JP2006044155A - Flame-retardant polyolefin resin tarpaulin with excellent heat creep resistance - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyolefin resin tarpaulin which does not contain chlorine/bromine-containing substance and shows high flame retardance, excellent heat creep resistance of a joint and if necessary, high stainproofing properties, and is suited for an oversized tent, a tent warehouse, a sun-screening tent, a construction cured sheet and an internally illuminated sign board. <P>SOLUTION: In this flame-retardant polyolefin resin tarpaulin, a specified amount of a cyclic iminoether side chain group-containing resin (preferably, the cyclic iminoether group is an oxazoline group) is blended in a polyolefin resin composition containing a non-halogen containing flame retardance imparting agent (a specific basic hindered amine compound is preferred). Further, a flame-retardant/heat creep-resistant polyolefin resin layer is formed on both face/back of the fibrous base cloth, and if necessary, a photocatalyst or a stainproofing layer containing a stainproof resin is formed on the flame-retardant/heat creep-resistant polyolefin resin layer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  TECHNICAL FIELD The present invention relates to a flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep resistance, and is particularly used for applications such as large tents (pavilions), tent warehouses, awning tents, building curing sheets, and internally illuminated signboards. The present invention relates to a tarpaulin made of a flame-retardant polyolefin resin having excellent heat-resistant creep resistance. More specifically, the present invention is a polyolefin resin tarpaulin for a membrane structure, which does not contain a chlorine / bromine-containing substance, has excellent flame retardancy, and particularly has excellent heat-resistant creep resistance at a sheet joint. It is about.

  Conventionally, the surface of synthetic fiber fabrics is soft polychlorinated for raw materials of membrane structures such as medium- and large-sized tents, awning tents, tent warehouses, and industrial material sheet materials such as building site curing sheets and sound insulation sheets for building sites. Tarpaulins coated with vinyl resin are widely used. In each of these application fields, high durability performance and flameproof performance are required (Japanese Industrial Standard, various industrial association standards, etc.). Polyvinyl chloride resin is a resin with excellent performance, processability, and cost, and is used in large quantities in daily goods. However, in recent social situations, toxic gas and toxic residue generation problems during incineration, the environment The movement to reduce the use of polyvinyl chloride resin as much as possible has been activated for reasons of protection and the possibility of suspected hormonal disruption of phthalates contained as plasticizers. Many people misunderstand that vinyl chloride resin is simply harmful. As a substitute resin for polyvinyl chloride resin, it has been tried to use polyolefin resins such as polyethylene resin, polypropylene resin, ethylene-vinyl acetate copolymer resin from the viewpoint of using halogen-free resin, and many household goods In the field of raw materials for membrane structures and industrial material sheets, it is still in the development stage. The reasons are 1). It is difficult to impart practically sufficient flame resistance to flammable polyolefin resins, and 2). If the resin is changed, it may be incompatible with Japanese Industrial Standards or various industry association standards. Reason 1) is based on the premise that flame resistance is imparted by adding chlorine / bromine-free substances, but in order to obtain flame resistance equivalent to that of polyvinyl chloride resin, a large amount of chlorine / bromine-free substances are required. To do. When this is performed, problems such as deterioration in processability, performance reduction, and high cost of the resulting resin composition are encountered. The reason for 2) is that the standard was originally built on the premise of processed products of polyvinyl chloride resin, so it is difficult to comply with the standard itself by changing the resin system. The addition of the flameproofing technology by means of making it more difficult to meet the standards. In addition, from the viewpoint of a fabric structure sewer, the texture and high-frequency fusion performance equivalent to those of soft polyvinyl chloride resin processed products are required. Therefore, among polyolefin resins, ethylene-acetic acid is soft and has high-frequency fusion properties. Tarpaulin development using vinyl copolymer resin (EVA) was conducted, blend of EVA and polyethylene resin, blend of EVA and ethylene-α-olefin copolymer resin, or two layers of EVA and polyethylene resin, Two layers of EVA and ethylene-α-olefin copolymer resin were used, and the one using ethylene- (meth) acrylic acid (ester) copolymer resin instead of EVA was studied. The polymer resin contains copolymer components such as vinyl acetate component and (meth) acrylic acid (ester) component, so the resin strength is low. Since a low melting point, hence heat creep resistance can not be obtained, either it has been difficult to meet the membrane structure standards. The heat-resistant creep property is an evaluation of the fracture strength of the joint part of the membrane structure, and the resin softens when exposed to a heat of 50 ° C. or more, particularly in summer, and the synthetic fiber fabric and the resin coating When the adhesion strength with the layer is extremely reduced, there are troubles such as peeling of the joints and breakage of yarns at the joints, and in order to avoid this trouble, it is necessary to conduct a heat-resistant creep resistance confirmation test. is there.

As a technique for improving the adhesion effect between the synthetic fiber fabric and the polyolefin resin coating layer, 1). Blend of ethylene-vinyl acetate copolymer resin and ethylene-α-olefin copolymer resin with ethylene-maleic anhydride-ethyl acrylate terpolymer (adhesive resin) and hydrous silicate A tarpaulin (for example, Patent Document 1: Japanese Patent Application Laid-Open No. 2003-176387) has been proposed in which the coated composition is used as a coating layer. In this method, the adhesion effect between the synthetic fiber fabric and the polyolefin resin coating layer is improved only at room temperature, but the heat-resistant creep resistance of the joint is still insufficient. The hydrous silicate and the adhesive resin interact to increase the melt viscosity during processing, and at the same time, the film sticks to the metal hot roll, so it is difficult to process the adhesive resin in a large amount. Further, there is a problem that the abrasion resistance of the tarpaulin obtained by blending ethylene-maleic anhydride-ethyl acrylate terpolymer is lowered. 2). Proposed methods include electron beam cross-linking of polyolefin resins and methods of electron beam cross-linking polyolefin resins containing compounds containing acrylic or allyl groups (for example, Patent Document 2: Japanese Patent Application Laid-Open No. 08-1874). Has been. In this method, the heat resistance of the polyolefin resin layer itself is improved, but the effect of improving the adhesion between the synthetic fiber fabric and the polyolefin resin coating layer and the heat resistance creep resistance of the joint cannot be obtained. In addition, tarpaulins subjected to electron beam crosslinking are difficult to heat-seal such as high-frequency fusion. 3). In a blend of ethylene-vinyl acetate copolymer resin and ethylene-α-olefin copolymer resin, Mg ₆ Al ₂ (OH) ₁₆ CO ₃ .4H ₂ O and Mg _4.5 Al ₂ (OH) ₁₃ CO _3. A method of blending a synthetic water-containing synthetic adsorbent such as 3.5H ₂ O (Patent Document 3: Japanese Patent Laid-Open No. 05-163390) has been proposed. Although this method improves the heat resistance and wear resistance of the polyolefin resin layer itself, it cannot provide an effect of improving the adhesion between the synthetic fiber fabric and the polyolefin resin coating layer, and still has a heat resistant creep of the joint. The nature is also insufficient. 4). As a tarpaulin having flame retardancy, a construction work sheet by coating a flame retardant composition in which an aqueous dispersion resin is blended with an ammonium polyphosphate compound, a metal hydroxide, and an oxazoline group-containing aqueous crosslinking agent (for example, patent documents) 4: JP 2002-3690 A). The sheet obtained by this method is used as a tent film material because the flame retardant composition is impregnated and fixed inside the yarn on a synthetic fiber base fabric or tarpaulin base fabric, and the texture is hard and the tear strength is weak. Is inappropriate. Moreover, no matter how much the liquid flame retardant composition is impregnated and applied to a coarse fabric such as a tarpaulin base fabric, the flame retardant composition drips from the coarse portion, and a waterproof membrane material useful as a tent membrane material is obtained. It is difficult. 5). A flame retardant laminate obtained by laminating a flame retardant film formed from a resin mixture obtained by mixing a flame retardant which is a NOR type light stabilizer, a melamine cyanurate and a phosphoric ester compound as a tarpaulin having flame retardancy ( For example, Japanese Patent Application Laid-Open No. 2004-174869) has been proposed. The laminate obtained by this method can obtain a relatively high flameproofing property with a relatively small amount of flame retardant, but as in Patent Documents 1 to 3, the synthetic fiber fabric and the polyolefin resin coating layer Since the effect of improving the adhesion is insufficient, it still does not reach the heat resistant creep property of the joint. In addition, a method of forming a polyolefin resin coating layer on both sides of a fibrous base fabric treated with an adhesive (for example, a polyurethane adhesive in combination with an isocyanate compound) has been tried. Adhesiveness with the resin-based resin layer is insufficient, and at the same time, there is a problem that the texture of the fibrous base fabric becomes hard and the tear strength is greatly reduced, and can eventually be used for a practical membrane structure. It was not a thing. In addition, in the method of kneading the isocyanate compound or carbodiimide compound into the film, a certain degree of adhesive strength improvement effect could be expected, or the film moldability was extremely lowered, and the film was hardly peeled off from the thermoforming roll. Because it has problems, it has never been put to practical use. In addition, the method of improving adhesion by interposing an ionomer resin between the fibrous base fabric and the polyolefin resin layer can surely provide an adhesive effect at room temperature, but it has an adhesive strength in a temperature atmosphere of 50 ° C or higher. However, there was anxiety at the joint of the membrane structure. In addition, these polyolefin resins are used in combination with various flame retardants for imparting flame resistance, but since a large amount of halogen-free flame retardant is required for imparting flame resistance to polyolefin resins, The problem of reduced resin strength due to flameproofing was inevitable, and in addition, the reliability of the joint strength was poor. Therefore, there was no flameproof and flexible polyolefin resin tarpaulin film material suitable for the membrane structure and excellent in heat-resistant creep resistance at the joint.

