JP2001322208A - Fire retardant polyolefinic resin coated sheet and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fire retardant polyolefinic resin coated sheet not containing a halogen-containing resin and a fire retardant, excellent in mechanical strength, flameproofness, processability and coloring properties and useful as an industrial material. SOLUTION: Upper and lower resin layers, which comprise a polyolefinic resin composition which contains 100 parts by weight of a polyolefinic resin and 5-35 parts by weight of red phosphorus particles and has a melt flow rate(MFR) (By a JIS K 6760 test method. temperature: 190 deg.C; load: 21.18N) pf 0.2-5.0 g/10 min, are formed on both surfaces of base cloth including cloth knitted from thermoplastic resin filament yarn to form the resin coated sheet. This resin coated sheet shows a dry heat shrinkage factor of 5-25% in both warp and weft directions when heated to 150 deg.C for 15 min.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is suitable for use in buildings, constructions, etc., and is excellent in flexibility, mechanical properties, abrasion resistance, outdoor durability, etc., and emits flammable gas, especially toxic gas. The present invention relates to a flame-retardant polyolefin-based resin-coated sheet containing no base fabric and containing a fabric base fabric. More specifically, the present invention does not generate halogen gas during combustion, and conforms to the fire prevention test specified by the Fire Service Law, a tent membrane material, a sheet warehouse membrane material, a curing sheet for a construction site, The present invention relates to a flame-retardant polyolefin-based resin-coated sheet that is useful as a sound insulation sheet for on-site use.

[0002]

2. Description of the Related Art In recent years, since halogens contained in vinyl chloride resin products are released as toxic gases during combustion, problems have been raised in terms of safety in waste disposal or flame. In view of such a social background, various measures for reducing the halogen content as much as possible have been studied. For example, as a substitute for vinyl chloride resin, a polyolefin resin is used, and a metal hydroxide, a metal oxide,
A non-halogen-containing flame-retardant resin composition in which a phosphorus-based compound or the like is added as a flame retardant has been proposed (Japanese Patent Application Laid-Open No. Sho.
JP-A-3-20348, JP-A-63-61055, JP-A-63-128038, JP-A-63-1
54760, JP-A-3-20342, etc.).

[0003] However, although the resin compositions according to these proposals are certainly non-halogen-containing compositions, in order to impart sufficient flame retardancy to the polyolefin resin, metal hydroxides (eg, magnesium hydroxide, hydroxide, etc.) are required. Aluminum or the like or a metal oxide (for example, antimony trioxide, zinc borate, titanium dioxide, etc.) needs to be added in a large amount of 100 to 300 parts by weight, and as a result, the processability of the polyolefin resin composition decreases, Problems such as a remarkable decrease in mechanical strength of the processed product are caused. In particular, when applied to sheet-shaped processed products, not only the texture becomes hard, but also there are problems such as fatigue deterioration due to bending and surface scratches easily attached, and the balance between practicality and flame retardancy. Is in a state where the balance with cost cannot be established well.

In order to reduce the amount of the non-halogen flame retardant, it has been proposed to use red phosphorus particles and heat-expandable graphite together with the above-mentioned non-halogen flame retardant as a flame retardant auxiliary ( JP-A 1-44632, JP-A 6-1
84330, JP-A-6-73251, JP-A-6-25476, and JP-A-8-302202. Although it is possible to obtain a flame-retardant composition by reducing the amount of the non-halogen flame retardant to some extent by these methods, it is still necessary that the amount of the non-halogen flame retardant is 50 parts by weight or more. Is still not at a level that can avoid a decrease in mechanical properties of the polyolefin resin composition. Also, the addition of red phosphorus particles causes the molded product to be colored reddish brown, and the addition of heat-expandable graphite causes the molded product to be colored black. There is a disadvantage that it cannot be used for applications that require

Conventionally, fiber reinforced products obtained by using a synthetic fiber knitted fabric as a core material and forming a conventional polyvinyl chloride resin layer on the surface thereof, for example, tents, sheet warehouses, curing sheets at construction sites, and buildings For applications such as on-site sound insulation sheets for buildings and structures, canvas or tarpaulin formed by coating or laminating a fiber woven fabric with a vinyl chloride resin composition layer is used. Since polyvinyl chloride resin itself has high flame retardancy, these construction canvases and tarpaulins contain 5 to 20 weight percent of a flame retardant such as antimony trioxide or aluminum hydroxide in the polyvinyl chloride resin. By using with a small amount of addition, it is possible to comply with the fire protection standard (Article 4: Fire Safety Law, JIS L-1091) stipulated by the Fire Service Law. However, when the resin constituting these canvases and tarpaulins is replaced with a polyolefin-based resin, the polyolefin-based resin itself is flammable. However, there is a problem that it is difficult to obtain sufficient flame retardancy by using only the above.

[0006] Therefore, in order to impart flame retardancy to the synthetic fiber woven fabric, a flame retarding agent in which a flame retardant is dispersed or dissolved in water or an organic solvent is impregnated or applied to the synthetic fiber woven fabric and dried. In addition, a method of making the synthetic fiber fabric flame-retardant by heat treatment is employed. For example, for non-halogen flame retardation of polyester fiber woven fabric, an oxygen index (LOI: JIS K7201) is 27 to 28 using an aliphatic phosphate flame retardant.
Degree of flame retardancy (Dyeing Industry Vol.32 N
o. 2). According to “Polymer Flame Retardation (page 105): Taiseisha”, this level of LOI: 27 to 28 corresponds to the flame retardant category. When designing a canvas or tarpaulin covered with a polyolefin resin using this flame retardant polyester fiber fabric, the flame retardant level of the polyolefin resin layer is also raised to the same LOI as the flame retardant polyester fiber fabric. There is a need to. Since the LOI of polyolefin-based resin (polyethylene resin, polypropylene resin) is 17.5 (flame retardation of polymer (page 122): Taisei Co., Ltd.), non-halogen such as magnesium hydroxide or aluminum hydroxide is used for this purpose. It is necessary to add a large amount of 100 to 200 parts by weight of a system flame retardant. As a result, as described above, the workability, mechanical properties, durability, abrasion resistance, etc. of the obtained flame retardant resin layer are significantly deteriorated. And is therefore impractical ("Polymer Digest" 1
988. Vol.10).

Accordingly, a flameproof sheet product obtained by making a polyolefin resin non-halogen flame-retardant has excellent mechanical strength, flexibility, abrasion resistance and outdoor durability, and also has good processability, coloring property and cost performance. An excellent polyolefin canvas or tarpaulin has not yet been developed.

[0008]

DISCLOSURE OF THE INVENTION The present invention solves the problem of mechanical property deterioration in the above-mentioned conventional non-halogen flame-retardant polyolefin-based resin-coated sheet, and conforms to the fire prevention test specified in the Fire Service Law. Provide a flame-retardant polyolefin-based resin-coated sheet that exhibits excellent flame retardancy, is excellent in processability, colorability, and low cost, contains a fabric base cloth, and is suitable for sheets for industrial materials. It is assumed that.

[0009]

SUMMARY OF THE INVENTION The present invention provides a non-halogen composition having the same mechanical properties and durability as a conventional industrial material sheet having a soft polyvinyl chloride resin coating layer, and having excellent flame retardancy. As a result of studying to provide a polyolefin resin sheet, a melt flow rate (MFR) obtained by blending 5-35 parts by weight of red phosphorus particles with respect to 100 parts by weight of a polyolefin resin in a flame-retardant polyolefin resin coated sheet. A) a polyolefin resin composition film of 0.2 to 5.0 g / 10 min on both surfaces of a fiber fabric woven from a multifilament yarn having a specific range of dry heat shrinkage obtained by spinning a specific thermoplastic resin; Polio that has a dry heat shrinkage of 5 to 25% or less in the warp and weft directions by heating at 150 ° C. for 15 minutes. At the same time that the polyolefin resin composition film and the fabric base fabric are quickly melted away from the fire source, the after-flame of the melted portion self-extinguishes, and ,
The present inventors have found that the mechanical properties and abrasion resistance of this sheet are excellent, and have completed the present invention.

The flame-retardant polyolefin-based resin-coated sheet of the present invention comprises a base fabric including a fabric woven from thermoplastic resin filament yarns, and front and back surfaces formed from a polyolefin-based resin composition on both sides of the base fabric. A composite sheet having a double-sided resin layer, wherein the polyolefin-based resin composition contains 100 parts by weight of a polyolefin-based resin and 5 to 35 parts by weight of red phosphorus particles mixed therewith, and 0.2 ~ 5.0g / 10min melt flow rate (MF
R) (according to the test method of JIS K 6760, provided that
Temperature: 190 ° C, Load: 21.18N (2.16kgf
)), And the composite sheet has a dry heat shrinkage in the warp and weft directions by heating at 150 ° C. for 15 minutes of 5 to 25%. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the thermoplastic resin forming the thermoplastic resin filament thread for the base fabric is preferably selected from a polyolefin resin, a polyester resin, and a polyamide resin. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the base fabric filament yarn is a multifilament yarn, a monofilament yarn, a tape yarn,
It is preferred to be selected from split yarns and split yarns. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the polyolefin-based resin composition has at least one selected from an inorganic pigment and an organic pigment in an amount of 1 to 20 parts by weight based on 100 parts by weight of the polyolefin-based resin. It may further comprise a seed coloring agent. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the thermoplastic resin filament yarn is selected from a polyethylene filament yarn, a polypropylene filament yarn, and a mixed filament yarn of a polyethylene resin and a polypropylene resin. It is preferable to consist of one or more kinds. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the base fabric is a woven fabric, which is heat-set, and heated at 150 ° C. for 15 minutes to 5 to 25% in the longitudinal and weft directions. Or it is not heat-set and exhibits a dry heat shrinkage of 5 to 25% in the warp and weft directions by heating at 150 ° C. for 15 minutes. Preferably, there is. In the flame-retardant polyolefin resin-coated sheet of the present invention, the red phosphorus particles, the surface of which is aluminum hydroxide, magnesium hydroxide, titanium oxide,
It is coated with at least one selected from zinc oxide, formalin resin, phenol resin, melamine resin, urea resin, and epoxy resin, and the average particle diameter of the surface-coated red phosphorus particles is 5 to 25 μm. preferable. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, a polyolefin-based resin protective layer that is colored without containing the red phosphorus particles is formed on at least one of the front and back double-sided polyolefin-based resin composition layers. You may. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the colored polyolefin-based resin protective layer comprises 5 to 50 parts by weight of a phosphoric acid compound component and 1 to 20 parts by weight of a chemical foaming agent component based on 100 parts by weight of the polyolefin resin. And a melt flow rate (MF) of 0.2 to 5.0 g / 10 min., Containing 1 to 20 parts by weight of a colorant component comprising at least one selected from inorganic pigments and organic pigments.
It is preferably formed of a colored polyolefin resin composition having R). In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the phosphoric acid-based compound component is a phosphate, a phosphate, a phosphate,
And at least one selected from condensed phosphates. In the flame-retardant polyolefin resin-coated sheet of the present invention, the condensed phosphate is at least one selected from ammonium polyphosphate, thermosetting resin-coated ammonium polyphosphate, and melamine polyphosphate.
Preferably, it contains a species. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the chemical blowing agent component comprises
It is preferable to include at least one selected from azo compounds, sulfohydrazide compounds, and nitroso compounds. In the flame-retardant polyolefin-based resin-coated sheet of the present invention, the thickness of the colored polyolefin-based resin protective layer is preferably 10 to 50% of the total thickness of the flame-retardant polyolefin-based resin-coated sheet. The method for producing a flame-retardant polyolefin-based resin-coated sheet of the present invention comprises a polyolefin-based resin composition on both front and back surfaces of a base fabric including a fabric woven from thermoplastic resin filament yarns, using a heating laminator. Adhering a film to form a composite sheet, wherein the polyolefin-based resin composition comprises 100 parts by weight of a polyolefin-based resin and 5 to 25 parts by weight of red phosphorus particles mixed therewith; .2 to 50 g / 10 min melt flow rate (MFR) (according to the test method of JIS K 6760,
However, temperature: 190 ° C, load: 21.18N (2.16N
kgf)), and in the attaching step using the heating laminator, the surface of the heat roll on the attaching side of the polyolefin resin composition film is 70 to
Heat to a temperature of 180 ° C. and raise the temperature of said base fabric to 12
The temperature is adjusted to 0 ° C. or lower, and the film is continuously heated and pressed to the base fabric. At this time, the dry heat shrinkage of the obtained composite sheet by heating at 150 ° C. for 15 minutes is 5
２５25%. In the method for producing a flame-retardant polyolefin-based resin-coated sheet of the present invention, a polyolefin-based resin protective layer that is colored without containing the red phosphorus particles is formed on at least one surface of the front and back double-sided polyolefin-based resin composition layers. May further be included. In the method for producing a flame-retardant polyolefin-based resin-coated sheet according to the present invention, the step of forming the polyolefin-based resin protective layer comprises applying a film of the polyolefin-based resin, or a coating liquid containing the polyolefin-based resin. May be carried out by coating and drying.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The flame-retardant polyolefin resin-coated sheet of the present invention comprises a base fabric containing a fabric woven from thermoplastic resin filament yarn, and a polyolefin resin composition on both surfaces of the base fabric. It is constituted by a composite sheet having the formed front and back resin layers. The polyolefin resin composition contains 100 parts by weight of the polyolefin resin and 5 to 35 parts by weight of red phosphorus particles mixed therein, and has a melt flow rate (MFR) of 0.2 to 5.0 g / 10 min. ) (JIS K 6760)
Test method. However, temperature: 190 ° C, load: 2
1.18 N (2.16 kgf)). The dry heat shrinkage of the composite sheet in the warp and weft directions by heating at 150 ° C. for 15 minutes is in the range of 5 to 25%.

The types of polyolefin resins used in the flame-retardant polyolefin resin-coated sheet according to the present invention include ethylene-α-olefin copolymer, low density polyethylene, medium density polyethylene, high density polyethylene, ethylene-vinyl acetate. Copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-methyl methacrylic acid copolymer, Examples include an ethylene-methyl methacrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-ethyl acrylate copolymer, and a mixture of two or more of these. As the polyolefin resin used in the present invention, those produced by a radical polymerization method or an ionic polymerization method can be used.

Examples of the polyethylene resin obtained by the radical polymerization method include a polymer obtained by copolymerizing ethylene alone or a copolymer of ethylene and a monomer capable of undergoing radical polymerization. Examples of the monomer capable of undergoing radical polymerization include unsaturated carboxylic acids such as acrylic acid and methacrylic acid, esterified products and acid anhydrides thereof, and vinyl esters such as vinyl acetate. Examples of the esterified product of the unsaturated carboxylic acid include ethyl acrylate, methyl methacrylate, and glycidyl methacrylate. These monomers can be used alone or in combination of two or more.

