layer of the halogen-free flame retardant particles (B), and is capable of high-frequency fusion according to any one of claims 17 to 22, wherein A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet having excellent fracture strength at the fused part . The light-resistant stabilizer (D) includes at least one selected from a benzotriazole compound, a benzophenone compound, a cyanoacrylate compound, a salicylate compound, and a hindered amine compound. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet , which is capable of high-frequency fusing as described above and has excellent fracture strength at a high-frequency fusing portion . The high-frequency melting according to any one of claims 17 to 24, wherein the flame retardant particle body of the halogen-free flame retardant particles (B) contains one or more of a phosphorus-containing compound, a nitrogen-containing compound, and an inorganic compound. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet that can be worn and has excellent fracture strength at a high-frequency fused portion . The phosphorus-containing compound for the flame retardant particle main body of the halogen-free flame retardant particles (B) is selected from red phosphorus, (metal) phosphate, (metal) organic phosphate, and ammonium polyphosphate. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet which is capable of high-frequency fusion and has excellent fracture strength at the high-frequency fusion part . The halogen-containing flame retardant particle main body nitrogen-containing compound of the halogen-free flame retardant particles (B) is an (iso) cyanurate compound, an (iso) cyanuric acid compound, a guanidine compound, a urea compound, and a derivative compound thereof. 26. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet, which is selected from the above, and is capable of high-frequency fusion bonding and excellent in fracture strength of the high-frequency fusion bonding portion . The inorganic compound for a flame retardant particle body of the halogen-free flame retardant particles (B) is selected from a metal oxide, a metal hydroxide, a metal composite oxide, and a metal composite hydroxide. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet that is capable of high-frequency fusion and has excellent fracture strength at a high-frequency fusion part . 19. The high-frequency fusion-bonding according to claim 17, wherein the fiber fabric for base fabric is made of filament yarn and has a porosity of 5 to 40%, and is excellent in fracture strength of the high-frequency fusion part. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet. 30. The high-frequency fusion bonding according to any one of claims 17, 18 and 29, wherein the treatment agent for the undertreatment of the fiber fabric for base fabric further contains a thermoplastic resin in addition to the silicon compound component. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet having excellent fracture strength at a high-frequency fused part . The fiber fabric for base fabric according to any one of claims 17, 18, 29 and 30, wherein the fiber fabric for the base fabric is flame-retarded by kneading or doping a flame retardant at the time of fiber formation, or by post-treatment after fiber formation. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet , which is capable of high-frequency fusion as described in item 1 and has excellent fracture strength at the high-frequency fusion part . The metallocene catalyst for producing the linear low density polyethylene resin includes an organic transition metal compound containing at least one of a cyclopentadienyl derivative and an indenyl derivative, and an alkylaluminoxane. A method for producing an acid rain-resistant flame-retardant polyolefin resin sheet which is capable of high-frequency fusion and has excellent fracture strength at the high-frequency fusion part . The thermoplastic resin (C) for the back surface thermoplastic resin layer is an ionomer resin, an acrylic resin, a vinyl acetate resin, a polyvinyl alcohol resin, an ethylene-vinyl acetate copolymer resin, a polyurethane resin, a polystyrene resin, The acid-resistant rain that is capable of high-frequency fusing according to claim 18 and has excellent breaking strength at a high-frequency fusing portion, comprising at least one selected from saturated polyester resins, polyamide resins, and modified resins thereof. Of flame retardant flame retardant polyolefin resin sheet. The thermoplastic resin (C) for the back surface thermoplastic resin is an ionomer resin, an acrylic resin, a vinyl acetate resin, a polyvinyl alcohol resin, an ethylene-vinyl acetate copolymer resin, a polyurethane resin, a polystyrene resin, or a saturated resin. At least one selected from polyester resins, polyamide resins, and modified resins thereof, phenol resins, melamine resins, urea resins, unsaturated polyester resins, epoxy resins, thermosetting polyurethane resins And an acid rain-resistant flame-retardant polyolefin system that is capable of high-frequency fusion and has excellent fracture strength at the high-frequency fusion part, comprising a blend with at least one selected from allyl phthalate resins Manufacturing method of resin sheet.