JP 2003-176387 A Japanese Patent Application Laid-Open No. 08-1874 JP 05-163390 A Japanese Patent Laid-Open No. 2002-3690 JP 2004-174869 A

  The present invention seeks to provide a polyolefin resin tarpaulin suitable for applications such as large tents, tent warehouses, awning tents, building curing sheets, and internally illuminated signboards. In particular, the present invention is a polyolefin-based tarpaulin that does not contain a chlorine / bromine-containing substance, has excellent flame retardancy, and has excellent heat-resistant creep resistance at the joint, and further has excellent antifouling properties. It is intended to provide resin tarpaulins.

  The present invention has been intensively studied in view of such points, and as a result, a cyclic iminoether side chain group-containing polymer is contained in a polyolefin resin composition containing a halogen-free flame retardant (preferably a specific basic hindered amine compound). By blending a specific amount (preferably a cyclic imino ether group is an oxazoline group), a polyolefin-based resin tarpaulin excellent in heat-resistant creep resistance can be obtained while having flame resistance comparable to that of a polyvinyl chloride resin. It is easy to heat-seal, antifouling layer containing a photocatalytic substance on the surface of tarpaulin, or antifouling layer made of acrylic resin, acrylic-silicon resin, fluorine resin, etc. It is possible to maintain the aesthetics of the tent membrane structure over a long period of time by forming an antifouling layer containing silica fine particles This has led to the completion of the present invention out.

〔但し、式（Ｉ）において、Ｒ¹及びＲ²は、それぞれ、互に独立して、水素原子、又は１８個の炭素原子を含む不活性炭化水素基を表し、ｎは１〜５の正の整数を表す〕
により表される環状イミノエーテル側鎖基を有する少なくとも１種の重合体を含み、前記耐熱クリープ性向上成分（３）の含有量が、前記樹脂成分（１）１００質量部に対し、０．５〜３０質量部の範囲内にある、ことを特徴とするものである。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記樹脂成分（１）が、ブレンド樹脂要素（ｂ）として、ポリエチレン樹脂、エチレン−α−オレフィン共重合体樹脂、軟質ポリプロピレン樹脂から選ばれた１種以上をさらに含むことが好ましい。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記樹脂成分（１）が、追加ブレンド樹脂要素（ｃ）として、Ａ−Ｂ−Ａ型スチレンブロック共重合樹脂（但し、Ａはスチレン重合体ブロックを表し、Ｂはブタジエン重合体ブロック、イソプレン重合体ブロック、もしくはビニルイソプレン重合体ブロックを表す。）、Ａ−Ｂ型スチレンブロック共重合樹脂（Ａ及びＢは、上記と同義である。）、スチレンランダム共重合樹脂、及び前記スチレン系共重合樹脂の水素添加樹脂から選ばれた１種以上を含むことが好ましい。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記樹脂成分（１）に含まれる前記主樹脂要素（ａ）に含まれる酢酸ビニル成分、および／または（メタ）アクリル酸（エステル）成分の合計質量が、前記ポリオレフィン系樹脂層の合計質量（但し前記ハロゲン非含有難燃付与剤成分を除く）に対して、５〜３０質量％であることが好ましい。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記ポリオレフィン系樹脂層と前記繊維性基布との積層界面において、前記耐熱クリープ性向上成分（３）中の環状イミノエーテル側鎖基開環のよる架橋構造が形成されていることが好ましい。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記環状イミノエーテル側鎖基含有樹脂が、オキサゾリン基含有共重合樹脂であることが好ましい。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記ハロゲン非含有難燃付与剤成分（２）が、少なくとも１種の塩基性ヒンダードアミン系化合物を含み、この塩基性ヒンダードアミン系化合物を下記式（II）：

〔但し、式（II）中、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ互に独立して、ａ）．水素原子、ｂ）．炭素原子数１〜２０の直鎖又は分枝アルキル基、ｃ）． -Ｏ- 、 -Ｓ- 、 -ＳＯ- 、 -ＳＯ₂-、 -ＣＯ- 、 -ＣＯＯ- 、 -ＯＣＯ- 、 -ＣＯＮＲ- 、 -ＮＲＣＯ- 及び -ＮＲ- から選ばれた１個以上を含む、炭素原子数１〜２０のアルキル基、ｄ）．炭素原子数３〜２０のアルケニル基、ｅ）．炭素原子数６〜１０の未置換アリール基、ｆ）．炭素原子数１〜２０のアルキル基、炭素原子数５〜１２のシクロアルキル基、及び炭素原子数７〜１５のフェニルアルキル基から選択された１〜３個の置換基を有するアリール基を表し、Ｒ⁷ は炭素原子数２〜１８のアルキル基、または炭素原子数５〜１２のシクロアルキル基を表す〕
により表されるヒンダードアミン構造を有するものであることが好ましい。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記表裏両面ポリオレフィン系樹脂層の少なくとも１面上に、酸化チタン（ＴｉＯ₂）、過酸化チタン（ペルオキソチタン酸）、酸化亜鉛（ＺｎＯ）、及び酸化錫（ＳｎＯ₂）から選ばれた１種以上の光触媒物質を含有する防汚層が形成されていることが好ましい。
本発明の耐熱クリープ性に優れた難燃ポリオレフィン系樹脂ターポリンにおいて、前記表裏両面ポリオレフィン系樹脂層の少なくとも１面上に、アクリル系樹脂、アクリル−シリコン樹脂、及びフッ素系樹脂から選ばれた１種以上の防汚樹脂、または前記防汚樹脂の１種以上とシリカ微粒子とを含む混合物からなる防汚層が設けられていることも好ましい。 The flame retardant polyolefin-based resin tarpaulin excellent in heat-resistant creep of the present invention is a fibrous base fabric and a film material including a polyolefin-based resin layer laminated on both front and back surfaces thereof,
The polyolefin resin layer includes a kneaded product of (1) a resin component, (2) a halogen-free flame retardant imparting component, and (3) a heat-resistant creep resistance improving component,
As the main resin element (a), the resin component (1) is one or more ethylene-based resins selected from ethylene-vinyl acetate copolymer resins and ethylene- (meth) acrylic acid (ester) copolymers. Including a copolymer resin,
The heat resistant creep resistance improving component (3) is represented by the following formula (I):

[In the formula (I), R ¹ and R ² each independently represent a hydrogen atom or an inert hydrocarbon group containing 18 carbon atoms, and n is a positive number of 1-5. Represents an integer of
And the content of the heat-resistant creep resistance improving component (3) is 0.5 with respect to 100 parts by mass of the resin component (1). It is in the range of ˜30 parts by mass.
In the flame-retardant polyolefin-based resin tarpaulin excellent in heat-resistant creep property of the present invention, the resin component (1) is selected from a polyethylene resin, an ethylene-α-olefin copolymer resin, and a soft polypropylene resin as the blend resin element (b). It is preferable that one or more selected ones are further included.
In the flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property of the present invention, the resin component (1) is an A-B-A type styrene block copolymer resin (provided that A is an additional blend resin element (c)). Represents a styrene polymer block, B represents a butadiene polymer block, an isoprene polymer block, or a vinyl isoprene polymer block.), An AB type styrene block copolymer resin (A and B are as defined above). .), One or more selected from styrene random copolymer resins and hydrogenated resins of the styrene copolymer resins.
In the flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property of the present invention, a vinyl acetate component and / or (meth) acrylic acid (ester) contained in the main resin element (a) contained in the resin component (1) ) The total mass of the components is preferably 5 to 30% by mass with respect to the total mass of the polyolefin-based resin layer (excluding the halogen-free flame retardant imparting agent component).
In the flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property of the present invention, the cyclic imino ether side chain in the heat-resistant creep property-improving component (3) at the lamination interface between the polyolefin resin layer and the fibrous base fabric. It is preferable that a cross-linked structure by group opening is formed.
In the flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property of the present invention, the cyclic imino ether side chain group-containing resin is preferably an oxazoline group-containing copolymer resin.
In the flame retardant polyolefin resin tarpaulin excellent in heat-resistant creep of the present invention, the halogen-free flame retardant imparting agent component (2) contains at least one basic hindered amine compound, and the basic hindered amine compound is Formula (II) below:

[However, in the formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a). A hydrogen atom, b). A linear or branched alkyl group having 1 to 20 carbon atoms, c). Including one or more selected from -O-, -S-, -SO-, -SO _2- , -CO-, -COO-, -OCO-, -CONR-, -NRCO- and -NR- An alkyl group having 1 to 20 carbon atoms, d). An alkenyl group having 3 to 20 carbon atoms, e). An unsubstituted aryl group having 6 to 10 carbon atoms, f). An aryl group having 1 to 3 substituents selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a phenylalkyl group having 7 to 15 carbon atoms; R ⁷ represents an alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms.
It is preferable that it has a hindered amine structure represented by these.
In the flame retardant polyolefin resin tarpaulin excellent in heat-resistant creep property of the present invention, titanium oxide (TiO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (on at least one surface of the front and back double-sided polyolefin resin layers) It is preferable that an antifouling layer containing one or more photocatalytic substances selected from ZnO) and tin oxide (SnO ₂ ) is formed.
In the flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property of the present invention, at least one surface selected from an acrylic resin, an acrylic-silicon resin, and a fluorine resin on at least one surface of the front and back double-sided polyolefin resin layers It is also preferred that an antifouling layer comprising the above antifouling resin or a mixture containing one or more of the antifouling resins and silica fine particles is provided.

  The tarpaulin of the present invention is a flexible sheet capable of high-frequency fusion bonding with a polyolefin resin, and in the polyolefin resin layer formed on the base fabric, a cyclic iminoether side chain group-containing polymer, particularly an oxazoline group-containing polymer. By including a specific amount of the copolymer resin, it is possible to obtain a tarpaulin excellent in heat resistance creep resistance of the sheet joint portion. In addition, the tarpaulin of the present invention can contain a specific amount of a specific basic hindered amine compound as a halogen-free flame retardant imparting agent in the polyolefin resin layer.・ Because a bromine-free flameproofing can be realized, the tarpaulin of the present invention is therefore a large tent (pavilion) designed without using polyvinyl chloride resin, tent warehouse, awning tent, building curing sheet, and interior illumination type Suitable for constituent film materials such as signboards. Furthermore, on the polyolefin resin layer of the tarpaulin of the present invention, a photocatalyst substance-containing layer, or a coating layer made of an antifouling resin such as an acrylic resin, an acrylic-silicon resin, and a fluorine resin, or the like, as necessary. By providing a coating layer containing silica fine particles in the soil resin, the adhesion of outdoor soil can be reduced. Therefore, the use of the tarpaulin of the present invention as a membrane structure makes it possible to maintain the aesthetics for a long time.

  The flame retardant polyolefin resin tarpaulin excellent in heat-resistant creep property of the present invention (hereinafter referred to as polyolefin resin tarpaulin) is a film material in which a polyolefin resin layer is laminated on both front and back surfaces of a fibrous base fabric, The polyolefin-based resin layer contains a kneaded product of a resin component (1), a halogen-free flame retardant imparting agent component (2), and a heat resistant creep resistance improving agent component (3). The resin component (1) has, as its main resin element, one or more ethylene copolymer resins selected from ethylene-vinyl acetate copolymer resins and ethylene- (meth) acrylic acid (ester) copolymers. The heat-resistant creeping component (3) contains a cyclic imino ether side chain group-containing polymer in a proportion of 0.5 to 30 parts by mass with respect to 100 parts by mass of the polyolefin resin. The resin component (1) of the polyolefin resin layer includes, in addition to the main resin element (a), a blend resin element comprising a polyethylene resin, a styrene-α-olefin copolymer resin and / or a soft polypropylene resin as necessary. (B) and A-B-A and AB type styrene block copolymers, styrene random copolymers, and an additional blend resin element (c) consisting of one or more of these hydrogenated resins. Also good. The halogen-free flame retardant component (2) preferably contains at least one basic hindered amine compound.

The ethylene-vinyl acetate copolymer resin and ethylene- (meth) acrylic acid (ester) copolymer used as the main resin element (a) in the polyolefin resin layer of the tarpaulin of the present invention are ethylene-vinyl acetate. Ethylene copolymers such as copolymer resins, ethylene-acrylic acid copolymer resins, ethylene-methacrylic acid copolymer resins, ethylene-acrylic acid ester copolymer resins, ethylene-methacrylic acid ester copolymer resins Includes resin. Specifically, this ethylene-based copolymer resin has an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer with a density of 0.880 to 0.960 g / cm ² , MFR. (Melt flow rate: 190 ° C., 2.16 kg load) is preferably 0.3 to 10 g / min. Moreover, it is preferable that the vinyl acetate component amount of ethylene-vinyl acetate copolymer resin is 12 to 60 weight%, More preferably, it is 15 to 40 mass%, and is especially 15 in the ethylene-based copolymer resin single use system. It is preferable that the content is ˜28% by mass because flexibility and high-frequency fusion property are particularly high. The amount of the (meth) acrylic acid component in the ethylene- (meth) acrylic acid (ester) copolymer is preferably 12 to 60% by weight, more preferably 15 to 40% by weight, In the case where the copolymer resin is used alone, the content is preferably 15 to 28% by mass because the flexibility and the high frequency fusion property are particularly high. When these ethylene-based copolymer resins have a vinyl acetate component amount or (meth) acrylic acid component amount, or a total amount of vinyl acetate component and (meth) acrylic acid component of less than 12% by mass, The high frequency fusion property may be insufficient. If it exceeds 60% by mass, the resulting tarpaulin may have insufficient wear resistance. In particular, if it exceeds 80% by mass, the texture of the obtained tarpaulin may become excessively hard.

The blend resin element (b) contained in the polyolefin resin layer of the polyolefin resin tarpaulin of the present invention is one selected from polyethylene resin, ethylene-α-olefin copolymer resin, and polypropylene resin alloy (soft polypropylene resin). The above is mentioned. The polyethylene resin preferably has a density of 0.850 to 0.930 g / cm ² and an MFR (melt flow rate: 190 ° C., 2.16 kg load) of 0.5 to 20 g / min. The polymer resin preferably has a density of 0.850 to 0.930 g / cm ² and MFR (melt flow rate: 190 ° C., 2.16 kg load) 0.3 to 30 g / 10 min, more preferably 1 to 20g / 10min. As the ethylene-α-olefin copolymer resin, a resin obtained by polymerization of an ethylene monomer and an α-olefin monomer having 3 to 18 carbon atoms, particularly an α-olefin monomer having 4 to 10 carbon atoms is preferable. Preferred α-olefins include, for example, propylene, butene-1,4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, and the like. Ethylene-α-olefin copolymer resins obtained by using two or more types can also be used. In particular, among polyethylene resins and ethylene-α-olefin copolymer resins, those polymerized in the presence of a metallocene catalyst are excellent in mechanical strength and are preferable. The soft polypropylene resin preferably has a density of 0.850 to 0.930 g / cm ² , MFR (melt flow rate: 230 ° C., 2.16 kg load), 0.5 to 50 g / 10 min, more preferably 1 to The soft polypropylene resin having a viscosity of 20 g / 10 min may be a propylene homopolymer, particularly a syndiotactic stereoregularity, or an ethylene-propylene copolymer or a propylene-α-olefin copolymer. Propylene / ethylene / propylene copolymer elastomer, propylene / ethylene / propylene / non-conjugated diene copolymer elastomer, and the like may be used. These copolymers may be random copolymers or block copolymers. These polypropylene copolymer elastomers are so-called reactor TPOs such as those in which propylene / ethylene components are graft-polymerized on polypropylene components, and those in which ethylene / propylene / non-conjugated diene components are graft-polymerized onto polypropylene components. However, it is preferable from the viewpoint of the processability and the high flexibility of the obtained tarpaulin. These polypropylene resins can be used in combination of two or more. Moreover, there is no limitation in particular in the manufacturing method, molecular weight distribution, etc. in each of a polyethylene resin, ethylene-alpha-olefin copolymer resin, and a soft polypropylene resin. The blend ratio of the elements (a) :( b) in the polyolefin resin of the resin elements (a) + (b) is preferably (a) :( b) = 20: 80 to 80:20, (a) The content of vinyl acetate and / or (meth) acrylic acid component in the resin blend of + (b) is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass. When the content of the vinyl acetate and / or (meth) acrylic acid component in the (a) + (b) resin blend is less than 5% by mass, the high frequency fusion property of the obtained tarpaulin may be insufficient. If it exceeds 30% by mass, the weather resistance and wear resistance may be deteriorated.