The polyethylene resin obtained by the ionic polymerization method is obtained by copolymerizing ethylene alone or ethylene and an α-olefin having 3 to 18 carbon atoms using a transition metal solid catalyst or a metallocene homogeneous catalyst. And the α-olefin is, for example, propylene, butene-1,4-methylpentene-
1, hexene-1, octene-1, decene-1, octadecene-1, and the like are used, and it is preferable to use an α-olefin having 4 to 10 carbon atoms. These α-olefins may be used alone or in combination of two or more.

The polyolefin-based resin used in the flame-retardant polyolefin-based resin-coated sheet of the present invention is not limited to the above-mentioned polyolefin-based resin, but includes ethylene-vinyl acetate copolymer and ethylene-acrylic acid copolymer. Polymer, ethylene-acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methacrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-methyl methacrylate copolymer Ethylene copolymers such as coalesced copolymers, ethylene-ethyl acrylate copolymers, and ethylene-ethyl acrylate copolymers can be preferably used because they have the advantage of high high-frequency weldability. Further, these ethylene-based copolymers may be used alone or in a blend composition of two or more, having a melt flow rate of 0.5 to 1
0 g / 10 min, especially 0.5 to 5.0 g / 10 min, and the copolymerized monomer content is 5 to 35% by weight, especially 15
What is 25% by weight can be suitably used in the present invention.
If the melt flow rate is less than 0.5 g / 10 min, it may be difficult to process the resulting flame-retardant polyolefin resin-coated sheet, and it may be 10 g / min.
If it is higher than 10 minutes, the strength and heat resistance of the obtained resin-coated sheet may be insufficient, and further, the adhesiveness may be increased to cause problems such as blocking. When the content of the copolymer monomer is less than 5% by weight, the high-frequency weldability of the obtained copolymer may be insufficient, and the content of the copolymer monomer may be less than 35%.
When the amount is more than the weight percentage, the mechanical strength of the obtained polyolefin-based resin film becomes insufficient, and the tackiness at the time of processing increases, which causes disadvantages such as extremely difficult forming processing.

Further, the polyolefin resin used in the flame-retardant polyolefin resin-coated sheet of the present invention has a melt flow rate of 0.1 for the purpose of increasing its mechanical resin strength and durability such as abrasion resistance. 5-10g / 10mi
n, metallocene catalyzed polyethylene, ethylene-α-olefin, low density polyethylene, medium density polyethylene,
Blend of a crystalline polyolefin resin composed of at least one kind of polypropylene or the like, and a copolymer resin composed of at least one kind selected from the ethylene-vinyl acetate copolymer resin and the ethylene-acrylic copolymer resin It is preferably a body. The blend ratio of the crystalline polyolefin-based resin and the copolymer resin is not particularly limited, but is based on 100% by weight of the polyolefin-based resin blend.
It is preferable from the viewpoint of high-frequency weldability that the total amount of monomers copolymerized with ethylene, that is, vinyl acetate and acrylic monomers, in the copolymer resin is 5 to 35% by weight. Further, the melt flow rate of the polyolefin resin blend used in the flame-retardant polyolefin resin coated sheet of the present invention is 0.5 to 10 g /
Preferably, it is 10 min. If the melt flow rate is less than 0.5 g / 10 min, it may be difficult to mold the resulting flame-retardant polyolefin resin-coated sheet. If it is higher than 10 g / 10 min, not only the mechanical strength and the heat creep resistance of the obtained resin-coated sheet become insufficient, but also disadvantages such as an increase in tackiness and occurrence of blocking may occur. .
When the content of the copolymer monomer contained in the polyolefin resin blend is less than 5% by weight, the high-frequency weldability of the obtained polyolefin resin composition layer may be insufficient, and the copolymer monomer content may be reduced. If the amount is more than 35% by weight, the mechanical strength of the obtained polyolefin-based resin film becomes insufficient, the tackiness at the time of processing increases, and molding processing may be difficult.

The polyolefin resin used in the flame-retardant polyolefin resin coated sheet of the present invention may be a polypropylene resin having a melt flow rate of 0.5 to 10 g / 10 min, in addition to the above polyolefin resins. For example, reactor polymerization resin of polypropylene, polypropylene and ethylene-propylene rubber (EPR rubber), or PP-EPR resin which is a polymer alloy thereof, reactor polymerization of polypropylene and ethylene-propylene-conjugated diene rubber (EPDM rubber) Resins, or a polymer alloy such as PP-EPDM resin may be blended and used.

The red phosphorus particles contained in the polyolefin-based resin composition of the flame-retardant polyolefin-based resin-coated sheet of the present invention can be obtained by converting yellow phosphorus into an inert gas atmosphere at 250-350.
It is converted by heating at a temperature of ° C. and is used as a powder having an average particle size of 5 to 25 μm. Also,
Red phosphorus particles that can be used in the present invention include aluminum hydroxide, magnesium hydroxide, titanium oxide, inorganic compounds of zinc oxide, or thermosetting resins such as formalin resin, phenol resin, melamine resin, urea resin, and epoxy resin. It is preferable to use red phosphorus particles whose surface is coated with at least one member selected from the group consisting of: In particular, white-treated red phosphorus particles surface-coated with titanium oxide are preferably used because they have high flexibility in coloring the flame-retardant polyolefin resin-coated sheet of the present invention.

The red phosphorus particles used in the polyolefin resin composition layer of the flame-retardant polyolefin resin coated sheet of the present invention are blended in an amount of 5 to 35 parts by weight based on 100 parts by weight of the polyolefin resin. If the amount of the red phosphorus particles is less than 5 parts by weight, the resulting polyolefin-based resin composition layer will have insufficient flame retardancy, failing to comply with the fire protection test standards of the Fire Defense Law. If the amount of the red phosphorus particles exceeds 35 parts by weight, the flame retardancy level does not saturate and does not improve, but rather the workability of the polyolefin resin composition layer (film) deteriorates, and the polyolefin resin layer obtained at the same time The mechanical strength of the resin composition layer (film) is significantly deteriorated. Also, based on 100 parts by weight of the polyolefin resin, 5 to 35 parts by weight of red phosphorus particles, especially 10 to 20 parts by weight.
The melt flow rate of the flame-retardant polyolefin-based resin composition containing 0.2 parts by weight is 0.2 to 5.0 g / 10 min.
And preferably 0.5 to 3.0 g / 10 min. When the melt flow rate is less than 0.2 g / 10 min, the processing fluidity of the obtained polyolefin-based resin composition deteriorates, and not only decreases the productivity, but also
The film surface appearance also deteriorates. On the other hand, if the melt flow rate exceeds 5.0 g / 10 min, not only the mechanical strength and the heat creep resistance of the obtained resin-coated sheet become insufficient, but also the adhesiveness increases and blocking occurs.

The polyolefin-based resin composition layer of the flame-retardant polyolefin-based resin-coated sheet of the present invention may be colored with an organic pigment, an inorganic pigment or the like, if necessary. Conventionally known azo pigments such as insoluble monoazo pigments, insoluble disazo pigments, azo lake pigments, condensed azo pigments, metal complex azo pigments, etc., phthalocyanine pigments, and dye lake pigments such as acid dye lake pigments and basic dye lake pigments Such,
Condensed polycyclic pigments such as anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, quinophthalone pigments, isoindoline pigments, and other nitroso pigments And alizarin lake pigments, metal complex azomethine pigments, aniline pigments and the like.

As the inorganic pigment, zinc oxide (zinc oxide)
Hua), titanium oxide (rutile type, anatase type), trioxide
Antimony, iron oxide, iron ferrosyanide (dark blue), oxide
Lead, chromium oxide, zirconium oxide, cobalt oxide and acids
Aluminum oxide composite (cobalt blue), edge oxide
Complex with zinc oxide and magnesium oxide (Kobal
Metal oxides, such as zinc sulfide and barium sulfate
Complex (lithopone), calcium sulfide,
Nd, zinc sulfide, zinc cadmium, cadmium sulfide
, Cadmium sulfide and selenium-cadmium composite
Things (cadmium red, cadmium orange, cadmium)
Mu Yellow) Compound of antimony sulfide and antimony trioxide
(Antimony vermilion), metal sulfides, barium sulfate
Metals such as calcium sulfate, lead sulfate, and basic lead sulfate
Sulfide, barium carbonate, calcium carbonate, magnesium carbonate
Metal, such as a composite of lead, lead carbonate and lead hydroxide (lead white)
Oxide, magnesium hydroxide, aluminum hydroxide (A
Lumina white), aluminum hydroxide and calcium sulfate
Complex (satin white), aluminum hydroxide and sulfuric acid bath
Metal hydroxides such as chromium compound (gloss white)
Material, lead chromate (lead), barium chromate, chromate
Composite of lead, lead molybdate and lead sulfate (chrome
Metal salts such as lyon), lead molybdate and sulfuric acid
Lead composite (molybdenum red), spinel type (XY_Two
O_Four) Structural oxide, rutile type [Ti (XY) O _Two〕Construction
Oxides, other carbon blacks, titanium black
, Acetylene black, graphite, silica, white car
Bon, diatomaceous earth, talc, clay, aluminum powder
Material, bronze powder, nickel powder, stainless steel powder, pearl face
Fees and the like.

Further, these organic pigments and inorganic pigments are used as melamine resins, benzoguanamine resins, urea resins,
A thermosetting resin-coated pigment obtained by mixing and filling a thermosetting resin such as a phenol resin or an epoxy resin into fine particles may be used. In addition, as products of these organic pigments and inorganic pigments, when used in coloring applications such as synthetic resin molded articles, films, synthetic fibers, and synthetic resin paints, in order to further improve dispersibility, a dispersant treatment is performed. It is preferred to use the processed pigments prepared. As a dispersant,
As aqueous dispersants, sodium lignin sulfonate, sodium alkyl sulfate, sodium alkylaryl sulfonate, formalin condensate of sodium naphthalene sulfonate, marcel soap, polyoxyethylene alkyl ether, polyoxyethylene aryl ether, styrene-maleic acid resin , Polyacrylic acid derivatives and the like, and as an oil dispersant, lecithin, sorbitan fatty acid ester, partial fatty acid ester of polyacrylic acid, alkylamine fatty acid salt, alkyldiamine,
Examples thereof include alkyl triamine and metal soap of naphthenic acid.

These organic pigments and inorganic pigments treated with a dispersant are added with a vehicle, a press cake, a resin, a wax, a plasticizer, water, and the like in order to improve the processability in various applications. And then
It is desirable to use a processed pigment adjusted to a form such as a flashed color, an aqueous liquid color, an oily liquid color, a paste color (vinyl toner color), a dry color, a wet color, a masterbatch, or a colored pellet.

In the production of the film for a polyolefin resin composition layer of the present invention, when the thermoplastic resin is subjected to melt kneading such as calendering, T-die extrusion and inflation, dry color, masterbatch, It is suitable to use colored pellets. Particularly for the molding and processing of olefin-based resin compositions, the form of colored pellets in which an organic pigment and an inorganic pigment are filled in a high concentration in a polyolefin resin such as polyethylene or polypropylene together with a dispersant and wax is more preferably used. it can. In addition, when the polyolefin resin is an aqueous emulsion as a raw material, an aqueous liquid color can be used, and when the solvent is a polyolefin resin coating agent, a flashed color, a paste color, a dry color, an oily liquid color, etc. Can be used.

As the colorant for the polyolefin resin composition layer of the flame-retardant polyolefin resin coated sheet of the present invention, an inorganic pigment and an organic pigment can be used in combination. The combination of these coloring materials is not particularly limited since it is a combination according to the desired hue adjustment. However, these inorganic pigments and / or organic pigments are based on 100 parts by weight of the polyolefin resin. Is preferably 1 to 20 parts by weight, particularly preferably 3 to 10 parts by weight. If the amount of the pigment is 1 part by weight or less, the coloring property of the polyolefin resin containing the red phosphorus particles may be insufficient, and the red phosphorus particles may not be concealed. On the other hand, if it exceeds 20 parts by weight, not only may the processability of the polyolefin resin composition layer film be deteriorated, but also the flame retardancy may be reduced.
The melt flow rate of the colored flame-retardant polyolefin-based resin composition is 0.2 to 5.0 g / 10 min, and particularly preferably 0.5 to 3.0 g / 10 min. When the melt flow rate is less than 0.2 g / 10 min, the processing fluidity of the obtained resin composition becomes poor,
Not only does the productivity decrease, but the film surface appearance may also deteriorate. If the melt flow rate exceeds 5.0 g / 10 min, not only the mechanical strength and the heat creep resistance of the obtained resin-coated sheet become insufficient, but also the adhesion may increase and blocking may occur. .

The above-mentioned polyolefin-based resin composition layer of the flame-retardant polyolefin-based resin-coated sheet of the present invention may contain, if necessary, an antistatic agent, an antioxidant, a weathering stabilizer such as a hindered amine compound, an ultraviolet absorber, Lubricants and the like can be added. In addition, as long as the properties of the obtained flame-retardant polyolefin-based resin-coated sheet are not impaired, an inorganic filler can be added and used in combination to reduce the production cost. As the inorganic filler, for example,
Examples include calcium carbonate, talc, clay, silica, glass powder and the like. Other commonly used additives such as plasticizers, softeners, stabilizers, foaming agents, surfactants, crosslinking agents, curing agents, conductive fillers, fungicides, antibacterial agents, etc. You may mix | blend in the range which does not deviate.

The method for producing the layer film for the polyolefin resin composition used in the present invention is not particularly limited. Red phosphorus particles, organic pigments, inorganic pigments and the like are included in the polyolefin resin used in the present invention. Any method can be used as long as it can be uniformly dispersed and mixed, and can be formed into a film. As a mixing method, each component such as red phosphorus particles and organic pigments and inorganic pigments and a polyolefin resin are melt-kneaded by a known method using, for example, a Banbury mixer, a kneader, a twin-screw kneader, and then granulated. Prepare a masterbatch of a polyolefin resin composition containing red phosphorus particles and organic pigments, inorganic pigments, and other components at a high concentration using a method or a Banbury mixer. A method of dry blending using a mixer such as a mixer or a Henschel mixer, and a method of melt-kneading and granulating with a single-screw extruder, a twin-screw extruder or the like after mixing can be adopted.

The film for the polyolefin resin composition layer used in the present invention can be produced by a known film processing technique such as a T-die method, an inflation method, or a calendering method. In order to surely and stably carry out the uniform dispersion in the polyolefin-based resin composition, the T-die method, and its molding processing temperature can be significantly lower than those of the inflation method. The calendar method is suitable. In the production of the film for a flame-retardant polyolefin-based resin composition layer of the present invention, it is desirable to perform a molding process by a calendering method in a temperature range of 80 to 200 ° C.

The thickness of the film for the polyolefin-based resin composition layer of the flame-retardant polyolefin-based resin-coated sheet of the present invention is preferably from 80 to 800 μm, particularly preferably from 130 to 450 μm. If the thickness is less than this range, it is difficult to mold, and when laminating on a fabric base fabric, the head of the film will be cut off by thermocompression bonding with the uneven part of the base fabric surface, impairing waterproofness, outdoor May not be used for tent and seat applications. The thickness is 800 μm.
If the thickness is larger than m, not only the calendering becomes difficult, but also it is heavy and lacks flexibility, and the handleability is deteriorated.

In order to form the flame-retardant polyolefin resin composition layer of the present invention on a base cloth, an aqueous composition obtained by dispersing and blending red phosphorus particles in a polyolefin resin emulsion is coated on the base cloth. It may be performed by coating and drying. As a method for forming a polyolefin-based resin composition layer using the polyolefin-based resin emulsion, the above-described emulsion composition for forming a polyolefin-based resin composition layer directly on a base fabric may be coated and applied; Alternatively, an emulsion for forming a polyolefin-based resin composition layer on release paper or a release film may be coated with the composition, dried, and laminated on a base fabric. Examples of the polyolefin resin emulsion include ethylene-vinyl acetate copolymer resin,
Emulsions such as vinyl acetate-ethylene copolymer resins, ethylene-acrylic acid copolymer resins, ethylene-acrylic acid copolymer ionomer resins, and ethylene-propylene copolymer resins can be used.

In order to form the polyolefin resin composition layer of the present invention, the above polyolefin resin is dissolved in an organic solvent, and a solvent composition obtained by dispersing and blending red phosphorus particles in this solution is coated and dried. .

The thermoplastic resin forming the thermoplastic resin filament yarn used for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention includes, for example, polyethylene resin, polypropylene resin, polyester resin, and the like.
It is preferable to be selected from polyamide resins and the like. Further, the filament yarn for the base fabric is preferably selected from a multifilament yarn, a monofilament yarn, a tape yarn, a split yarn and a split yarn, and more preferably selected from multifilament yarns. These yarns can be manufactured by a usual thermoplastic filament yarn manufacturing method. For example, as a method of spinning the multifilament yarn, for example, the thermoplastic resin is heated to a temperature equal to or higher than a melting temperature (melting point) to obtain a fluid viscous melt, which is then subjected to a specific caliber (0.2 to 0.2 mm). Through a spinneret having pores of about 0.6 mmφ), air, nitrogen,
A method of extruding into an inert cooling medium such as water and rapidly cooling and solidifying to obtain a long fiber spun raw yarn using a conventionally known melt spinning method and a production method using equipment is used.

The unstretched long fiber spun yarn is stretched 3.0 to 5.0 times by, for example, heating at 80 to 100 ° C. or cold stretching at about normal temperature to arrange the microstructure of the fiber. The fibers can be crystallized to have strength. This drawing step may be incorporated in the spinning step, and it is preferable that the drawing step and the multifilament twisting step are performed simultaneously. Further, a two-stage heat treatment may be performed if necessary. These melt spinning speeds are not particularly specified because the spinning speeds are different depending on the thermoplastic resin used and the equipment, and for example, the spinning speed when melt spinning from a polyester resin is 1,000.
-10,000 m / min, especially 2,000-6,000
Those spun at a speed of m / min can be preferably used.

The standard of the multifilament yarn used for the fiber fabric of the flame-retardant polyolefin resin-coated sheet of the present invention is, for example, 100 to 100 spun from the above-mentioned thermoplastic resin and given an arbitrary number of twists. Multifilament yarns of 2200 denier, preferably 200 to 1600 denier, more preferably 250 to 1100 denier can be used. If the multifilament yarn is less than 100 denier, the resulting sheet may have insufficient tear strength, and if it exceeds 2200 denier, the breaking strength and tear strength will certainly improve, but the yarn diameter will increase and the In some cases, the thickness of the sheet becomes large, and the handleability of the sheet becomes insufficient.

The filament yarn used for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention is preferably a filament yarn spun from a polyethylene resin or a polypropylene resin, a polyethylene resin and a polypropylene resin. And a mixed yarn of a multifilament yarn spun from a polyethylene resin and a multifilament yarn spun from a polypropylene resin. As the polyethylene resin used as a raw material of the polyethylene resin filament yarn (particularly, the multifilament yarn), for example, a density of 0.94 to 0.94 obtained by a medium-to-low pressure polymerization method of an ethylene monomer is used.
High-density polyethylene having 0.97 g / cm ³ , a crystallinity of 70 to 95%, and a melt flow rate of 0.4 to 1.2 can be preferably used from the viewpoint of fiber strength and melt spinnability. As a polypropylene resin as a raw material of a polypropylene resin filament yarn (particularly, a multifilament yarn), for example, an isotactic structure obtained by polymerizing a propylene monomer using a stereoregular catalyst such as a Ziegler-Natta catalyst is used. Polypropylene can be preferably used from the viewpoint of fiber strength and spinnability. In addition, a polypropylene resin filament yarn and a mixed filament yarn of a polyethylene resin and a polypropylene resin are formed by, for example, slitting a polypropylene resin film or a mixed film of a polyethylene resin and a polypropylene resin into a tape shape and stretching it 5 to 15 times. After the molecular orientation, the fiber may be split into fibers by mechanical operation and twisted.

The dry heat shrinkage (JIS L-1073) of the polyethylene filament yarn, the polypropylene filament yarn, and the polyethylene-polypropylene blended filament yarn is 5 to 15 when heated at 120 ° C. for 15 minutes.
It is preferably 25%, particularly preferably within 5 to 15%. When the dry heat shrinkage ratio is less than 5%, the fiber fabric is quickly melted when the flame-retardant polyolefin-based resin sheet obtained in the flameproof test is fired, and the physical shrinkage behavior which is away from the fire source is inferior. Of the melted end of the steel tends to occur, and as a result, it may not conform to the item of the carbonized area of the flameproof standard specified in the Fire Service Law. Further, when the dry heat shrinkage exceeds 25%, the fiber fabric is quickly melted during flame application and has excellent physical shrinkage behavior away from the fire source, but the workability and heat resistance of the flame-retardant sheet of the present invention are excellent. Creep properties may be insufficient.

As the filament yarn used for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention, a multifilament yarn spun from a polyester resin is preferably used. Examples of the polyester resin as a raw material of the polyester multifilament yarn include polyethylene terephthalate (PET) obtained by polycondensation of terephthalic acid and ethylene glycol, and polybutylene terephthalate (PBT) obtained by polycondensation of terephthalic acid and butylene glycol. No.
Among them, polyester fibers melt-spun from polyethylene terephthalate resin are preferably used in view of fiber strength and melt spinnability. In addition, polyethylene terephthalate may contain about 5% by weight of a copolymer monomer such as isophthalic acid, naphthalenedicarboxylic acid, adipic acid, and diethylene glycol, in addition to the above monomers. A polyester multifilament yarn having a dry heat shrinkage (JIS L-1073) of from 5 to 25%, especially from 5 to 15% when heated at 150 ° C. for 15 minutes is preferably used. When the dry heat shrinkage ratio is less than 5%, the fiber fabric is quickly melted during flame of the flame-retardant polyolefin-based resin-coated sheet to be obtained in the flameproof test, and the physical shrinkage behavior is inferior to the fire source. The residual flame of the molten end of the sheet is liable to occur, and as a result, it may not conform to the item of the carbonization area of the flameproof standard specified in the Fire Service Law. Further, when the dry heat shrinkage exceeds 25%, the base fabric is rapidly melted upon flame application and has excellent physical shrinkage behavior away from the fire source, but the workability of the flame-retardant sheet of the present invention is excellent. And heat creep resistance may be insufficient.

A multifilament yarn spun from a polyamide resin can be used as the filament yarn used for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention. Examples of the polyamide resin used as a raw material of the polyamide multifilament yarn include nylon 6 obtained by ring-opening polymerization of ε-caprolactam and nylon 66 obtained by polycondensation of adipic acid and hexamethylenediamine. Dry heat shrinkage of the polyamide multifilament yarn obtained from these nylon 6 and nylon 66 (JIS standard L-107)
3) is preferably 5 to 25% when heated at 150 ° C. for 15 minutes, and more preferably 5 to 15%. When the dry heat shrinkage ratio is less than 5%, the flame retardant polyolefin-based resin-coated sheet obtained at the time of flame in the flameproof test, the fiber fabric is quickly melted, and the physical shrinkage behavior that goes away from the fire source is inferior. Of the molten end of the steel tends to occur, and as a result, it may not conform to the item of the carbonized area of the flameproof standard specified in the Fire Service Law. Further, when the dry heat shrinkage exceeds 25%, the fiber fabric is quickly melted during flame application and has excellent physical shrinkage behavior away from the fire source, but the workability of the flame-retardant sheet of the present invention is excellent. And insufficiency in heat creep resistance.

The filament yarn used for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention is:
It may be a colored filament yarn spun from a thermoplastic resin containing a colorant such as an organic pigment, an inorganic pigment, or a dye.

The base fabric that can be used in the flame-retardant polyolefin resin-coated sheet of the present invention includes a woven fabric, a knitted fabric,
Any of non-woven fabrics is possible, but when practically used for industrial materials, woven fabrics are preferred because they have an excellent balance of physical properties in the warp and weft directions. As the woven fabric, for example, a plain woven fabric having a minimum unit structure of a weaving structure using two warps and wefts each, a twill woven fabric having a minimum unit structure of a weaving structure using three warps and wefts each, and a warp And a satin woven fabric having at least 5 wefts each as the minimum unit structure of the weaving structure. As the woven fabric for the base fabric of the flame-retardant polyolefin resin-coated sheet of the present invention, a woven fabric having openings is used. When used, a bridge fusion effect at the time of heat lamination of a polyolefin-based resin film can be obtained. As such an apertured woven cloth, a plain woven cloth, which can be easily designed to freely adjust the weaving density of the aperture, is particularly preferable. It is most preferable to use a plain woven fabric from the viewpoint of the balance of the physical properties of the flame-retardant polyolefin-based resin sheet of the present invention in the warp and weft directions. The weaving of these woven fabrics can be performed using a conventionally known loom such as a shuttle loom or a shuttleless loom (rapier type, gripper type, water jet type, air jet type).

The flame-retardant polyolefin resin coating of the present invention
Thread density of warp and weft of base fabrics that can be used for sheets
Although there is no particular limitation on, for example, melting from the above thermoplastic resin
100 to 2200 denier mulch obtained by melt spinning
10 to 50 filament yarns per inch, for example
One inch of 250 denier multifilament yarn was hit
20 to 30 or 500 to 1000 denier
15 to 25 filament yarns per inch, or
1500 denier multifilament yarn per inch
Open plain weave with a weave density of about 10 to 20
Woven fabric is suitable. Also, these blank plain weave fabrics
As a basis weight of 50 to 500 g / m ^TwoSuitable for
ing.

The fabric for the base fabric which can be used for the flame-retardant polyolefin resin-coated sheet of the present invention includes, for example, any of the polyethylene multifilament yarn, the polypropylene multifilament yarn, and the polyethylene-polypropylene mixed multifilament yarn. Alternatively, the cloth woven by mixing is subjected to a known heat setting treatment, and its dry heat shrinkage (JIS A-6008) at 150 ° C. for 15 minutes is 5% to 25%, preferably 5 to 15%. Or a woven fabric that has not been heat-set, but has a dry heat shrinkage of 5 to 25%, preferably 5 to 15% when heated at 150 ° C. for 15 minutes. When the dry heat shrinkage of the woven fabric is less than 5%, when the flame-retardant polyolefin-based resin-coated sheet obtained in the flameproof test is fired, the fiber fabric is quickly melted and physically shrinks away from the fire source. In addition, after-flame tends to occur at the molten end of the sheet, and as a result, it may not conform to the item of the carbonization area of the flameproof standard specified in the Fire Service Law. Further, when the dry heat shrinkage exceeds 25%, the fiber fabric is quickly melted during flame application and has excellent physical shrinkage behavior away from the fire source, but the workability of the flame-retardant sheet of the present invention is excellent. And the heat creep resistance becomes insufficient.

As the base fabric which can be used for the flame-retardant polyolefin-based resin-coated sheet of the present invention, for example, a fiber fabric woven by the polyester multifilament yarn is dried by heating at 150 ° C. for 15 minutes by heat setting. Shrinkage (JIS standard A-6008) is 5% to 25
%, Especially a woven fabric controlled within 5 to 15%, or
A woven fabric having a dry heat shrinkage of 5 to 25%, particularly preferably 5 to 15%, when heated at 150 ° C. for 15 minutes without heat setting is preferable. When the dry heat shrinkage of the woven fabric is less than 5%, when the flame-retardant polyolefin-based resin-coated sheet obtained in the flameproof test is fired, the fiber fabric is quickly melted and physically shrinks away from the fire source. In addition, after-flame tends to occur at the molten end of the sheet, and as a result, it may not conform to the item of the carbonization area of the flameproof standard specified in the Fire Service Law. Further, when the dry heat shrinkage exceeds 25%, at the time of flame, the fiber fabric is quickly melted, and although excellent in physical shrinkage behavior away from the fire source, the workability of the flame-retardant sheet of the present invention, The heat creep resistance may be insufficient.

The fabric for the base fabric used in the flame-retardant polyolefin resin-coated sheet of the present invention may be subjected to a flame-retardant treatment, if necessary, or may be a flame-retardant fiber. May be woven fabric. Examples of the flame-retarded fabric include a phosphoric ester compound flame retardant, an ammonium polyphosphate compound flame retardant, an (iso) cyanuric acid derivative compound flame retardant, a cyanamide compound flame retardant, and urea, depending on the type of the fiber. Flame retardant containing one or more selected from flame retardants based on water or an organic solvent, or an emulsion or latex as a dispersion medium, and a flame retardant dispersed or dissolved therein. And those obtained by impregnating the fiber fabric with the chemical treating agent, drying and heat-treating. Further, as the fiber which has been made flame retardant in advance, one selected from the above flame retardants at the stage of spinning the yarn from a thermoplastic resin such as a polyethylene resin, a polypropylene resin, a polyester resin or a polyamide resin.
Flame-retarded fiber melt-spun by blending more than one kind, or polyester obtained by substituting a part of raw material monomer with phosphate ester-containing monomer or halogen-containing monomer at the stage of synthesizing thermoplastic resin Resin, flame-retarded fibers melt-spun from polyamide resin, but to impart excessive flame retardancy to the base fabric used in the flame-retardant polyolefin resin-coated sheet of the present invention,
In the flameproof test specified in the Fire Service Law, the flameproofing balance may be deteriorated in the carbonized area. In order to impart the flame retardancy to these fiber cloths, it is preferable that the fiber olefin resin layer film of the present invention is subjected to an appropriate flame retardation treatment in accordance with the melting and self-extinguishing levels.