  The resin component (1) of the polyolefin-based resin layer of the polyolefin-based resin tarpaulin of the present invention includes a styrene-based copolymer for the purpose of imparting flexibility, heat resistance, processability, and paintability to the obtained film material. A polymer resin can be included as an additional blend resin element (c). The styrene copolymer resin is an ABA type styrene block copolymer resin (A represents a styrene polymer block, B represents a butadiene polymer block, an isoprene polymer block, or a vinyl isoprene polymer block. .), AB type styrene block copolymer resin (A and B are as defined above), styrene random copolymer resin, and hydrogenated resins of these styrene copolymer resins That's it. Specifically, as the ABA type styrene block copolymer resin, for example, styrene-butadiene-styrene block copolymer resin (SBS), styrene-isoprene-styrene block copolymer resin (SIS), Styrene-vinylisoprene-styrene block copolymer resin (SVIS) or the like is used, and the ABA type hydrogenated styrene block copolymer resin is, for example, a hydrogenated resin of styrene-butadiene-styrene block copolymer resin. Examples include a styrene-ethylene-butene-styrene block copolymer resin (SEBS), a styrene-ethylene-propylene-styrene block copolymer resin (SEPS) which is a hydrogenated resin of a styrene-isoprene-styrene block copolymer resin, and the like. The AB type styrene copolymer resin includes, for example, a styrene-butadiene block copolymer resin (SB) and a styrene-isoprene block copolymer resin (SI), and as an AB type hydrogenated block copolymer resin. For example, styrene-ethylene-butene block copolymer resin (SEB), which is a hydrogenated resin of styrene-butadiene block copolymer resin, and styrene-ethylene-butene block copolymer, which is a hydrogenated resin of styrene-isoprene block copolymer resin. Polymerized resin (SEP) and the like are included. The blend ratio of the elements (a) and (c) in the element (a) + (c) is preferably (a) :( c) = 20: 80 to 80:20, and (a) :( c The content of the vinyl acetate and / or the (meth) acrylic acid component in the resin blend is preferably 5 to 30% by mass, and more preferably 10 to 20% by mass. When the content of the vinyl acetate and / or (meth) acrylic acid component in the resin element (a) + (c) blend is less than 5% by mass, the high frequency fusion property of the obtained tarpaulin may be insufficient. In addition, if it exceeds 30% by mass, the weather resistance and wear resistance of the obtained tarpaulin may be insufficient. Also, the blend ratio of the resin elements (a), (b), and (c) in the resin element (a) + (b) + (c) blend resin is [(a) + (b)]: (c) = It is preferably 20:80 to 80:20, and the content of vinyl acetate and / or (meth) acrylic acid component in this resin blend is preferably 5 to 30% by mass, particularly 10 to 20 More preferably, it is mass%. When the content of vinyl acetate and / or (meth) acrylic acid component in the resin blend of [(a) + (b)] + (c) is less than 5% by mass, the obtained tarpaulin has high frequency fusion property. When it exceeds 30% by mass, weather resistance and abrasion resistance may be insufficient. As the styrene copolymer resin for the resin element (c), a resin dissolved in an organic solvent can be used as a primer agent for the polyolefin resin tarpaulin of the present invention.

オキサゾリン基を含む単量体の具体的として、２−ビニル−２−オキサゾリン、５−メチル−２−ビニル−２−オキサゾリン、４，４−ジメチル−２−ビニル−２−オキサゾリン、４，４−ジメチル−２−ビニル−５，５−ジヒドロ−４Ｈ−１，３−オキサゾリン、４，４，６−トリメチル−２−ビニル−５，６−ジヒドロ−４Ｈ−１，３−オキサゾリン、２−イソプロペニル−２−オキサゾリン、４，４−ジメチル−２−イソプロペニル−２−オキサゾリンなどのビニルオキサゾリン類が挙げられるかこれらに限定されるものではない。上記環状イミノエーテル側鎖基含有樹脂の配合混練量は、ポリオレフィン系樹脂層中の樹脂成分（１）（樹脂要素（ａ）のみ、樹脂要素（ａ）＋（ｂ）、樹脂要素（ａ）＋（ｃ）及び樹脂要素（ａ）＋（ｂ）＋（ｃ）を含む）１００質量部に対して、０．５〜３０質量部であることが好ましく、より好ましくは２〜２０質量部である。前記配合混練量が０．５質量部未満では、得られるターポリンの高周波融着部の破壊強度および耐熱クリープ性の向上効果が不十分であり、またそれが３０質量部を越えると、繊維性基布と得られるポリオレフィン系樹脂層との間の接着力が飽和して、寄与効果の増大が無く、却ってポリオレフィン系樹脂層を脆くしたり、ターポリンの柔軟性を硬くすることがある。またカレンダー加工などのフィルム成形性にも悪影響を及ぼすことがある。環状イミノエーテル側鎖基含有重合体は、ペレット状、フレーク状、粉末状の何れの形態で供給されてもよい。環状イミノエーテル側鎖基含有樹脂重合体含有耐熱クリープ性向上成分（３）の配合混練効果は、ポリオレフィン系樹脂層内部に例えばオキサゾリン基の開環による耐熱性の架橋構造を形成すること、と、更にポリオレフィン系樹脂層と繊維性基布との積層界面に、オキサゾリン基の開環のよる架橋接着構造が形成することによって得られ、それによってターポリンの耐熱特性を向上し、特にシート接合部においては耐熱クリープ性を飛躍的に向上させることが可能となる。 The cyclic iminoether side chain group-containing resin blended and kneaded in the polyolefin resin layer of the polyolefin resin tarpaulin of the present invention as the heat resistant creep resistance improving component (3) is an ethylene containing a cyclic iminoether group of the formula (I) Any of a self-polymer of a polymerizable unsaturated monomer or a copolymer of a cyclic imino ether group-containing monomer and another monomer may be used.
The other ethylenically unsaturated monomer copolymerizable with the cyclic imino ether group-containing monomer is not particularly limited as long as it is a monomer that does not react with the cyclic imino ether group. In particular, styrene, o-methyl styrene, p-methyl styrene. Styrene substitutes such as α-methylstyrene are preferred. Other copolymerizable monomers include vinyl aromatics such as vinyl naphthalene and vinyl anthracene, vinyl cyanides such as (meth) acrylonitrile, acrylic esters such as acrylic esters and methacrylic esters, and (meth) acrylamides. , Unsaturated acrylamides such as N-methylol (meth) acrylamide, vinyl esters such as vinyl acetate and vinyl propionate, vinyl ethers such as methyl vinyl ether, α-olefins such as ethylene and propylene, vinyl chloride, vinylidene chloride, etc. And a halogen-containing α, β-unsaturated monomer, and one or a mixture of two or more thereof can be used. The content of the monomer component containing a cyclic iminoether group contained in the cyclic iminoether side chain group-containing copolymer resin is preferably 0.1% by mass or more, particularly 1 to 20 in terms of the charge ratio of the monomer for polymerization. More preferably, it is mass%. If the charge ratio of the cyclic imino ether group-containing monomer is less than 0.1% by mass, the effect of improving the fracture strength of the high-frequency fused portion and the heat-resistant creep property of the resulting polymer is dilute, so a large amount of cyclic imino ether side It is necessary to add a chain group-containing resin. In the cyclic imino ether side chain group-containing resin used in the present invention, the cyclic imino ether group is particularly an oxazoline group represented by the following formula (III) (R ¹ = R ² = H, n = 2 in formula I) Is preferred.

Specific examples of the monomer containing an oxazoline group include 2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4- Dimethyl-2-vinyl-5,5-dihydro-4H-1,3-oxazoline, 4,4,6-trimethyl-2-vinyl-5,6-dihydro-4H-1,3-oxazoline, 2-isopropenyl Vinyloxazolines such as 2-oxazoline and 4,4-dimethyl-2-isopropenyl-2-oxazoline may be mentioned or not limited thereto. The compounding and kneading amount of the cyclic iminoether side chain group-containing resin is the resin component (1) in the polyolefin-based resin layer (resin element (a) only, resin element (a) + (b), resin element (a) + It is preferably 0.5 to 30 parts by mass, more preferably 2 to 20 parts by mass with respect to 100 parts by mass (including (c) and the resin elements (a) + (b) + (c)). . If the blending and kneading amount is less than 0.5 parts by mass, the effect of improving the fracture strength and heat-resistant creep resistance of the high-frequency fusion part of the tarpaulin obtained is insufficient, and if it exceeds 30 parts by mass, the fibrous base The adhesive force between the cloth and the resulting polyolefin resin layer is saturated, there is no increase in the contribution effect, and on the contrary, the polyolefin resin layer may be made brittle or the flexibility of the tarpaulin may be increased. In addition, film formability such as calendering may be adversely affected. The cyclic imino ether side chain group-containing polymer may be supplied in any form of pellets, flakes, and powders. The compounding and kneading effect of the cyclic imino ether side chain group-containing resin polymer-containing heat-resistant creep resistance improving component (3) is to form a heat-resistant crosslinked structure by, for example, ring opening of an oxazoline group inside the polyolefin-based resin layer, Furthermore, it is obtained by forming a cross-linking adhesive structure by the ring opening of the oxazoline group at the lamination interface between the polyolefin resin layer and the fibrous base fabric, thereby improving the heat resistance characteristics of the tarpaulin, particularly in the sheet joint portion. It becomes possible to drastically improve the heat resistant creep resistance.