For laminating the base fabric and the film for the polyolefin resin composition layer, the film may be laminated on only one side of the base fabric or on both sides thereof. In consideration of the above, it is preferable to laminate the polyolefin resin composition layer film on both surfaces of the base fabric. In addition, as a method of lamination, an adhesive layer may be provided between the polyolefin-based resin composition layer film and the base fabric, or lamination and fusion may be performed without an adhesive. The method of laminating the base fabric used for producing the flame-retardant polyolefin-based resin-coated sheet of the present invention and the film for the polyolefin-based resin composition layer is a calendar topping method in which the film is molded and thermally laminated on the base fabric simultaneously. Method, or a T-die laminating method, or a film is formed once by a calendering method, a T-die method, an inflation method, etc., and then laminated on a base fabric by thermocompression bonding using a laminator. A method may be used.
For the production of the flame-retardant polyolefin-based resin-coated sheet according to the present invention, a method of thermocompression bonding a polyolefin-based resin composition layer film formed by a calendering method and a polyester fiber plain woven base fabric is efficient and economical. It is a target. At this time, the weave structure of the plain weave base fabric is more preferably a plain weave. Further, when the method for forming a film for a polyolefin-based resin composition layer used in the flame-retardant polyolefin-based resin-coated sheet of the present invention is carried out by coating and drying a blended composition using a polyolefin-based resin emulsion. As the fibrous plain weave base fabric, a non-through plain weave with high yarn density may be used.

On the surface of the colored polyolefin resin composition layer of the flame-retardant polyolefin resin coated sheet of the present invention, a protective layer made of a colored polyolefin resin containing no red phosphorus particles may be provided. The colored polyolefin resin protective layer containing no red phosphorus particles preferably contains a non-halogen flame retardant and is flame retarded, and the phosphoric acid compound flame retardant 5 per 100 parts by weight of the polyolefin resin ~ 50 parts by weight and chemical blowing agent 1-20
Color protective layer formed from a composition having a melt flow rate (MFR) of 0.2 to 5.0 g / 10 min by blending 1 to 20 parts by weight of an inorganic pigment and / or an organic pigment. It is preferable that

The polyolefin resin which can be used for the colored polyolefin resin protective layer of the flame-retardant polyolefin resin coated sheet of the present invention is selected from the polyolefin resins which can be used for the flame-retardant polyolefin resin composition layer of the present invention. Melt flow rate (MFR: JIS
K6760) is 0.5 to 10 g / 10 min, preferably 0.5 to 5.0 g / 10 min, and the copolymer monomer content is selected from those of 5 to 35% by weight, preferably 15 to 25% by weight. Is preferred. If the melt flow rate is less than 0.5 g / 10 min, it may be extremely difficult to mold the resulting colored polyolefin-based resin protective layer, and if it is higher than 10 g / 10 min, the resulting protective layer may Not only is the abrasion resistance and heat resistance inferior, but also blocking may occur due to increased tackiness. When the copolymerized monomer content is less than 5% by weight, the high-frequency weldability of the obtained protective layer may be insufficient, and when the copolymerized monomer content is more than 35% by weight, it is obtained. In some cases, the mechanical strength of the protective layer becomes insufficient and the tackiness at the time of processing increases, which makes the forming process extremely difficult.

Further, the polyolefin resin which can be used for the colored polyolefin resin protective layer is intended to impart sufficient mechanical resin strength and durability such as abrasion resistance to the protective layer.
A melt flow rate of 0.5 to 10 g / 10 min, at least one selected from crystalline polyolefin resins such as metallocene-catalyzed polyethylene, ethylene-α-olefin, low-density polyethylene, medium-density polyethylene, and polypropylene; It is preferable that the resin is a blend with at least one selected from a vinyl acetate copolymer resin and the above-mentioned ethylene-acrylic copolymer resin. There is no particular limitation on the blending ratio, but the high-frequency welding property is that the total amount of the vinyl acetate component and the acrylic acid component is 5 to 35% by weight based on 100% by weight of the polyolefin resin blend. Preferred from a viewpoint. Further, these melt flow rates are 0.5 to 10 g / 10 mi.
The blend of n can be used more suitably for the colored polyolefin-based resin protective layer of the flame-retardant polyolefin-based resin-coated sheet of the present invention. Melt flow rate is 0.5g / 10mi
If it is less than n, molding of the resulting colored polyolefin-based resin protective layer may be extremely difficult. On the other hand, if it is higher than 10 g / 10 min, not only the abrasion resistance and heat creep resistance of the sheet become insufficient, but also the adhesion may increase and blocking may occur. When the content of the copolymerized monomer is less than 5% by weight, the high-frequency weldability of the obtained protective layer is insufficient, and when the content of the copolymerized monomer is more than 35% by weight, the mechanical properties of the obtained protective layer are reduced. In some cases, the mechanical strength becomes insufficient, and the tackiness during processing increases, which makes the forming processing extremely difficult.

As the polyolefin resin used for the colored polyolefin resin protective layer, in addition to the above-mentioned polyolefin resin, a melt flow rate of 0.5
10 to 10 g / 10 min of a polypropylene resin such as polypropylene, a reactor polymerized resin of polypropylene and ethylene-propylene rubber (EPR rubber), or a PP-EPR resin which is a polymer alloy thereof, or a polypropylene and ethylene-propylene-conjugated diene-based resin A reactor polymerized resin with rubber (EPDM rubber), or a polymer alloy such as PP-EPDM resin may be blended and used.

As the non-halogen flame retardant used in the colored polyolefin resin protective layer, as the phosphoric acid compound, one or more selected from phosphoric acid esters, phosphates, phosphoric acid ester salts and condensed phosphates can be used. Two or more kinds can be used in an amount of 5 to 50 parts by weight based on 100 parts by weight of the polyolefin resin. Among these phosphoric acid compounds, it is particularly preferable to use a condensed phosphate. The condensed phosphate is selected from ammonium polyphosphate, thermosetting resin-coated ammonium polyphosphate, and melamine polyphosphate.
Preferably, one or more species are used. Ammonium polyphosphate having a polymerization degree of 200 or more is preferably used, and furthermore, the surface of ammonium polyphosphate is coated with a thermosetting resin such as a melamine resin, a urea resin, or a phenol resin to be hardly soluble in water. Are preferably used. Further, the degree of polymerization of ammonium polyphosphate is 20
If it is less than 0, the ammonium polyphosphate becomes water-soluble, and the water resistance of the colored polyolefin-based resin protective layer is reduced, and the durability of the flame-retardant effect is poor. It may be. As the condensed phosphorus compound used for the colored polyolefin resin protective layer,
Degree of polymerization 600-1200 surface treated with melamine resin
Ammonium polyphosphate is preferably used. If the addition amount of these phosphoric acid-based flame retardants is less than 5%, the flame retardancy of the resulting flame-retardant polyolefin resin sheet is insufficient, and the flame retardancy test specified in the Fire Defense Law cannot be satisfied. There is. When the amount exceeds 50 parts by weight, not only does the processability of the obtained resin composition deteriorate, but also the abrasion resistance of the colored polyolefin-based resin protective layer becomes insufficient.

Examples of the chemical foaming agent used for the colored polyolefin resin protective layer include azo compounds such as azodicarbonamide and azobisisobutyronitrile, and N, N'-.
Nitroso compounds such as dinitrosopentamethylenetetramine and N, N'-dimethyl-N, N'-dinitrosoterephthalamide, and sulfonyl hydrazides such as p, p'oxybis (benzenesulfonylhydrazide), benzenesulfonylhydrazide and toluenesulfonylhydrazide One to two or more of the compounds can be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the polyolefin resin. In particular, it is preferable to use azodicarbonamide alone or to use 50% by weight or more of the added amount of the chemical blowing agent. Azodicarbonamide is composed of not only pyrolysis products gas (N ₂ , CO, CO ₂ , NH ₃ ) but also urazole,
Biurea, isocyanuric acid, nitrogen-containing decomposed solids and sublimates such as shea merit are by-produced, and these nitrogen-containing decomposed solids and sublimates have high flame retardancy due to a synergistic effect with the phosphoric acid compound. can get. If the added amount of these chemical foaming agents is less than 1% by weight, the flame retardancy of the obtained flame-retardant polyolefin resin sheet becomes insufficient, and the flame retardancy test specified in the Fire Defense Law cannot be satisfied. is there.
When the amount exceeds 20 parts by weight, not only does the processability of the obtained resin composition deteriorate, but also the abrasion resistance of the colored polyolefin-based resin protective layer may be insufficient.

It is preferable that these chemical foaming agents are uniformly dispersed without being thermally decomposed during the formation of the colored polyolefin-based resin layer of the flame-retardant polyolefin-based resin-coated sheet of the present invention. If the chemical blowing agent is thermally decomposed during molding, not only will the resulting sheet have significantly poor flame resistance,
It is not preferable because the appearance of the sheet is also impaired. In addition, inorganic salts such as zinc oxide, lead oxide, tribasic lead sulfate, dibasic lead phosphite, lead stearate, and stearic acid are used as thermal decomposition aids for chemical foaming agents as long as they do not interfere with molding. The decomposition rate can be controlled by using an appropriate amount of a metal soap such as barium or calcium stearate, or urea.

As the inorganic pigment and the organic pigment used in the colored polyolefin resin protective layer, the inorganic pigment and the organic pigment can be used alone or in combination. Combinations of these coloring materials are combined according to the desired hue, and the composition thereof is not particularly limited. However, these inorganic pigments and / or organic pigments are used with respect to 100 parts by weight of the polyolefin resin. The amount of addition
The amount is preferably 1 to 20 parts by weight, more preferably 3 to 10 parts by weight.

A resin composition obtained by blending the polyolefin resin usable for the colored polyolefin resin protective layer with the phosphoric acid compound, the chemical foaming agent, and the inorganic pigment and / or the organic pigment. Has a melt flow rate (MFR: JIS K6760) of 0.5 to 10
g / 10 min, preferably 0.5 to 5.0 g / min.
More preferably, it is 10 min. If the melt flow rate is less than 0.5 g / 10 min, it may be extremely difficult to mold the resulting colored polyolefin resin protective layer, and if it is higher than 10 g / 10 min,
The resulting colored polyolefin-based resin protective layer may have insufficient abrasion resistance and heat resistance, and may further increase adhesion and cause blocking.

The film for the protective layer of the colored polyolefin resin can be produced by a known film processing technique such as a T-die method, an inflation method or a calendering method. ing. For the production of the colored polyolefin-based resin protective layer of the present invention, it is most desirable to carry out calender molding in a temperature range of 80 to 200 ° C. The colored polyolefin-based resin film may be adhered on at least one of the front and back double-sided polyolefin-based resin composition layers to form a protective layer, or a coating liquid containing the colored polyolefin-based resin May be applied and dried to form a protective layer.

The thickness of the colored polyolefin-based resin protective layer is 10 to 50% of the thickness of the flame-retardant polyolefin-based resin-coated sheet (the sum of the thickness of the base fabric and the thickness of the front and back resin layers). Is preferred. This thickness is 10%
If it is less than 10, the molding process becomes difficult, and the hue concentration that conceals the hue of the flame-retardant polyolefin-based resin-coated sheet when laminated on the surface of the flame-retardant polyolefin-based resin composition layer may be insufficient. . On the other hand, if the thickness exceeds 50%, the resulting laminated sheet may have a poor flameproofing balance, making it difficult to meet the flameproofing test prescribed in the Fire Service Law, or may be obtained. In some cases, the sheet becomes heavy and lacks flexibility, resulting in poor handling.

As a method of laminating the colored polyolefin-based resin protective layer film, an adhesive layer may be provided between the colored polyolefin-based resin protective layer film and the flame-retardant polyolefin-based resin composition layer. You may laminate | stack without an agent. The method of laminating the colored polyolefin-based resin protective layer film and the flame-retardant polyolefin-based resin composition layer is performed at the same time as the molding of the colored polyolefin-based resin protective layer film, on the flame-retardant polyolefin-based resin composition layer. Calendar topping method for heat laminating to
Alternatively, a T-die laminating method can be used, or a colored polyolefin-based resin protective layer film is formed once by a calendering method, a T-die method, an inflation method, etc. Although there is a method of laminating on the flame-retardant polyolefin-based resin composition layer, the production of the flame-retardant polyolefin-based resin-coated sheet according to the present invention uses a colored polyolefin-based resin protective layer film molded and processed by a calendar method. A method of thermocompression bonding on the flame-retardant polyolefin-based resin composition layer is efficient and economical and is desirable.

For forming the colored polyolefin resin protective layer, an aqueous composition obtained by dispersing and blending the phosphorus compound, the chemical foaming agent, and the inorganic pigment and / or the organic pigment into a polyolefin resin emulsion. A method of coating and drying the product on the resin composition layer may be used. As a method for forming a colored polyolefin-based resin protective layer using the polyolefin-based resin emulsion, a coating application of the emulsion composition for forming the colored polyolefin-based resin protective layer directly on the flame-retardant polyolefin-based resin composition layer is performed. -A method of forming by drying may be used. Alternatively, the emulsion for forming the colored polyolefin-based resin protective layer may be coated and dried on a release paper or a release film, and this may be laminated on the flame-retardant polyolefin-based resin composition layer. Examples of the polyolefin resin emulsion include ethylene-vinyl acetate copolymer resin, vinyl acetate-ethylene copolymer resin, ethylene-acrylic acid copolymer resin,
Ethylene-acrylic acid copolymerized ionomer resin, ethylene-propylene copolymerized resin and the like can be used. Further, for forming the colored polyolefin-based resin protective layer, a solution obtained by dissolving the polyolefin-based resin in an organic solvent may be used to form the phosphorus-based compound, the chemical foaming agent, the inorganic pigment and / or A method in which an organic pigment is dispersed and compounded, and the obtained composition is coated and dried may be used.

In the method for producing a flame-retardant polyolefin-based resin-coated sheet of the present invention, in the production step of adhering the film for a flame-retardant polyolefin-based resin composition layer to both surfaces of the base fabric, It is preferable to use a heat laminator having a section, a dry laminating section (comprising a chrome-plated steel driving heating roll and a rubber-coated steel pressing roll), and a winding section. In the heat laminator, the temperature of the heat roll on the film passage side of the flame-retardant polyolefin-based resin composition layer is controlled to 70 ° C. or more and 180 ° C. or less by using an auxiliary heating device such as an infrared heater, if necessary, using an electric heater system, oil. Heating is performed by either a medium method or a steam method, and the temperature of the heat roll on the cloth passing side or the heat passing side of the base cloth on which the flame-retardant polyolefin-based resin composition layer is heat-bonded is set to 1
A production method in which the film for the front-side flame-retardant polyolefin-based resin composition layer and the film for the back-side flame-retardant polyolefin-based resin composition layer are heat-adhered continuously in one step, one side at a time, adjusted to 20 ° C. or lower. It is preferable to use The dry heat shrinkage in the warp and weft directions of the flame-retardant polyolefin resin sheet obtained by this production method is 150 ° C., 15 ° C.
It is preferable to be within 5 to 25% in minute heating.
If the dry heat shrinkage is less than 5%, it may not conform to the fireproof test specified in the Fire Service Law, and if the dry heat shrinkage exceeds 25%, the sheets may be joined by high frequency welding. Alternatively, when the bonding is performed by high-temperature hot-air fusion, the bonded portion may contract to cause distortion in the sheet.

[0060]

EXAMPLES Next, the present invention will be described more specifically with reference to the following examples, but the flame-retardant polyolefin resin-coated sheet of the present invention is not limited to the scope of these examples.

In the following Examples and Comparative Examples, the flame retardancy of the flame-retardant polyolefin resin-coated sheet of the present invention was evaluated.
Test methods such as oxygen index (LOI) evaluation, abrasion resistance evaluation, shear strength retention rate of high frequency welder joint pieces, and heat creep resistance are as follows. (I) Flameproofness of sheet Article 4 of the Fire Service Act (JIS standard L-1091: A-
(2 method section 3: heating for 2 minutes) and evaluated according to the following criteria. ：: Carbonized area 40 cm ² or less, residual flame time 5 seconds or less, residual dust time 20 seconds or less, carbonized distance 20 cm or less. X: One or more of the items of carbonization area, afterflame time, residual dust time, and carbonization distance exceeded the standard values.

(II) Flame Retardancy of Films and Sheets Evaluated according to the limiting oxygen index defined in JIS K-7231. (III) Abrasion resistance of sheet The loss of abrasion was determined by JIS L-1096: abrasion strength test C method (Taber type method: abrasion wheel CS-18: load 1 kg) and evaluated according to the following criteria. ：: Weight loss of 30 mg or less △: Weight loss of 31 to 99 mg ×: Weight loss of 100 mg or more

(IV) Shear strength retention of high-frequency welder joint pieces Two sheets are aligned with their front sides facing each other, the ends of each sheet are overlapped with a width of 3 cm, and a 3 cm × 30 cm weld bar ( Tooth profile: 9 linear projections with 3 cm width at regular intervals / 25.4 mm, convex height 0.5 mm: 9 linear projections with 3 cm width at regular intervals / 25.4 mm, concave depth 0. (5 mm) with a high-frequency welder (YF-7000 manufactured by Yamamoto Vinita Co., Ltd .: output 7 KW). A test piece having a test piece width of 3 cm and a test piece length of 30 cm, including the bonding portion, was collected from the obtained bonding sheet and used as a sample for measuring the shear strength. (Measurement of shear strength is based on JIS L-109
6: According to the tensile strength A method. ) Welder fusion conditions : fusion time 4 to 10 seconds, cooling time 4
Anode current 0.4 ~ 2.0A, weld bar temperature 40 ~ 6
The 0 ° C. shear strength retention was determined assuming that the shear strength value of a high-frequency welder-bonded test piece obtained from a composition containing no flame retardant in the polyolefin resin was 100%. Shear strength retention (%) = (Shear strength value of bonded sheet obtained from composition containing flame retardant) × (Shear strength value of bonded sheet obtained from composition not containing flame retardant) × 100

(V) Heat Creep Resistance of High-Frequency Welder Fusion Bonded Joint The same sample as the shear strength measurement sample used for the shear strength retention (IV) of the high-frequency welder joint piece was prepared and used as a test piece. Heat creep resistance test : A test piece having a test piece width of 3 cm and a test piece length of 30 cm including a joint portion was sampled from the above welded joint sheet and used as a heat-resistant creep test piece. A creep tester (Toyo Seiki Seisaku-sho, Ltd .: (100 LDR type) was used to evaluate a heat creep resistance test at 50 ° C. × 25 kgf load × 24 hours. ：: After 24 hours, there was no breakage of the joint, and the load of 25 kgf was endured. ×: The bonded portion was peeled and broken within 24 hours.

(VI) Dry heat shrinkage ratio: 40 cm in warp and 40 cm in weft from base cloth or test sheet
The test specimens were sampled, and in accordance with JIS A-6008, three marks of 30 cm in the meridian direction and three marks in the 30 cm latitudinal direction were marked at intervals of 10 cm, respectively, and allowed to stand in a gear oven at 150 ° C. for 15 minutes. After the placement, the test piece was returned to room temperature, and the lengths of the reference lines in the warp direction and the weft direction were measured to determine the shrinkage of the fabric or sheet. Dry heat shrinkage = (30 cm−measured value of standard line length cm) / (30 c
m) x 100 (%)

Example 1 100 parts by weight of ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635: Tosoh Corporation: vinyl acetate content 25 wt%, melt flow rate 2.4 g / 10 min), and red phosphorus particles (100 parts by weight) 1) (trademark: Novaled 280C)
(Titanium oxide surface-treated product): 15
Parts by weight, and as an additive, a lubricant (trademark: LTP
-2: Kawaken Fine Chemical Co., Ltd.) 1.0 part by weight,
0.3 parts by weight of an ultraviolet absorber (trademark: Tinuvin P: Ciba Specialty Chemicals Co., Ltd.) and titanium oxide as a coloring agent (trademark: Hikkonmaster HCM2060 White: titanium oxide content 65% by weight: Dainichi Seika Kogyo Co., Ltd.) (5% by weight) and 5 parts by weight of cyanine green (trademark: High Conc Master HCM1560 Green: 20% by weight of cyanine green: Dainichi Seika Kogyo Co., Ltd.) .
25 parts by weight), and the mixture was kneaded with a two-roll mixer set at 130 ° C. for 5 minutes, and a 0.2 mm-thick flame-retardant polyolefin-based resin composition film was calender-rolled from the kneaded composition. Molded. Roll kneading property of this kneading composition and calender moldability are good,
A light green colored film with good appearance was obtained. The oxygen index (LOI) of this film is 34.3
Met.

340 denier polypropylene (PP)
Plain weave fabric obtained by weaving multifilament yarns (Product number: MS-3112: Mitsubishi Rayon Co., Ltd .: yarn density warp: 25 / 2.54 cm, weft: 26 / 2.54 cm)
Was heat-set with a heat-setting machine set to a hot-air condition of 140 ° C. The dry heat shrinkage of this plain weave fabric at 150 ° C. for 15 minutes was 18.7% in the warp direction and 1 in the weft direction.
It was 4.6%. Next, the polyolefin-based resin composition film is bonded to both sides of the plain weave fabric by thermocompression bonding using a laminator, and the flame-retardant polyolefin-based resin of the present invention having a thickness of 0.5 mm and a weight of 450 g / m ^2. A coated sheet was prepared. Under the setting conditions of the laminator at this time, the hot roll temperature on the passing side of the film for the polyolefin resin composition layer was 120 ° C., the hot roll temperature on the passing side of the fiber cloth was 80 ° C., and the pressing pressure was 10 kg / cm.
² , and the bonding speed was 10 m / min. 150 of the obtained flame-retardant polyolefin resin-coated sheet
The dry heat shrinkage at 15 ° C. for 15 minutes was 16.5% in the warp direction and 12.4% in the weft direction, and the LOI was 30.4. Blending of a polyolefin resin composition layer film,
Tables 1 and 2 show the performance of the base cloth and the results of the tests (I) to (VI).

Example 2 A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 1. However, an ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635: Tosoh Corporation) 1 blended in the polyolefin resin composition layer film 1
Instead of 00 parts by weight, 100 parts by weight of an ethylene-acrylic acid copolymer resin (trade name: ACLIFT WH-206: Sumitomo Chemical Co., Ltd .: methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 min) is used. Was. As the coloring agent, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used, but cyanine green (trademark: High Conc Master HCM1560 Green: Dainichi Seika Industry) 5 parts by weight of condensed azo red (trade name: Hikkonmaster HCM1170 Red: 20% by weight of condensed azo red: Dainichi Seika Kogyo Co., Ltd.) was used instead of 5 parts by weight. The addition amount of only the pigment component was 4.25 parts by weight. According to the same procedure as in Example 1, the same film as in Example 1 was laminated and stuck on both sides of the same heat-set treated polypropylene multifilament plain weave fabric, and the thickness was changed to pink to a thickness of 0.5.
A flame-retardant polyolefin-based resin-coated sheet of the present invention having a thickness of 450 g / m ² and a weight of 450 mm was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 16.6% in the warp direction and 12.7% in the weft direction, and the LOI was 28.5. Tables 1 and 2 show the blending of the polyolefin resin composition layer film, the performance of the base fabric, and the results of the above tests (I) to (VI).

Example 3 In the same manner as in Example 1, a flame-retardant polyolefin resin-coated sheet was produced. However, 50 parts by weight of 100 parts by weight of the ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635: Tosoh Corporation) blended in the polyolefin resin composition layer film was a low-density polyethylene resin (trade name). : Kernel KF281: Nippon Polychem Co., Ltd .: Melt flow rate 2.5g / 10min) 5
Replaced with 0 parts by weight. As the coloring agent, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as it was, but cyanine green (trade name: High Conc Master HC)
M1560 Green: Cyanine Blue (trademark: High Conc Master H) instead of 5 parts by weight of Dainichi Seika Kogyo Co., Ltd.
CM1617 Blue: Cyanine blue content 20% by weight: 5 parts by weight of Dainichi Seika Kogyo Co., Ltd. was used. The addition amount of only the pigment component was 4.25 parts by weight. Using the same procedure as in Example 1, and using the same heat-set treated polypropylene multifilament plain weave open fabric used in Example 1, light blue colored 0.5 mm thick, 450 g weight / M ² of the flame-retardant polyolefin-based resin-coated sheet of the present invention. 150 ° C. of the obtained flame-retardant polyolefin resin sheet
The dry heat shrinkage per minute was 16.9% in the warp direction and 12.8% in the weft direction, and the LOI was 28.7. Table 1 shows the composition of the film for the polyolefin resin composition layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).
And 2.

Example 4 A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 3. However, the polypropylene multifilament plain weave fabric (with heat setting treatment)
Instead of 750 denier polyester (PET) multifilament yarn, a plain weave open fabric (part number: T-75475: Teijin Limited: 19 yarn warp yarns /
(2.54 cm, 20 wefts / 2.54 cm), which was used without heat setting. A flame-retardant polyolefin-based resin-coated sheet of the present invention having the same composition and the same coloring as in Example 3, having a thickness of 0.6 mm and a weight of 490 g / m ² was obtained. However, the dry heat shrinkage of the obtained flame-retardant polyolefin resin-coated sheet at 150 ° C. for 15 minutes was 9.4% in the warp direction and 8.2% in the weft direction, and the LOI was 2
8.7. Mixing of the film for the polyolefin-based resin composition layer, the performance of the fabric for the base fabric, and the above tests (I) to
Tables 1 and 2 show the results of (VI).

Example 5 A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 3. However, in place of the polypropylene multifilament plain weave fabric (with heat setting treatment), a plain weave fabric woven from 420 denier polyamide (nylon) multifilament yarn (product number: AKN-4425: Asahi Kasei Corporation: Yarn density warp 24
Book / 2.54 cm, 24 wefts / 2.54 cm), and used without heat setting. The same composition and the same coloration as in Example 3, thickness 0.53 mm, weight 465 g /
m ² of the flame-retardant polyolefin-based resin-coated sheet of the present invention was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin-coated sheet at 150 ° C. for 15 minutes was 7.4% in the warp direction and 7.1% in the weft direction, and the LOI was 28.
It was 7. Formulation of the film for the polyolefin-based resin composition layer, the performance of the fabric for the base fabric, and the tests (I) to (V)
The results of I) are shown in Tables 1 and 2.

Example 6 A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 1. However, an ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635: Tosoh Corporation) blended in the polyolefin resin composition layer film
Instead of 100 parts by weight, 50 parts by weight of ethylene-acrylic acid copolymer resin (trade name: Acryft WH-206: 20% by weight of methyl methacrylate, Sumitomo Chemical Co., Ltd., melt flow rate 2.0 g / 10 min), and Density polyethylene resin (trademark: Kernel KF281: Nippon Polychem Co., Ltd.): Melt flow rate 2.5 g / 10 min
) And 50 parts by weight of red phosphorus particles (1) (trade name: Nova Red 280C (titanium oxide surface-treated product)):
15 parts by weight of red phosphorus particles (2) (trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) was used instead of 15 parts by weight of Rin Kagaku Kogyo Co., Ltd. As the colorant, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) is used as it is, and cyanine green (trademark: High Conc Master HCM1560 Green: Dainichi Seika Industry Co., Ltd.) )) Instead of 5 parts by weight, 2 parts by weight of carbon black (trademark: High Conc Master HCM1717 Black: carbon black content: 10% by weight: Dainichi Seika Kogyo Co., Ltd.) was used. The addition amount of only the pigment component was 3.45 parts by weight. By the same procedure as in Example 1, using the same heat-set treated polypropylene multifilament plain weave open fabric as used in Example 1, gray colored 0.5 mm thick, weight 450 g / M ² of the flame-retardant polyolefin-based resin sheet of the present invention. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 1
6.7%, 12.5% in the latitude direction, and LOI is 2
8.5. Mixing of the film for the polyolefin-based resin composition layer, the performance of the fabric for the base fabric, and the above tests (I) to
Table 1 and Table 2 show the results of (VI).

Example 7 A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 6. However, in place of the polypropylene multifilament plain weave fabric (with heat setting treatment), a plain weave fabric made from 750 denier polyester (PET) multifilament yarn (product number: T-75475: Teijin Limited: Yarn density warp 19 /
(2.54 cm, 20 wefts / 2.54 cm) were used without heat setting. A flame-retardant polyolefin-based resin-coated sheet of the present invention having a thickness of 0.6 mm and a weight of 490 g / m ² having the same composition and the same coloring as in Example 6 was obtained. 150 of the obtained flame-retardant polyolefin resin-coated sheet
The dry heat shrinkage in 15 ° C. for 15 minutes is 9.8% in the longitudinal direction,
It was 8.4% in the latitudinal direction, and the LOI was 28.5. Blending of a polyolefin resin composition layer film,
Tables 1 and 2 show the performance of the base fabric and the results of the tests (I) to (VI).