  The halogen-free flame retardant component (2) contained in the polyolefin resin layer of the polyolefin resin tarpaulin of the present invention has an alkoxy group having 2 to 18 carbon atoms at the N-position of the hindered amine structure shown in the formula (II), Or it is preferable that the basic hindered amine type compound which has 1 or more types of substituents chosen from the C5-C12 cycloalkoxy group is included, and a). Phosphorus atom-containing compounds such as red phosphorus, metal phosphates, metal organic phosphates, phosphate derivatives, ammonium polyphosphate, and ammonium polyphosphate derivative compounds, b). Nitrogen-containing compounds such as (iso) cyanurate compounds, (iso) cyanuric acid compounds, guanidine compounds, urea compounds, and derivatives thereof, c). One or more of inorganic compounds such as silicon compounds, metal hydroxides, metal oxides, metal carbonate compounds, metal sulfate compounds, boric acid compounds, and inorganic compound complexes can be used in combination. In the present invention, preferred halogen-free flame retardants for use in combination with basic hindered amine compounds are specifically phosphoric esters, (melamine-coated) ammonium polyphosphate, melamine cyanurate, magnesium hydroxide, water. Aluminum oxide, antimony oxide, zinc borate, or the like can be used. (Hereinafter, these halogen-free flame retardants are referred to as combined halogen-free flame retardants.)

The content of the basic hindered amine compound for the halogen-free flame retardant imparting agent component (2) is such that the resin component (1) (resin element (a) only, resin element (a) + (b ), Resin element (a) + (c), resin element (a) + (b) + (c) included) is preferably 0.05 to 5 parts by mass, more preferably 100 parts by mass Is 0.5-3 parts by mass. When the content of the basic hindered amine compound is less than 0.05 parts by mass, the flame retardancy of the obtained tarpaulin may be insufficient, and a combination halogen-free flame retardant imparting agent may be added in a large amount. It may be necessary. Moreover, when it exceeds 5 mass parts, the workability of a polyolefin-type resin layer, especially calendar workability may become inadequate, and also a flame retardance may fall. Use of the combined halogen-free flame retardant imparting agent is preferably 5 to 60% by mass, more preferably 10 to 30% by mass, based on the total mass of the resin component (1). If the content of the combined use halogen-free flame retardant exceeds 60% by mass, the processability of the resulting polyolefin-based resin layer becomes insufficient, and the joint strength, abrasion resistance, and heat resistance creep resistance of the obtained tarpaulin. May become insufficient. The basic hindered amine compound for halogen-free flame retardant component (2) preferably has at least one, particularly two or more hindered amine structures of the formula (II) in its molecular structure, and these hindered amines. The N-position of the structure has a substituent selected from an alkoxy group having 2 to 18 carbon atoms or a cycloalkoxy group having 5 to 12 carbon atoms, and two or more formulas (II) per molecule The substituents —OR ⁷ may be the same as or different from each other. When the molecular weight of the basic hindered amine compound is preferably 500 or more, more preferably 900 or more, and even more preferably 1500 or more, the residual retention in the resulting polyolefin resin layer is further improved.
As the basic hindered amine compound used in the film material of the present invention, it is particularly preferable that all of R ³ , R ⁴ , R ⁵ and R ⁶ in the hindered amine structural formula represented by the formula (II) are methyl groups. . R ⁷ is i). An alkyl group having 2 to 18 carbon atoms, that is, an N-position of the hindered amine structure of the formula (II) substituted with an alkoxy group having 2 to 18 carbon atoms, particularly preferably an alkoxy group having 6 to 12 carbon atoms Ii). A cycloalkyl group having 5 to 12 carbon atoms, that is, a cycloalkoxy group having 5 to 12 carbon atoms, preferably a cycloalkoxy group having 5 to 6 or 8 carbon atoms, in the hindered amine structure of the formula (II) A group, particularly preferably one substituted with a cyclohexyloxy group is preferred. Specific examples of basic hindered amine compounds include bis (N-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,4-bis [(N-cyclohexyloxy-2,2 , 6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine, 2,4-bis [(N-cyclohexyloxy-2,2,6,6) -Tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine and the like.

  Silica is added to the polyolefin resin layer of the polyolefin resin tarpaulin of the present invention for the purpose of improving its workability, workability at the time of tarpaulin sewing (blocking resistance and slip resistance) and high frequency induction heat generation. Also good. In addition, a lubricant may be added to the polyolefin-based resin layer in order to improve processability during the production of the polyolefin-based resin layer using a calendar. Silica is produced by a general wet method, dry synthesis method, or airgel synthesis method, and can be one having an average particle size of 1 to 20 μm, particularly synthetic amorphous silica of 2 to 10 μm. It is preferable to use it. It is preferable that the addition amount of a silica is 2-15 mass parts with respect to 100 mass parts of total mass of the resin component (1). If it is less than 2 parts by mass, the effect of improving high-frequency induction heat generation may be insufficient, and if it exceeds 15 parts by mass, the processability of the resulting polyolefin resin layer, particularly during calendar processing, will be insufficient. The film appearance may be unsatisfactory or the resin strength may be reduced, which may adversely affect the durability properties such as scratch resistance of the resulting tarpaulin. The lubricant contains at least one of a phosphate ester, aliphatic amide, and montanic acid lubricant, and the amount added is 0.1 to 3 parts by mass with respect to 100 parts by mass of the total mass of the resin component (1). It is preferable to be within the range. Further, as a polyolefin resin layer additive, one or more pigments, ultraviolet absorbers, HALS, antioxidants, etc. may be added depending on the application and purpose. It can also be used by mixing appropriately. Moreover, the addition amount can also be set suitably.

  As a method for forming the polyolefin resin layer film of the polyolefin resin tarpaulin of the present invention, known molding methods such as a T-die extrusion method, an inflation method, a calendar method, and the like can be used. In particular, when a calendering method is used for manufacturing a pigmented film or processing with many color changing operations, it can be easily carried out with less compound loss. Although there is no limitation in particular in the thickness of the polyolefin resin film obtained by a calendar process, it is preferable that it is 80-500 micrometers, More preferably, it is 130-450 micrometers. If the thickness of the film is less than 80 μm, the molding process is difficult, and when it is laminated to the fibrous base fabric, the head of the film may be cut off at the intersection of the fibrous base fabric, and the waterproofness may be impaired. Furthermore, the durability of the tarpaulin and the joint strength may be made insufficient. On the other hand, if it is thicker than 500 μm, the obtained tarpaulin becomes heavy and hard, and the workability such as folding and carrying may be lowered.

  The fibrous base fabric that can be used in the polyolefin-based resin tarpaulin of the present invention may be either a woven fabric or a knitted fabric. Examples of the woven fabric include plain weave, twill weave, and satin weave. Particularly, when a plain weave fabric is used, the balance of warp and weft physical properties of the obtained polyolefin resin sheet is improved. The warp and weft yarns of the fibrous base fabric may be any of synthetic fiber, natural fiber, semi-synthetic fiber, inorganic fiber, or a mixed fiber composed of two or more of these, but its workability and versatility In consideration, it is preferable to use synthetic fiber yarns such as polypropylene fiber, polyethylene fiber, vinylon fiber, polyester fiber, aromatic polyester fiber, nylon fiber, aromatic polyamide fiber, acrylic fiber, polyurethane fiber and the like. Moreover, you may use multifilament yarns, such as glass fiber, a silica fiber, an alumina fiber, and a carbon fiber, as an inorganic fiber. These fiber yarns may have any shape such as multifilament yarn, short fiber spun yarn, monofilament yarn, split yarn, tape yarn, etc., but use multifilament yarn. Is preferred. As the fiber woven fabric used for the polyolefin resin tarpaulin of the present invention, the cyclic imino ether group of the cyclic imino ether group-containing resin is formed at the lamination interface between the warp / weft yarn of the fibrous base fabric and the polyolefin resin layer. Plain woven fabric with multifilament fiber yarns composed of fibers that can form a cross-linking adhesive structure (especially oxazoline group) with a ring opening, such as polyester fibers, nylon fibers, polypropylene fibers, vinylon fibers, and mixed fibers thereof Is preferably used.