Example 8 A flame-retardant polyolefin resin-coated sheet was produced in the same manner as in Example 6. However, in place of the polypropylene multifilament plain weave fabric (with heat setting treatment), a plain weave fabric woven from 420 denier polyamide (nylon) multifilament yarn (product number: AKN-4425: Asahi Kasei Corporation: Yarn density warp 24
Book / 2.54 cm, 24 wefts / 2.54 cm) were used without heat setting. A flame-retardant polyolefin resin-coated sheet of the present invention having a thickness of 0.53 mm and a weight of 465 g / m ² having the same composition and the same color as in Example 6 was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin-based resin-coated sheet at 150 ° C. for 15 minutes is 7.
7% and 7.3% in the latitude direction, and the LOI was 28.5. Tables 1 and 2 show the blending of the polyolefin resin composition layer film, the performance of the base fabric, and the results of the tests (I) to (VI).

[0075]

[Table 1]

[0076]

[Table 2]

Evaluation of Performance of Examples 1 to 8 The flame-retardant test of the flame-retardant polyolefin resin-coated sheet of the present invention obtained in Examples 1 to 8 based on the firefighting method (J
In the IS standard L-1091), any of the test pieces of Examples 1 to 8 was separated from the fire source due to the melting and thermal contraction of the sheet after the flame contact, and quickly prevented the spread of fire, and at the same time the flame contact portion was formed. The ignited flame self-extinguished due to the excellent flame retardant effect of the red phosphorus particles blended with the polyolefin resin, and as a result, all the sheets of Examples 1 to 8 passed the fire prevention regulations of the Fire Service Law. In addition, since these flame-retardant polyolefin-based resin-coated sheets can obtain sufficient flame retardancy by adding a small amount of a flame retardant, the strength of the polyolefin-based resin is not significantly impaired. Therefore, the flame-retardant polyolefin-based resin-coated sheet of the present invention was extremely excellent in durability such as abrasion resistance, shear strength at a joint and heat creep resistance.

Example 9 100 parts by weight of an ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635: Tosoh Corporation: vinyl acetate content 25 wt%, melt flow rate 2.4 g / 10 min), and red phosphorus particles (100 parts by weight) 1) (trademark: Novaled 280C:
15 parts by weight of Rin Kagaku Kogyo Co., Ltd. and 1.0 part by weight of a lubricant (trademark: LTP-2: Kawaken Fine Chemical Co., Ltd.) and an ultraviolet absorber (trademark: Tinuvin P: Ciba Specialty Chemicals Co., Ltd.)
0.3 parts by weight of titanium oxide (trade name: High Conc Master HCM2060 White: titanium oxide content: 65% by weight: Dainichi Seika Kogyo Co., Ltd.) 5 parts by weight Addition of 3.
25 parts by weight), and the mixture was kneaded with a two-roll mixer set at 130 ° C. for 5 minutes, and a 0.2 mm-thick polyolefin resin composition layer film was calendered from the kneaded composition by calender rolling. Molded. The roll kneadability and calender moldability of the kneaded composition were good, and a film having a good appearance with a light reddish maroon was obtained. The oxygen index (LOI) of this film was 35.
It was 6.

Next, a plain weave fabric (product number: 340 denier polypropylene multifilament yarn) was woven.
MS-3112: Mitsubishi Rayon Co., Ltd .: Yarn density warp 25
Book / 2.54 cm, 26 wefts / 2.54 cm) into 140
Heat setting was performed using a heat setting machine set to hot air conditions of ° C. The dry heat shrinkage of this plain weave fabric at 150 ° C. for 15 minutes is 18.7% in the warp direction and 14.6% in the weft direction.
Met. Next, the polyolefin-based resin composition layer film was bonded to both sides of the plain weave fabric by thermocompression bonding using a laminator to a thickness of 0.5 mm and a weight of 45.
A flame-retardant polyolefin-based resin-coated sheet of 0 g / m ² was obtained. Under the setting conditions of the laminator at this time, the hot roll temperature on the passing side of the film for the polyolefin resin composition layer is 120 ° C., the hot roll temperature on the passing side of the fiber fabric is 80 ° C., and the pressing pressure is 10 kg / cm ^2. And the bonding speed was 10 m / min.

Next, an ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635: Tosoh Corporation): vinyl acetate content 25 wt%, melt flow rate 2.4 g / 10 mi
n) 100 parts by weight of ammonium polyphosphate (trademark: Hostaflam AP-745 (EXOLIT IFR)
23): Clariant Japan K.K .: Melamine resin surface coating type, polymerization degree n = 1000) 30 parts by weight,
Chemical foaming agent (trademark: Uniform AZ L-10: Otsuka Chemical Co., Ltd.): decomposition temperature 199 ° C, gas generation amount 240ml /
g) of 5 parts by weight, and as an additive, a lubricant (trade name: LTP-2: Kawaken Fine Chemical Co., Ltd.)
1.0 part by weight, 0.3 part by weight of an ultraviolet absorber (trade name: Tinuvin P: Ciba Specialty Chemicals Co., Ltd.)
Titanium oxide as a colorant (trademark: High Conc Master H)
CM2060 white: titanium oxide content 65% by weight:
Dainichi Seika Industry Co., Ltd.) and Cyanine Green (trademark:
High Conc Master HCM1560 Green: 20% by weight of cyanine green: 5 parts by weight of each of Dainichi Seika Kogyo Co., Ltd., and the resulting compound (4.25 parts by weight as the addition of only the pigment component) (5% by weight) (3.2% as a pigment component only addition)
(5 parts by weight) was kneaded with a two-roll mixer set at 130 ° C. for 5 minutes, and a 0.12 mm-thick film for a colored polyolefin-based resin protective layer was calendered from the kneaded composition. The roll kneadability and calender moldability of the kneaded composition were good, and a light green colored film having a good appearance was obtained. The oxygen index (LOI) of this film was 31.4.

Next, this colored polyolefin-based resin protective layer film was bonded to one surface of the previously prepared flame-retardant polyolefin-based resin-coated sheet by thermocompression bonding using a laminator to obtain a thickness of 0.62 mm and a weight of 560 g. / M ² ,
A flame-retardant polyolefin resin sheet with a colored protective layer was obtained. Under the setting conditions of the laminator at this time, the hot roll temperature on the side passing the film for the colored polyolefin resin protective layer is 120 ° C., the hot roll temperature on the side passing the flame-retardant polyolefin resin sheet is 80 ° C., and the pressing pressure is 10
kg / cm ² and the bonding speed was 10 m / min. 150 ° C. of the flame-retardant polyolefin resin sheet having the obtained colored polyolefin resin protective layer on one side
The dry heat shrinkage in 15 minutes was 15.5% in the warp direction and 12.2% in the weft direction, and the LOI of the sheet was 29.4.
Met. Tables 3 to 5 show the composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Example 10 In the same manner as in Example 9, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, an ethylene-vinyl acetate copolymer resin (trade name: Ultracene 63) blended in the polyolefin resin composition layer film.
5: Tosoh Corporation) Instead of 100 parts by weight, ethylene-
Acrylic acid copolymer resin (trademark: ACLIFT WH-20)
6: Sumitomo Chemical Co., Ltd .: Methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 min) 1
00 parts by weight were used. Further, using the same heat-set treated polypropylene multifilament plain weave fabric used in Example 9, a flame-retardant polyolefin-based material having a thickness of 0.5 mm and a weight of 450 g / m ² , which was colored in light red maroon. A resin sheet was obtained. Next, the same protective layer film as used in Example 9 was used as the colored polyolefin-based resin layer film. However, as the coloring agent, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as it was, but the cyanine green (trademark: High Conc Master HCM1560 Green: Dainichi Seika Kogyo) 5 parts by weight of condensed azo red (trademark: Hikkonmaster HCM1170 Red: 20% by weight of condensed azo red: Dainichi Seika Kogyo Co., Ltd.) was used instead of 5 parts by weight. Is 4.25 parts by weight). A 0.66 mm thick, 560 g weight having a polyolefin resin protective layer colored on one side in pink by the same procedure as in Example 9.
/ M ² flame-retardant polyolefin resin coated sheet was obtained.
150 of the obtained flame-retardant polyolefin resin sheet
The dry heat shrinkage at 15.degree. C. for 15 minutes was 15.3% in the warp direction and 12.4% in the weft direction, and the LOI was 28.3.
Table 3 shows the composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).
To Table 5 below.

Example 11 A flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced in the same manner as in Example 9. However, an ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635: blended in the polyolefin resin composition layer film):
50 parts by weight of 100 parts by weight of Tosoh Corporation are low-density polyethylene resins (trademark: Kernel KF281:
Nippon Polychem Co., Ltd .: Melt flow rate 2.5g / 1
0 min). Further, the same polyolefin-based resin composition layers as those used in Example 9 were formed on both sides of a heat-set treated polypropylene multi-filament plain weave fabric, and the thickness of the polyolefin resin composition was reduced to 0.1 mm. A flame-retardant polyolefin resin sheet having a thickness of 5 mm and a weight of 450 g / m ² was obtained. Next, the same protective layer film as that used in Example 9 was used as the colored polyolefin-based resin layer film. However, as the coloring agent, titanium oxide (trademark: High Conc Master HCM20)
60 White: 5 parts by weight of Dainichi Seika Kogyo Co., Ltd. was used as it was, but cyanine green (trademark: High Conc Master HCM1560 Green: Dainichi Seika Kogyo Co., Ltd.) 5
Instead of parts by weight, cyanine blue (trademark: High Conc Master HCM1617 Blue: cyanine blue content 2)
0% by weight: 5 parts by weight of Dainichi Seika Kogyo Co., Ltd. was used.
(4.25 parts by weight as addition of pigment component only). A polyolefin resin protective layer colored in light blue on one side by the same procedure as in Example 9 and having a thickness of 0.62
A flame-retardant polyolefin resin sheet having a protective layer having a thickness of 560 g / m ^{2 and} a thickness of 560 mm was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 15.1% in the warp direction and 12.6% in the weft direction, and the LOI was 28.5. Tables 3 to 5 show the composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Example 12 In the same manner as in Example 11, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, in place of the polypropylene multifilament plain weave fabric (with heat setting treatment), a plain weave fabric made from 750 denier polyester (PET) multifilament yarn (product number: T-75475: Teijin Limited: Yarn density warp 19 / 2.54cm, weft 20 / 2.54c
m) was used without heat-setting. Example 11
According to the same procedure as that described above, a 0.72 m thick light-blue colored polyolefin-based resin protective layer is provided on one side.
m, a flame-retardant polyolefin resin-coated sheet with a protective layer having a weight of 600 g / m ² was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 9.4% in the warp direction and 8.2% in the weft direction, and the LOI was 28.4. Tables 3 to 5 show the composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Example 13 In the same manner as in Example 11, a flame-retardant polyolefin resin-coated sheet with a colored protective layer was produced. However, ethylene-polyethylene resin composition layer film
Of 100 parts by weight of a vinyl acetate copolymer resin (trade name: Ultracene 635: Tosoh Corporation), 70 parts by weight thereof were ethylene-acrylic acid copolymer resin (trade name: Acryft WH)
-206: Sumitomo Chemical Co., Ltd .: Methyl methacrylate content 20 wt%, melt flow rate 2.0 g / 10 mi
n). Furthermore, the polypropylene multifilament plain weave fabric (with heat setting treatment)
Instead of plain denim open cloth woven from 420 denier polyamide (nylon) multifilament yarn (product number: AKN-4425: Asahi Kasei Corp .: yarn density warp 24 / 2.54 cm, weft 24/2. 54 cm) was used without heat setting. According to the same procedure as that of Example 11, a polyolefin resin protective layer colored in light blue is provided on one surface, the thickness is 0.65 mm, and the weight is 57.
A flame-retardant polyolefin resin-coated sheet with a protective layer of 5 g / m ² was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 7.6% in the warp direction and 7.2% in the weft direction, and the LOI was 2
8.6. Formulation of the film for the polyolefin-based resin composition layer, formulation of the film for the colored polyolefin-based resin protective layer, performance of the fabric for the base fabric, and the above tests (I) to
Tables 3 to 5 show the results of (VI).

Example 14 In the same manner as in Example 9, a flame-retardant polyolefin resin-coated sheet provided with a colored protective layer was produced. However, an ethylene-vinyl acetate copolymer resin (trade name: Ultracene 635:
Instead of 100 parts by weight of Tosoh Corporation, an ethylene-acrylic acid copolymer resin (trade name: Acryft WH-206: Sumitomo Chemical Co., Ltd. methyl methacrylate content: 20 wt.
%, Melt flow rate 2.0 g / 10 min) and 50 parts by weight of a low-density polyethylene resin (trade name: Kernel KF2)
81: Nippon Polychem Co., Ltd .: Melt flow rate 2.5
g / 10 min) and 50 parts by weight of red phosphorus particles (1) (trade name: Nova Red 280C (Titanium oxide surface-treated product: Rin Kagaku Kogyo Co., Ltd.)). 2) (Trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) 15 parts by weight was used. A maroon-colored thickness of 0.5 using the same heat-set polypropylene multifilament plain weave fabric used in Example 9.
Thus, a flame-retardant polyolefin resin sheet having a thickness of 450 g / m ² and a weight of 450 mm was obtained. Next, the same protective layer film as that used in Example 13 was laminated on both surfaces of the flame-retardant polyolefin-based resin-coated sheet as a colored polyolefin-based resin layer film. However, 5 parts by weight of titanium oxide (trademark: High Conc Master HCM2060 White: Dainichi Seika Kogyo Co., Ltd.) was used as a coloring agent, but cyanine green (trade name: High Conc Master HC)
M1560 Green: The use of 5 parts by weight of Dainichi Seika Kogyo Co., Ltd. was omitted. (The addition of only the pigment component is 3.2
5 parts by weight). According to the same procedure as that of Example 9, a flame-retardant polyolefin-based resin sheet having a protective layer and having a thickness of 0.74 mm and a weight of 670 g / m ² having a polyolefin-based resin protective layer colored white on both sides was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 15.3% in the warp direction and 12.7% in the weft direction, and the LOI was 28.3. Tables 3 to 5 show the composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Example 15 In the same manner as in Example 14, a polyolefin resin-coated sheet provided with a colored protective layer was prepared. However, instead of the polypropylene multifilament plain weave fabric (with heat setting treatment), 750 denier polyester (P
ET) Plain weave open fabric woven from multifilament yarn (product number: T-75475: Teijin Limited: yarn density 19 warps / 2.54 cm, weft 20 yarns / 2.54 cm) without heat set treatment did. According to the same procedure as that of Example 14, a flame-retardant polyolefin-based resin sheet having a protective layer having a thickness of 0.84 mm and a weight of 710 g / m ² having a white polyolefin-based resin protective layer on both surfaces was obtained. The dry heat shrinkage of the obtained flame-retardant polyolefin resin sheet at 150 ° C. for 15 minutes was 9.6% in the warp direction and 8.8 in the weft direction.
3% and LOI was 28.8. Tables 3 to 5 show the composition of the film for the polyolefin-based resin composition, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Example 16 In the same manner as in Example 14, a polyolefin resin-coated sheet with a colored protective layer was prepared. However, instead of the polypropylene multifilament plain weave fabric (with heat set treatment), a plain weave fabric (article number: AKN-4425: Asahi Kasei Corporation) woven from 750 denier polyamide (nylon) multifilament yarn is used instead of the polypropylene multifilament plain weave fabric (with heat setting treatment). (Yarn density 24 warps / 2.54 cm, weft 24 threads / 2.54 cm)
Was used without heat set treatment. According to the same procedure as that of Example 14, a flame-retardant polyolefin-based resin composition sheet having a protective layer and having a thickness of 0.77 mm and a weight of 685 g / m ² having a white polyolefin-based resin protective layer on both sides was obtained.
150 of the obtained flame-retardant polyolefin resin sheet
The dry heat shrinkage at 15 ° C. for 15 minutes is 7.8% in the longitudinal direction,
The latitudinal direction was 6.9%, and the LOI was 28.4. Blending of a polyolefin resin composition layer film,
Tables 3 to 5 show the blending of the film for the colored polyolefin resin protective layer, the performance of the fabric for the base cloth, and the results of the tests (I) to (VI).

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

[Table 5]

Performance Evaluation of Examples 9 to 16 Flameproofing test based on the firefighting method of the flame-retardant polyolefin resin sheet with a colored protective layer of the present invention obtained in Examples 9 to 16 (JIS standard L -1091) indicates that the test piece of any of the examples melts after the flame contact, and the sheet melts and shrinks by heat, thereby moving away from the fire source to quickly prevent the spread of fire, and at the same time, the flame igniting the flame contact portion is a polyolefin resin. Self-extinguishing due to the excellent flame-retardant effect of the red phosphorus particles blended in Example 1. As a result, all of the sheets in the Examples passed the fireproof regulations of the Fire Service Law. Further, these flame-retardant sheets can obtain sufficient flame retardancy by adding a small amount of a flame retardant, so that the strength of the polyolefin resin is not significantly impaired. Therefore, the flame-retardant polyolefin-based resin sheet of the present invention was extremely excellent in durability such as abrasion resistance, shear strength at a joint and heat creep resistance. Further, the flame-retardant polyolefin-based resin sheet of the present invention, by providing a colored polyolefin-based resin protective layer containing a non-halogen-based flame retardant on the surface of the sheet,
Coloring flexibility was obtained.

Comparative Example 1 A polyolefin resin-coated sheet was produced in the same manner as in Example 9. However, red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product)) blended in the polyolefin resin composition layer film:
Instead of using 15 parts by weight of Rin Kagaku Kogyo Co., Ltd., 150 parts by weight of magnesium hydroxide (trade name: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) is blended, and a colored polyolefin-based protective layer film is used. From the composition components, 30 parts by weight of ammonium polyphosphate and 5 parts by weight of a chemical blowing agent were omitted.
A polyolefin resin-coated sheet having a colored protective layer having a thickness of 0.62 mm and a weight of 590 g / m ² was obtained by the same composition and coloring as in Example 9, and by the same procedure. The dry heat shrinkage of the obtained polyolefin resin-coated sheet at 150 ° C. for 15 minutes was 15.1% in the warp direction and 11.8% in the weft direction.
And the LOI was 20.2. Tables 6 to 8 show the composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Comparative Example 2 In the same manner as in Example 10, a polyolefin resin-coated sheet was prepared. However, red phosphorus particles (1) (trademark: Nova Red 280C (titanium oxide surface-treated product)) blended in the polyolefin resin composition layer film:
15 parts by weight of Rin Kagaku Kogyo Co., Ltd. were omitted, and instead, 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended. A polyolefin resin-coated sheet with a colored protective layer having a thickness of 0.62 mm and a weight of 590 g / m ² was obtained by the same blending and coloring as in Example 10, and by the same procedure. The dry heat shrinkage of the obtained polyolefin resin sheet at 150 ° C. for 15 minutes was 15.7% in the warp direction and 12.0% in the weft direction, and the LOI was 26.3. Formulation of the film for the polyolefin-based resin composition layer, formulation of the film for the colored polyolefin-based resin protective layer, performance of the fabric for the base fabric, and the above tests (I) to
Table 6 to Table 8 show the results of (VI).

Comparative Example 3 In the same manner as in Example 3, a polyolefin resin-coated sheet was prepared. However, 15 parts by weight of red phosphorus particles (1) (trade name: Nova Red 280C (titanium oxide surface-treated product): Rin Kagaku Kogyo Co., Ltd.) blended in the polyolefin resin composition layer film are omitted, and instead. Magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.)
150 parts by weight were blended. According to the same composition and coloring and the same procedure as in Example 3, the thickness was 0.5 mm, and the weight was 480 g /.
As a result, a polyolefin resin sheet having no protective layer of m ² was obtained. 150 of the obtained polyolefin-based resin-coated sheet
The dry heat shrinkage at 15 ° C. for 15 minutes was 15.4 in the longitudinal direction.
%, The latitude direction was 12.3%, and the LOI was 24.2. Tables 6 to 8 show the blending of the polyolefin resin composition layer film, the performance of the base fabric, and the results of the tests (I) to (VI).

Comparative Example 4 A polyolefin resin-coated sheet similar to that of Example 4 (without a protective layer) was prepared. However, the red phosphorus particles (1) blended in the polyolefin resin composition layer film
(Trademark: Novaled 280C (Titanium oxide surface treated product): Rin Kagaku Kogyo Co., Ltd.) 15 parts by weight was omitted, and instead, magnesium hydroxide (Trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) 150 parts by weight was omitted. Was blended. According to the same composition and coloring as in Example 4, and a similar procedure, a thickness of 0.6 mm was obtained.
A polyolefin resin sheet having a weight of 520 g / m ² was obtained. 150 ° C. of the obtained polyolefin resin sheet,
The dry heat shrinkage in 15 minutes was 9.6% in the warp direction and 9.3% in the weft direction, and the LOI was 24.2. Table 6 shows the composition of the film for the polyolefin resin composition layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).
To Table 8 below.

Comparative Example 5 The same polyolefin resin-coated sheet as in Example 5 (without a protective layer) was prepared. However, 15 parts by weight of red phosphorus particles (1) (trade name: Nova Red 280C (titanium oxide surface-treated product): Rin Kagaku Kogyo Co., Ltd.) blended in the polyolefin resin composition layer film were omitted. Instead, 150 parts by weight of magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was blended. The same composition and coloring as in Example 5 and a thickness of 0.53
A polyolefin-based resin-coated sheet having a thickness of 505 g / m ^{2 and} a thickness of 505 mm was obtained. The dry heat shrinkage of the obtained polyolefin resin-coated sheet at 150 ° C. for 15 minutes is 7.6% in the warp direction and 7.3% in the weft direction, and the LOI is 24.
It was 2. Formulation of the film for the polyolefin-based resin composition layer, the performance of the fabric for the base fabric, and the tests (I) to (V)
Tables 6 to 8 show the results of I).

Comparative Example 6 In the same manner as in Example 14, a polyolefin resin-coated sheet with a colored protective layer was prepared. However, 15 parts by weight of red phosphorus particles (2) (trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film were omitted,
Instead, magnesium hydroxide (trademark: Kisuma 5A:
150 parts by weight of Kyowa Chemical Industry Co., Ltd. were blended. Also,
30 parts by weight of ammonium polyphosphate and 5 parts by weight of a chemical foaming agent, which were blended in the colored polyolefin resin protective layer film, were omitted, and instead of these, magnesium hydroxide (trademark: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) ) 10
0 parts by weight were blended. 0.74 mm in thickness and 730 g in weight by the same formulation and coloring as in Example 14, and the same procedure.
/ M ² of the polyolefin resin-coated sheet. 150 ° C., 15 ° C. of the obtained polyolefin resin-coated sheet
The dry heat shrinkage in 1 minute was 14.4% in the warp direction and 11.7% in the weft direction, and the LOI was 22.3. The composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base cloth, and the results of the above tests (I) to (VI) are shown in Tables 6 to 6.
It is shown in Table 8.

Comparative Example 7 In the same manner as in Example 15, a polyolefin resin-coated sheet with a colored protective layer was prepared. However, 15 parts by weight of red phosphorus particles (2) (trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film were omitted, and Instead of magnesium hydroxide (trademark: Kisuma 5)
A: 150 parts by weight of Kyowa Chemical Industry Co., Ltd. was blended. Further, 30 parts by weight of ammonium polyphosphate and 5 parts by weight of a chemical foaming agent which are blended in the colored polyolefin resin protective layer film were omitted, and instead of these, magnesium hydroxide (trade name: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) ) 150
Parts by weight were blended. The same formulation and coloring as in Example 15,
0.84mm in thickness and 770g / m in weight by the same procedure
^Thus, a polyolefin-based resin sheet ² was obtained. The dry heat shrinkage of the obtained polyolefin resin sheet at 150 ° C. for 15 minutes was 9.7% in the warp direction and 9.2% in the weft direction, and the LOI was 23.8. Formulation of the film for the polyolefin-based resin composition layer, formulation of the film for the colored polyolefin-based resin protective layer, performance of the fabric for the base fabric,
Tables 6 to 8 show the results of the tests (I) to (VI).

Comparative Example 8 In the same manner as in Example 16, a polyolefin resin-coated sheet with a colored protective layer was prepared. However, 15 parts by weight of red phosphorus particles (2) (trademark: Hishigard CP (aluminum hydroxide surface-treated product): Nippon Chemical Industry Co., Ltd.) blended in the polyolefin resin composition layer film were omitted, and Instead of magnesium hydroxide (trademark: Kisuma 5)
A: 150 parts by weight of Kyowa Chemical Industry Co., Ltd. was blended. Also, 30 parts by weight of ammonium polyphosphate compounded in the colored polyolefin resin protective layer film was omitted,
Instead, magnesium hydroxide (trademark: Kisuma 5A:
100 parts by weight of Kyowa Chemical Industry Co., Ltd. were blended. A polyolefin resin-coated sheet having a thickness of 0.77 mm and a weight of 755 g / m ² was obtained by the same blending and coloring and the same procedure as in Example 16. The dry heat shrinkage of the obtained polyolefin resin-coated sheet at 150 ° C. for 15 minutes is
The longitudinal direction was 7.5%, the latitudinal direction was 7.1%, and the LOI was 23.0. Formulation of the film for the polyolefin-based resin composition layer, formulation of the film for the colored polyolefin-based resin protective layer, performance of the fabric for the base fabric, and the above tests (I) to
Table 6 to Table 8 show the results of (VI).

[0101]

[Table 6]

[0102]

[Table 7]

[0103]

[Table 8]

Performance Evaluation of Comparative Examples 1 to 8 In Comparative Examples 1 to 8, fire-fighting was performed by changing a large amount of magnesium hydroxide instead of red phosphorus particles as a flame retardant in a polyolefin resin layer film. In a flameproof test based on the law (JIS standard L-1091),
After the flame contact, the test pieces of all the comparative examples fired at the same time as the sheet was melted, and accelerated fire spread by heat shrinking in the fired state. The ignited flame could not be extinguished by self-extinguishing due to the flame-retardant effect of magnesium hydroxide, and was completely burned. As a result, all the sheets of the comparative examples did not conform to the fire prevention regulations of the Fire Service Law. Further, the sheets of these comparative examples are not only insufficient in flame retardancy even by adding a large amount of flame retardant, but also have extremely poor durability such as abrasion resistance, shear strength of joints and heat creep resistance. It greatly impaired the strength of the polyolefin-based resin, and was not practical. (Abrasion resistance was good only in Comparative Examples 1 and 2)

Comparative Example 9 The same polyolefin resin-coated sheet with a protective layer as in Example 9 was produced. However, the heat setting treatment of a plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd.) in which the 340-denier polypropylene multifilament yarn was woven was omitted. 15 of this plain weave fabric
The dry heat shrinkage at 0 ° C. for 15 minutes was 34.6 in the warp direction.
% And 31.3% in the weft direction. Also, 30 parts by weight of ammonium polyphosphate compounded in the colored polyolefin resin protective layer film was omitted, and instead, 150 parts by weight of magnesium hydroxide (trade name: Kisuma 5A: Kyowa Chemical Industry Co., Ltd.) was compounded. . A polyolefin resin sheet with a colored protective layer having a thickness of 0.65 mm and a weight of 605 g / m ² was obtained by the same blending and coloring and the same procedure as in Example 9. The dry heat shrinkage of the obtained polyolefin resin sheet at 150 ° C. for 15 minutes was 2
8.6%, 26.3% in latitude, and LOI is 2
7.4. However, since the heat setting of the polypropylene plain weave fabric was omitted, the thermal shrinkage of the polypropylene plain weave fabric (base fabric) was large in the heat lamination process of the flame-retardant polyolefin resin film,
Workability and sheet appearance were remarkably poor. Tables 9 to 11 show the composition of the film for the polyolefin-based resin composition layer, the composition of the film for the colored polyolefin-based resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).
Shown in

Comparative Example 10 A polyolefin resin-coated sheet having a protective layer was produced in the same manner as in Example 10. However, the heat setting temperature of the plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd.) in which the 340 denier polypropylene multifilament yarn was woven was changed from 140 ° C to 170 ° C. The dry heat shrinkage of this plain weave fabric at 150 ° C. for 15 minutes was 3.3% in the warp direction and 3.0% in the weft direction. A polyolefin resin sheet with a colored protective layer having a thickness of 0.62 mm and a weight of 560 g / m ² was obtained by the same blending and coloring and the same procedure as in Example 10. The dry heat shrinkage of the obtained polyolefin resin sheet at 150 ° C. for 15 minutes was 3.1% in the warp direction and 2.8% in the weft direction, and the LOI was 28.0. Formulation of the film for the polyolefin-based resin composition layer, formulation of the film for the colored polyolefin-based resin protective layer, performance of the fabric for the base fabric,
Tables 9 to 11 show the results of the tests (I) to (VI).