  Although there is no restriction | limiting in the kind of multifilament yarn used for the fibrous base fabric of this invention, The thing of 139 dtex (125 denier)-2222 dtex (2000 denier), especially 278 dtex (250 denier)-1111 dtex (1000 denier) It is preferable to use a multifilament yarn. Further, the fibrous base fabric used in the present invention is preferably a plain plain weave. There is no particular limitation on the number of warp yarns and weft threads of the woven fabric for fibrous base fabric, but multifilament yarns of 139 dtex (125 denier) to 2222 dtex (2000 denier) per warp / weft 2.54 cm (1 inch) 8 to 38 woven fabrics obtained, for example, when using a 555 dtex (500 denier) multifilament yarn, a plain woven fabric obtained with 14 to 24 implantations per 1 inch. In the case of using 1111 dtex (1000 denier) multifilament yarn, a plain woven fabric obtained by driving about 12 to 22 per 2.54 cm (1 inch) can be used. Moreover, it is preferable that the porosity (missing) of these fibrous base fabrics is 5 to 30%, More preferably, it is 8 to 24%. If the porosity is less than 5%, the flexibility of the tarpaulin obtained due to the yarn density being too high, and the bridge between the two polyolefin resin films formed on the front and back surfaces of the fibrous base fabric In some cases, the fusing property or mutual bridging fusing property is lowered, and the dynamic durability is insufficient. If the porosity exceeds 30%, the flexibility of the resulting base fabric and the bridge fusing property of the film will be improved, but the dimensional stability of the tarpaulin obtained will be low due to the low fiber yarn content in the weft direction. May be insufficient, and the tear strength may be reduced. The porosity is expressed by a value (%) obtained by calculating a percentage of the area of the fiber yarn in the unit area of the fibrous base fabric and subtracting the value from 100. For the measurement of the porosity, it is preferable to use an area of 10 cm in the warp direction × 10 cm in the weft direction as a unit area. In addition, the fibrous base fabric may be preliminarily applied with an adhesive, resin impregnation processing, water absorption prevention treatment, flameproofing treatment, and the like. For example, the above-mentioned styrenic copolymer resins (SBS, SIS, SVIS, SEBS, SEPS, SB, SI, SEP, SEP, and the like, as well as these styrenic copolymer resins and isocyanate compounds are used for the adhesion treatment of the fibrous base fabric. , An aziridine compound, an oxazoline compound, a carbodiimide compound or the like in combination with a crosslinking agent) dissolved in an organic solvent or finely dispersed.

  In the polyolefin resin tarpaulin of the present invention, a polyolefin resin film is laminated on both the front and back surfaces of the fibrous base fabric. Lamination methods include calender topping method, T-die extrusion laminating method, calender method, T-die extrusion method, inflation method for thermal lamination on each side of the fibrous base fabric simultaneously with the molding process of polyolefin resin film. For example, a method may be used in which a polyolefin resin film is molded by a method or the like, and two sheets are thermocompression-bonded simultaneously on both front and back surfaces of a fibrous base fabric using a laminator. In the production of the polyolefin resin tarpaulin of the present invention, when a method of thermocompression bonding a polyolefin resin film molded by a calender method to a fibrous base fabric is used, the polyolefin resin layer and the fibrous base fabric are laminated on the interface. The formation of a crosslinked adhesive structure by ring opening of the cyclic imino ether group (particularly the oxazoline group) of the cyclic imino ether side chain group-containing resin is easy and highly efficient. At this time, since the two polyolefin resin films on the front and back sides are melt-bridged through the voids in the fibrous base fabric, the contact surface area between the polyolefin resin layer and the fibrous base fabric increases, and the cyclic imino Since the cross-linked structure by the ether side chain group-containing resin is uniformly formed on the side surface of the yarn, it is possible to enhance the adhesion effect by the resin bridge, and the heat resistant creep resistance of the present invention is excellent. A flame retardant polyolefin resin tarpaulin can be obtained.

When the polyolefin-based resin tarpaulin of the present invention is used as a raw material for membrane structures such as medium- and large-sized tents, awning tents, and tent warehouses, an antifouling layer is particularly provided on one or more surfaces of the tarpaulin in order to maintain its aesthetics. It may be formed. As an antifouling layer, i). One or more photocatalytic substance-containing layers selected from titanium oxide (TiO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), tin oxide (SnO ₂ ), or ii). An antifouling layer containing one or more antifouling resins selected from acrylic resins, acrylic-silicon resins, and fluorine resins, or an antifouling layer in which silica fine particles are blended with the antifouling resin is included.

The photocatalyst substance-containing layer used for the antifouling layer preferably contains 9 to 70% by mass of a photocatalyst substance and 25 to 90% by mass of a metal oxide gel and / or a metal hydroxide gel. It is preferable that 1-20 mass% of the total mass of the silicon compound is included, the thickness thereof is preferably 0.1-10 μm, and the coating film contains these compounds. Can be applied to the surface of the polyolefin resin layer and dried. At this time, it is preferable to provide an intermediate protective layer for protecting the polyolefin resin layer from the active action of the photocatalyst material between the polyolefin resin layer and the photocatalyst material-containing layer. The photocatalytic substance may be one or more selected from titanium oxide (TiO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), and tin oxide (SnO ₂ ). The photocatalytic activity can be enhanced by doping a metal such as Pt, Rh, RuO ₂ , Nb, Cu, Sn, or NiO and a metal oxide. The photocatalytic substance is composed of silica, (synthetic) zeolite, titanium zeolite, zirconium phosphate, calcium phosphate, hydrotalcite, hydroxyapatite, silica alumina, calcium silicate, diatomaceous earth, etc., and an average primary particle size of 0.01 to 10 μm. The photocatalytic substance may be supported on 0.05 to 5 μm inorganic porous fine particles. The photocatalyst-supported particles are formed by surface treatment of inorganic porous fine particles to which a sol-gel thin film production process using a metal alcoholate containing a photocatalytic substance is applied. Further, the metal oxide gel and the metal hydroxide gel are specifically silica sol, alumina sol, zirconia sol, niobium oxide sol, etc., and these fix the photocatalytic substance in the coating film, and at the same time, the photocatalyst due to the porous property of these. The activity ability can be made efficient. As the silicon compound, polysiloxane can be used, and those obtained by hydrolysis and polycondensation of an alkoxysilane compound by a sol-gel method are preferable.

  As the photocatalytic substance, titanium oxide is preferably used. As the titanium oxide, titanium oxide sol, an alkali neutralized product of titanium oxide sol, peroxotitanic acid, or the like is preferably used. Further, as titanium oxide, hydrochloric acid peptizer type anatase titania sol having an average crystallite diameter of 5 to 20 nm, nitrate peptizer type anatase titania sol, and the like can be used. The content of the photocatalyst in the photocatalyst containing layer is preferably 10 to 70% by mass. As described above, the thickness of the photocatalytic substance-containing layer is preferably 0.1 to 10 μm, and more preferably 1 to 5 μm. When the thickness of the photocatalyst substance-containing layer is less than 0.1 μm, the antifouling property of the tarpaulin of the present invention is insufficient, and when it exceeds 10 μm, the antifouling layer is likely to be cracked by bending. In addition, for the purpose of improving the abrasion resistance and the bending strength of the antifouling layer, the photocatalyst substance-containing layer preferably contains a silane coupling agent (alkoxysilane compound) with respect to the mass of the photocatalyst substance-containing layer. 10 mass%, more preferably 0.1 to 5 mass% can be added in combination, and by this, a polycondensation of the alkoxysilane compound hydrolyzed by the sol-gel method inside the antifouling layer Can be made. The intermediate protective layer provided between the photocatalytic substance-containing layer and the polyolefin resin layer includes a fluorine resin, a silicone resin, an acrylic-silicone copolymer resin, a fluoroolefin-acrylic copolymer resin, an acrylic resin, and the like. A blend with a fluoroolefin resin, an organosilicate compound, or a low-condensate thereof (for example, tetramethoxysilane having a multimerization degree of 2 to 10 or tetraethoxysilane) and a thin film with a hydrolyzate (silanol group-containing silane compound) These include, if necessary, hydrophilic fine particles such as silica and colloidal silica from the viewpoint of improving adhesion to the photocatalyst substance-containing layer, and in order to further improve the coating film durability, A ring agent (alkoxysilane compound) can be added. These intermediate layers can be formed by applying and drying the coating composition.