Comparative Example 11 In the same manner as in Example 3, a polyolefin resin-coated sheet without a protective layer was produced. However, a plain weave fabric woven from the 340-denier polypropylene multifilament yarn (product number: MS-3112: Mitsubishi Rayon Co., Ltd.)
Was changed from 140 ° C. to 170 ° C. The dry heat shrinkage of this plain weave fabric at 150 ° C. for 15 minutes was 3.3% in the warp direction and 3.0% in the weft direction. A polyolefin resin-coated sheet having a thickness of 0.5 mm and a weight of 450 g / m ² was obtained by the same blending and coloring and the same procedure as in Example 3. The dry heat shrinkage of the obtained polyolefin resin sheet at 150 ° C. for 15 minutes was 2.1% in the warp direction and 1.8% in the weft direction.
I was 28.1. Tables 9 to 11 show the composition of the film for the polyolefin resin composition layer, the composition of the film for the colored polyolefin resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Comparative Example 12 In the same manner as in Example 4, a polyolefin resin-coated sheet without a protective layer was produced. However, a plain weave open fabric (product number: T-75475: Teijin Limited) in which the 750 denier polyester multifilament yarn was woven was subjected to heat setting at 200 ° C. The dry heat shrinkage of this plain weave fabric at 150 ° C. for 15 minutes was 2.6% in the warp direction and 2.2% in the weft direction. 0.6 mm thick according to the same composition and coloring and the same procedure as in Example 4,
A polyolefin resin-coated sheet having a weight of 490 g / m ² was obtained. 1 of the obtained polyolefin resin-coated sheet
The dry heat shrinkage at 50 ° C. for 15 minutes is 2.4 in the longitudinal direction.
%, The weft direction 2.0%, and the LOI was 29.3. Tables 9 to 11 show the composition of the film for the polyolefin resin composition layer, the composition of the film for the colored polyolefin resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Comparative Example 13 In the same manner as in Example 5, a polyolefin resin-coated sheet without a protective layer was produced. However, a plain weave open cloth (product number: AKN-4425: Asahi Kasei Corporation) obtained by weaving the above-mentioned 420 denier polyamide (nylon) multifilament yarn was subjected to heat setting at 200 ° C. The dry heat shrinkage of this plain weave fabric at 150 ° C. for 15 minutes was 2.4% in the warp direction and 2.1% in the weft direction. A polyolefin resin-coated sheet having a thickness of 0.53 mm and a weight of 465 g / m ² was obtained by the same blending and coloring and the same procedure as in Example 5. The dry heat shrinkage of the obtained polyolefin-based resin-coated sheet at 150 ° C. for 15 minutes was 2.2% in the warp direction and 1.9% in the weft direction.
OI was 28.7. Tables 9 to 11 show the composition of the film for the polyolefin resin composition layer, the composition of the film for the colored polyolefin resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Comparative Example 14 In the same manner as in Example 14, a polyolefin resin-coated sheet having a double-sided colored protective layer was prepared. However, the heat setting treatment of a plain weave fabric (product number: MS-3112: Mitsubishi Rayon Co., Ltd.) in which the 340-denier polypropylene multifilament yarn was woven was omitted. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes is as follows:
It was 34.6% in the warp direction and 31.3% in the weft direction. A polyolefin resin-coated sheet having a thickness of 0.74 mm and a weight of 670 g / m ² was obtained by the same blending and coloring and the same procedure as in Example 14. The dry heat shrinkage of the obtained polyolefin resin-coated sheet at 150 ° C. for 15 minutes is
28.6% in the longitude direction, 26.3% in the latitude direction, and LO
I was 26.8. However, since the heat setting of the polypropylene plain weave fabric was omitted, the heat shrinkage of the polypropylene plain weave fabric was large in the heat lamination process of the flame-retardant polyolefin resin film, and the workability and sheet appearance were remarkably poor. Was. Tables 9 to 11 show the composition of the film for the polyolefin resin composition layer, the composition of the film for the colored polyolefin resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

Comparative Example 15 A polyolefin resin-coated sheet having a double-sided colored protective layer was prepared in the same manner as in Example 15, except that the above-mentioned 750 was used.
A heat-set treatment was applied to a plain weave open fabric (product number: T-75475: Teijin Limited) in which denier polyester multifilament yarn was woven under a heat condition of 200 ° C. The dry heat shrinkage at 150 ° C. of this plain weave fabric is
It was 2.6% in the warp direction and 2.2% in the weft direction. Example 15
0.8 thickness by the same formulation and coloring, and the same procedure
A polyolefin resin-coated sheet having a thickness of 4 mm and a weight of 710 g / m ² was obtained. The dry heat shrinkage of the obtained polyolefin resin-coated sheet at 150 ° C. for 15 minutes was 2.4% in the warp direction and 1.9% in the weft direction, and the LOI was 28.
It was 7. Formulation of a film for a polyolefin-based resin composition layer, formulation of a film for a colored polyolefin-based resin protective layer, performance of a fabric for a base fabric, and the above tests (I) to (VI)
Tables 9 to 11 show the results.

Comparative Example 16 In the same manner as in Example 16, a polyolefin resin-coated sheet having a double-sided colored protective layer was prepared. However, the 420
Plain weave fabric woven from denier polyamide (nylon) multifilament yarn (product number: AKN-442)
5: Asahi Kasei Co., Ltd.) was subjected to a heat setting treatment at 200 ° C. The dry heat shrinkage of the plain weave fabric at 150 ° C. for 15 minutes is 2.4% in the warp direction and 2.10% in the weft direction.
1%. A polyolefin resin-coated sheet having a thickness of 0.77 mm and a weight of 680 g / m ² was obtained by the same blending and coloring and the same procedure as in Example 16. The dry heat shrinkage of the obtained polyolefin-based resin-coated sheet at 150 ° C. for 15 minutes was 2.2% in the warp direction and 1.9% in the weft direction, and the LOI was 28.1. Tables 9 to 11 show the composition of the film for the polyolefin resin composition layer, the composition of the film for the colored polyolefin resin protective layer, the performance of the fabric for the base fabric, and the results of the above tests (I) to (VI).

[0113]

[Table 9]

[0114]

[Table 10]

[0115]

[Table 11]

Performance Evaluation of Comparative Examples 9 to 16 In the sheets of Comparative Examples 10 to 13, Comparative Examples 15 and 16, the same red phosphorus as in Example was used as the flame retardant of the polyolefin resin composition layer film. Even when particles are used, the thermal contraction rate of the fiber fabric base cloth used is small, so the flamed part is inferior in the behavior of moving away from the fire source after flame contact, and the flame contact end is wound in the shape of a claw toward the fire source. Shrink to form a partially vertical state, and cannot self-extinguish, but burns down. As a result, the sheets of these comparative examples are subjected to the fire protection test (JIS standard L
-1091). Further, although the sheets of Comparative Examples 9 and 14 conform to the fireproof test of the Fire Service Law, the heat shrinkage of the fiber fabric base cloth is too large, making the production of the sheets difficult and at the same time the sheet appearance. It was not practical, for example, the joints shrank violently during fusion welding of the high-frequency welder. Furthermore, in the sheets of Comparative Examples 10 and 11, the heat shrinkage of the fiber fabric base fabric woven from the polypropylene multifilament yarn was extremely reduced by the heat setting treatment, so that the polypropylene multifilament yarn microstructure Joint shear strength, to cause a decrease in crystallinity of
This impaired the strong physical properties of the sheet itself, such as the heat creep resistance of the joint, and was not practical at all.

[0117]

The flame-retardant polyolefin-based resin-coated sheet of the present invention has excellent flame retardancy conforming to the fire protection test of the Fire Service Law, and also has excellent processability and coloring properties. Was. Further, the flame-retardant polyolefin-based resin-coated sheet of the present invention is an extremely durable sheet that has sufficiently solved the problem of a decrease in mechanical properties, which was a conventional problem. Therefore, the flame-retardant polyolefin-based resin-coated sheet of the present invention is used as a substitute for a conventionally used flexible polyvinyl chloride processed sheet, particularly for a tent film material requiring flame resistance, a film material for a sheet warehouse, Curing sheet for construction site,
This sheet is suitable for industrial materials such as sound insulation sheets for construction sites.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/00 C08K 3/00 3/32 3/32 5/00 5/00 5/23 5/23 5 / 32 5/32 5/43 5/43 5/521 5/521 9/00 9/00 C08L 23/00 C08L 23/00 F term (reference) 4F072 AA04 AA05 AA08 AB04 AB05 AB06 AB28 AD04 AE07 AE09 AE23 AF01 AF02 AF11 AF14 AF15 AG22 AK05 AK06 AL17 4F100 AA04B AA04C AA04H AA18B AA18C AA19B AA19C AA21 AA21B AA21C AA25B AA25C AA36B AA36C AA36H AH03B AH03C AH03H AH10B AH10C AH10H AK01A AK03A AK03B AK03C AK07 AK32B AK32C AK33B AK33C AK36B AK36C AK41A AK46A AK53B AK53C AK62A AK62B AK62C AK66A AK66B AK66C AK68 AK70 BA03 BA06 BA10B BA10C BA13 CA01B CA01C CA07 CA08B CA08C CA13B CA13C CA19 DE01B DE01C DG04A DG12A EH012 EH462 EJ192 EJ422 GB07 HB00 JA03 JA06B JA06C JA20B JA20C JB16A JJ07 J00L Y00A YY00B YY00C 4J002 BB031 BB041 BB051 BB061 BB071 BB081 BB121 BB151 DA027 DA037 DA056 DA087 DA097 DE077 DE097 DE107 DE117 DE127 DE137 DE147 DE187 DG027 DG047 DG057 DJ007 DJ0 077 DJ070 007 017

Claims (16)

[Claims] 1. A composite sheet comprising: a base fabric including a fabric woven from thermoplastic resin filament yarns; The polyolefin-based resin composition comprises 100 parts by weight of a polyolefin-based resin, 5 to 35 parts by weight of red phosphorus particles mixed therein, and 0.2 to 5.0 g / 10.
Melt flow rate (MFR) per minute (JIS K67)
According to 60 test methods. However, temperature: 190 ° C, load:
21.18 N (2.16 kgf)), and the composite sheet has a dry heat shrinkage of 5 to 25% in the warp and weft directions by heating at 150 ° C. for 15 minutes. Flame-retardant polyolefin resin-coated sheet. 2. The flame-retardant polyolefin resin-coated sheet according to claim 1, wherein the thermoplastic resin forming the thermoplastic resin filament thread for the base cloth is selected from a polyolefin resin, a polyester resin, and a polyamide resin. . 3. The filament yarn for a base fabric is selected from a multifilament yarn, a monofilament yarn, a tape yarn, a split yarn, and a split yarn.
The flame-retardant polyolefin-based resin-coated sheet according to claim 1. 4. The polyolefin-based resin composition further contains 1 to 20 parts by weight of at least one colorant selected from inorganic pigments and organic pigments based on 100 parts by weight of the polyolefin-based resin. Claim 1
The flame-retardant polyolefin-based resin-coated sheet according to 1. 5. The thermoplastic resin filament yarn,
The flame-retardant polyolefin-based resin-coated sheet according to claim 1, comprising at least one selected from a polyethylene filament yarn, a polypropylene filament yarn, and a mixed filament yarn of a polyethylene resin and a polypropylene resin. 6. The base fabric is a woven fabric, which is heat-set and exhibits a dry heat shrinkage of 5 to 25% in the warp and weft directions by heating at 150 ° C. for 15 minutes. Or wherein it is not heat-set and exhibits a dry heat shrinkage of 5 to 25% in the warp and weft directions by heating at 150 ° C. for 15 minutes. Flame retardant polyolefin resin coated sheet. 7. The red phosphorus particles whose surface has aluminum hydroxide, magnesium hydroxide, titanium oxide, zinc oxide, formalin resin, phenol resin, melamine resin,
The flame-retardant polyolefin-based resin coating according to claim 1, which is coated with at least one selected from a urea resin and an epoxy resin, and the surface-coated red phosphorus particles have an average particle size of 5 to 25 µm. Sheet. 8. The polyolefin resin protective layer which is colored without containing the red phosphorus particles is formed on at least one of the front and back double-sided polyolefin resin composition layers. The flame-retardant polyolefin-based resin-coated sheet according to any one of the preceding claims. 9. The colored polyolefin-based resin protective layer comprises 5 to 50 parts by weight of a phosphoric acid-based compound component and 1 to 20 parts of a chemical foaming agent component based on 100 parts by weight of the polyolefin-based resin.
Parts by weight and 1 to 20 parts by weight of a colorant component composed of at least one selected from inorganic pigments and organic pigments,
The flame-retardant polyolefin resin-coated sheet according to claim 8, which is formed of a colored polyolefin resin composition having a melt flow rate (MFR) of 0.2 to 5.0 g / 10 minutes. 10. The flame retardant according to claim 9, wherein the phosphate compound component includes at least one selected from a phosphate, a phosphate, a phosphate, and a condensed phosphate. Polyolefin resin coated sheet. 11. The condensed phosphate is ammonium polyphosphate, thermosetting resin-coated ammonium polyphosphate,
The flame-retardant polyolefin-based resin-coated sheet according to claim 10, comprising at least one selected from melamine and melamine polyphosphate. 12. The flame-retardant polyolefin-based resin-coated sheet according to claim 9, wherein the chemical foaming agent component contains at least one selected from azo compounds, sulfohydrazide compounds, and nitroso compounds. 13. The flame-retardant polyolefin-based resin according to claim 8, wherein the thickness of the colored polyolefin-based resin protective layer is 10 to 50% of the total thickness of the flame-retardant polyolefin-based resin-coated sheet. Cover sheet. 14. A composite sheet is formed by attaching a film made of a polyolefin-based resin composition on both front and back surfaces of a base fabric including a fabric woven from thermoplastic resin filament yarns using a heating laminator. The polyolefin-based resin composition comprises 100 parts by weight of a polyolefin-based resin and 5 to 25 parts by weight of red phosphorus particles mixed therein, and has a melt flow of 0.2 to 50 g / 10 minutes. Rate (MFR) (JIS K 676
0, except that the temperature is 190 ° C and the load is 2
1.18 N (2.16 kgf)), in the attaching step using the heating laminator,
The surface of the heat roll on the application side of the polyolefin-based resin composition film is heated to a temperature of 70 to 180 ° C., and the temperature of the base fabric is adjusted to 120 ° C. or lower, and the film is continuously connected to the base fabric. Heat and pressure bonding, and at this time,
A method for producing a flame-retardant polyolefin-based resin-coated sheet, comprising controlling the dry heat shrinkage of the obtained composite sheet by heating at 150 ° C. for 15 minutes to 5 to 25%. 15. The method according to claim 14, further comprising a step of forming a colored polyolefin-based resin protective layer without containing the red phosphorus particles on at least one surface of the front and back double-sided polyolefin-based resin composition layers. For producing a flame-retardant polyolefin-based resin-coated sheet. 16. The step of forming the polyolefin-based resin protective layer is carried out by attaching a film of the polyolefin-based resin or applying a coating liquid containing the polyolefin-based resin and drying. , Claim 1
6. The method for producing a flame-retardant polyolefin-based resin-coated sheet according to 5.