The antifouling layer may be an antifouling resin comprising at least one selected from an acrylic resin, an acrylic-silicon resin, and a fluorine resin, and the antifouling resin further contains silica fine particles. It may be. The antifouling layer made of the fluororesin may be a film or a coating film. For forming an antifouling layer with a coating film, it is preferable to use a fluoroolefin copolymer resin that is soluble in an organic solvent or an aqueous dispersion of a fluoroolefin copolymer resin. Moreover, it is preferable to use what contains the hydroxyl group which can produce | generate a crosslinked part by combined use with a hardening | curing agent as a fluoroolefin copolymer resin in molecular structure. Specific examples of fluoroolefin monomers include vinyl fluoride (VF), vinylidene fluoride (VdF), trifluoroethylene (TrEE), tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), and hexafluoropropylene (HFP). ) And the like, and a monomer having an olefin skeleton such as ethylene, propylene, and α-olefin containing one or more fluorine atoms in the structural unit, and in particular, a VdF copolymer resin containing VdF is an organic solvent. It is preferable as the antifouling resin of the present invention because of its excellent solubility in water. These specifically include VdF-TFE copolymer resin, VdF-CTFE copolymer resin, TFE-CTFE copolymer resin, VdF-TFE-CTFE copolymer resin, and the like. A third component such as TrEE or HFP may be included. In particular, the fluoroolefin copolymer resin soluble in an organic solvent is a copolymer resin of a fluoroolefin and a vinyl monomer represented by CF ₂ = CFX (X is —H, —F, —CF ₃ ). Is preferred. Commercially available products of such paint-type fluororesins include: Lumiflon (Asahi Glass Co., Ltd.), Trademark: Cefral Coat (Central Glass Co., Ltd.), Trademark: Zaffron (Toa Gosei Co., Ltd.), Trademark: Zeffle (Daikin Kogyo Co., Ltd.), Trademark: Fluonate (Dainippon Ink Industry Co., Ltd.), Trademark: Floren (Nippon Synthetic Rubber Co., Ltd.), Trademark: Kainer (Atchem), and the like. These fluoroolefin copolymer resins contain reactive groups such as hydroxyl groups and carboxyl groups in the copolymerized vinyl component, and curing agents (crosslinking agents) such as isocyanate compounds, aziridine compounds, oxazoline compounds, carbodiimide compounds, and melamine compounds. Wear resistance of the coating film obtained by reacting with fluoroolefin copolymer resin (solid content) in terms of solid content, preferably 1 to 20 mass%, more preferably 3 to 15 mass% And weather resistance can be improved. Of these, isocyanate compounds are particularly preferred because of their excellent reactivity with hydroxyl groups, and aliphatic polyisocyanate compounds and alicyclic polyisocyanate compounds are particularly preferred from the viewpoint of weather resistance. Further, as the fluoroolefin copolymer resin soluble in an organic solvent, a copolymer resin of the above fluoroolefin monomer and an acrylic monomer can be used, and the fluoroolefin-acrylic copolymer resin thus obtained can be used. The fluoroolefin component is preferably contained in a proportion of 35 to 85 mol%, more preferably 40 to 70 mol% as a total amount.

  The antifouling layer acrylic resin is, for example, an alkyl acrylate ester having an alkyl group having 1 to 18 carbon atoms, such as methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate. , And polymers of n-hexyl acrylate, etc .; alkyl methacrylates having 1 to 18 carbon atoms in the alkyl group, such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, methacryl A polymer of n-butyl acid and 2-ethylhexyl methacrylate can be selected. The acrylic resin may be a copolymer resin of two or more of the above monomers. The acrylic resin may contain up to about 30% by mass of a copolymerizable monomer that can be copolymerized with an acrylic monomer. These include, for example, ethylenically unsaturated carboxylic acids, acrylamide compounds, and hydroxyl groups. (Meth) acrylic acids, epoxy group-containing (meth) acrylic acids, α-olefins, vinyl ethers, alkenyls, vinyl esters, aromatic vinyl compounds, and the like. The acrylic resin can be blended with a fluoroolefin copolymer resin, and the blend amount (solid content) of the acrylic resin is based on 100 parts by mass of the fluoroolefin copolymer resin (solid content). The amount is preferably 5 to 75 parts by mass, and more preferably 10 to 50 parts by mass. Particularly for acrylic resins, 0.01 to 5% by mass of an ultraviolet absorber relative to the acrylic resin, in particular, a polymer compound obtained by grafting an ultraviolet absorber to an acrylic copolymer resin, and an ultraviolet absorber for an acrylic compound. From the viewpoint of weather resistance, it is preferable to contain 1 to 5% by mass of the grafted polymerizable compound with respect to the acrylic resin. As the acrylic resin, an acrylic-silicon resin grafted with a hydrolyzate of a silane coupling agent can also be used.

Silica in acrylic resin, acrylic-silicon resin, fluororesin (fluoroolefin copolymer resin), or blend of fluororesin (fluoroolefin copolymer resin) and acrylic resin that forms an antifouling layer When fine particles are blended, the effect of suppressing rain streak stains is obtained, and silica fine particles are blended with a hydrophobic resin system such as a fluororesin or a blend of a fluororesin and an acrylic resin. Therefore, the surface can be improved to be hydrophilic, and these are effective in suppressing rain stripe stains. The effect of preventing rain stains is remarkable when silica fine particles are blended with a fluororesin, but in secondary workability such as tarpaulin lap joint, especially high frequency fusion, hot air fusion, etc. A blend of acrylic resin with silica fine particles is most preferred. The blend ratio of the fluororesin and the acrylic resin is preferably 5 to 75 parts by mass, more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the fluororesin. The silica (SiO ₂ ) fine particles are selected from amorphous silica such as anhydrous silica synthesized by a dry method and hydrous silica synthesized by a wet method. In particular, wet silica having a large number of silanol groups (Si—OH groups) on the surface is preferable because of its excellent hydrophilicity imparting effect. Synthetic silica having an average agglomerated particle size (Cole counter method) of 1 to 20 μm, particularly 2 to 10 μm, and a BET specific surface area of 40 to 400 m ² / g is excellent in hydrophilicity imparting effect and is preferable. It is preferable that the compounding quantity of a silica fine particle is 10-200 mass parts with respect to 100 mass parts of antifouling resin solid content, More preferably, it is 30-100 mass parts. If the blending amount of the silica fine particles is less than 10 parts by mass, a sufficient rain streak stain inhibiting effect may not be obtained. If the blending amount exceeds 200 parts by mass, the resulting antifouling layer has insufficient wear strength. And the durability of the tarpaulin may be insufficient. Further, colloidal silica such as silica sol of an aqueous dispersion medium obtained by cation exchange of a sodium silicate solution or silica sol having a BET average particle diameter of 10 to 20 nm using an organic solvent as a dispersion medium may be used.

  In forming the antifouling layer, it is preferably formed through a primer layer formed on the polyolefin resin layer. Examples of the primer agent include the aforementioned styrene copolymer resins (SBS, SIS, SVIS, SEBS, SEPS, SB, SI, SEP, SEP, and the like, and these styrene copolymer resins and isocyanate compounds, aziridine compounds, oxazolines. A compound or a combination product of a crosslinking agent such as a carbodiimide compound) dissolved in an organic solvent or a finely dispersed dispersion can be used. Examples of the method for applying the above-described antifouling layer-forming coating agent on the polyolefin resin layer (or intervening primer layer) of tarpaulin include, for example, gravure coating method, micro gravure coating method, comma coating method, roll coating method, reverse A roll coat method, a bar coat method, a flow coat method, a spray coat, or the like can be selected. The antifouling layer preferably has a thickness of 0.1 to 50 μm (the photocatalytic substance-containing layer is a 0.1 to 10 μm coating film). If the antifouling layer thickness is less than 0.1 μm, the antifouling effect of the obtained tarpaulin may be insufficient and may not last long. If the antifouling layer thickness exceeds 50 μm, the required number of coatings However, the antifouling effect may not be obtained. Further, on the back surface of the tarpaulin on which the antifouling layer is formed, a back surface coating layer is preferably formed by an acrylic resin, a fluorine resin, or a blend of a fluorine resin and an acrylic resin. By doing so, the thermal fusion property of the tarpaulin lap joint is improved. The back coating layer is particularly preferably a combination of the same resin type as the antifouling layer.

  For the joining and sewing of the polyolefin resin tarpaulin of the present invention, it is possible to use a thermal fusion method such as a high frequency (welder) fusion method, a hot plate fusion method, a hot air fusion method, or an ultrasonic fusion method. In particular, the high frequency fusion method is preferable because it is highly versatile, efficient, and economical. In particular, in the high-frequency fusion method and thermal fusion method, the ring-opening of the cyclic iminoether side chain group-containing resin contained in the polyolefin-based resin layer, generation of the cross-linked adhesive structure, and generation of the cross-linked structure have been completed. Heat melting to make it possible, and by doing so, the lamination / contact interface between the polyolefin resin film and the fibrous base fabric and the cross-linked structure inside the polyolefin resin layer become more dense, and a higher level of heat-resistant creep resistance can be obtained. Is possible.

ＪＩＳ Ａ １３２２法
実施例・比較例で得られたサンプルを用い、ＪＩＳ Ａ １３２２の加熱試験から、３０秒加熱・２分加熱を抜粋し評価を実施した。評価基準は以下に示し、防炎２級以上で防炎性が良好であるとの判断基準とした。

≪防炎性≫
傾斜角３０度、及び垂直の屋外設置試料について、初期の試料を基準とし、屋外曝露６ヶ月後、１２ケ月後の試料表面の色差ΔＥ値を測定し、防汚性を下記のように判定した。（色差ΔＥ値はＪＩＳ Ｚ−８７２９による）
ΔＥ＝ ０〜 ５未満：○：汚れが軽微で初期の状態を維持して いる。
ΔＥ＝５〜１０未満： △ ：汚れ、または雨筋汚れが目立つが水 洗除去可能である。
ΔＥ＝１０以上 ： × ：汚れと雨筋が酷く、水洗除去が困難 である。
上記試験結果を表４〜表８に記す。 The present invention will be further described with reference to the following examples and comparative examples, but the present invention is not limited to the scope of these examples.
Evaluation method << Measurement of shear strength >>
The ends of two polyolefin resin tarpaulins are linearly overlapped with a width of 4 cm and a weld bar of 4 cm x 30 cm (tooth shape: convex part is 4 cm wide linearly shaped with 9 intervals / 25.4 mm, convex part height 0.5 mm: High-frequency welder fusion machine (YF-7000, manufactured by Yamamoto Vinita Co., Ltd.) equipped with 9 linear recesses of 9 cm / 25.4 mm and recess depth of 0.5 mm with equidistant recesses of 4 cm width: output 7 kW ) Was used for high-frequency fusion bonding of tarpaulins. In addition, a sample having a width of 3 cm including the fusion bonded portion is taken, a shear test (JIS standard L1096) of the fusion bonded portion is performed, and the fracture strength is measured and the fracture state of the bonded portion is visually evaluated according to the following criteria. did.
Evaluation criteria
○: The body is destroyed.
Δ: The joint is destroyed.
X: The joint portion is broken due to thread dropout.
≪Heat resistance creep test≫
The heat-resistant creep test is the same as that for measuring the shear strength described above. From the welder fusion sheet, a test piece having an overlap width of 4 cm, a test piece width of 3 cm, and a test piece length of 30 cm is taken as a heat-resistant creep test piece. The heat resistance creep resistance test was evaluated using a machine (Toyo Seiki Seisakusho Co., Ltd .: 100 LDR type) at 1/10 load of 60 ° C. × main body breaking strength.
Evaluation criteria
○: After 24 hours, the joint is not broken and can withstand the load. <Breakdown time>
(Triangle | delta): A junction part shears and destroys in less than 24 hours. <Breakdown time>
X: The joint breaks and breaks within 1 hour. <Breakdown time>
Fracture state: The state of shear fracture is visually observed and recorded. (Joint thread breakage breakage, body breakage, etc.)
≪Processability≫
A 6-inch diameter two roll (test roll) was used, the gap between the rolls was set to 1 mm, and the resin kneading temperature was set to 150 ° C. 100 g of a polyolefin resin compound used in the following Examples and Comparative Examples was added to this test roll, the compound was kneaded for 20 minutes, and the release state of the core compound from the roll was visually observed and evaluated.
≪Fireproofing≫
As a flameproof evaluation method, evaluation was performed by the following evaluation method.
JIS L 1091 method The samples obtained in the examples and comparative examples have a mass exceeding 450 g / m ² , so the A-2 method (45 ° Meckel burner method, 2 minutes heating, 6 seconds ignition) and In consideration of the combustibility of the membrane material, evaluation was made by two methods, D method (flame contact test). The evaluation criteria are shown below, and the criteria for determining that the flameproof property is good are Category 3 or higher by Method A-2 and Category 2 or higher.

JIS A 1322 method Using the samples obtained in Examples and Comparative Examples, 30 seconds of heating and 2 minutes of heating were extracted from the heating test of JIS A 1322, and evaluated. The evaluation criteria are shown below, and used as criteria for determining that the flameproofness is 2nd grade or higher and that the flameproofness is good.

≪Fireproofing≫
With respect to samples installed outdoors at an inclination angle of 30 degrees and vertically, the color difference ΔE value of the sample surface after 6 months of outdoor exposure and 12 months later was measured based on the initial sample, and the antifouling property was determined as follows. . (Color difference ΔE value is according to JIS Z-8729)
ΔE = 0 to less than 5: ○: Dirt is slight and the initial state is maintained.
ΔE = less than 5 to 10: Δ: Dirt or rain streak is conspicuous, but can be removed by washing with water.
ΔE = 10 or more: ×: Dirt and rain streaks are severe, and it is difficult to remove with water.
The test results are shown in Tables 4-8.

Example 1
In the presence of 80 parts by mass of an ethylene-vinyl acetate copolymer resin (trademark: Evertate K2010, MFR 3.0, density 0.950, VA content 25% by mass, manufactured by Sumitomo Chemical Co., Ltd.) and a metallocene catalyst A polyolefin resin blend composed of 20 parts by mass of polymerized linear low density polyethylene resin (trademark: Kernel KF270, MFR 2.0, density 0.907, manufactured by Nippon Polychem Co., Ltd.) Part, (2,4-bis [(N-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethyl) as a basic hindered amine compound Amino) -s-triazine), 2 parts by mass, melamine-coated ammonium polyphosphate (polymerization degree n = 1000, trademark: exolite AP4) 2: 25 parts by mass of Clariant Japan Co., Ltd.) and 25 parts by mass of melamine cyanurate (trade name: MC640: manufactured by Nissan Chemical Co., Ltd.) are mixed, and the cyclic imino ether group is further mixed. As a cyclic iminoether side chain group-containing resin which is an oxazoline group, 5 parts by mass of a copolymer of styrene and 2-isopropenyl-2-oxazoline (2-isopropenyl-2-oxazoline copolymerization ratio 5% by mass); 10 parts by mass of synthetic amorphous silica (trademark: NIPSEAL E200A, average particle size 3 μm, manufactured by Nippon Silica Kogyo Co., Ltd.) and phosphate ester lubricant (trademark: LTP-2, manufactured by Kawaken Fine Chemical Co., Ltd.) 2 Parts by weight, 5 parts by weight of a rutile titanium dioxide pigment, 0.2 parts by weight of a benzophenone-based ultraviolet absorber, and 0.2 parts by weight of a phenol-based antioxidant. The resulting blend was kneaded for 5 minutes with a test roll set at a temperature of 150 ° C. (two rolls with a 6-inch diameter: manufactured by Nishimura Seisakusho Co., Ltd.), and the VA content in the resin blend was 20% by mass. I got a compound. The obtained compound was calendered on the test roll with a polyolefin resin film having a thickness of 0.17 mm. Next, this film was made into a polyester plain woven fabric (555.5 dtex (500 denier) polyester multifilament, yarn density warp 21 yarns / 2.54 cm × weft yarn 21 yarns / 2.54 cm, porosity 18%, mass 80 g / m ^2. ) And a laminator having a heat roll set to 150 ° C. and a pressure-bonding roll pair on both front and back surfaces, and a halogen-free flame-retardant polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was produced. .

Example 2
A polyolefin-based resin tarpaulin was produced in the same manner as in Example 1. However, in the polyolefin resin blend for the polyolefin resin layer of Example 1, 20 parts by mass of a linear low density polyethylene resin (trademark: Kernel KF270, manufactured by Nippon Polychem Co., Ltd.) was added to polypropylene as an EPR-PP reactor resin. Type resin (trade name: Catalloy KS-353P: MFR 0.45 g / 10 min / 230 ° C., EPR 60 mass%, PP 40 mass%: Sun Allomer Co., Ltd.) 20 parts by mass. The VA-containing mass in the obtained resin blend was 20% by mass. Moreover, 2 mass parts of basic hindered amine compounds of Example 1 were changed to 2 mass parts of basic hindered amine compounds (trademark: FLAMESTAB NOR 116FF) manufactured by Ciba Specialty Chemicals. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 3
In the same manner as in Example 1, a polyolefin-based resin tarpaulin was produced. However, in the polyolefin resin blend for the polyolefin resin layer of Example 1, 20 parts by mass of a linear low density polyethylene resin (trademark: Kernel KF270, manufactured by Nippon Polychem Co., Ltd.) was added to a styrene copolymer resin (trademark). : Hibler 7125 (HVS-3): Styrene-hydrogenated vinylisoprene-styrene copolymer resin: MFR 6.0 g / 10 min / 230 ° C .: Styrene content 20% by mass: manufactured by Kuraray Co., Ltd.) 20 parts by mass . The VA-containing mass in the obtained resin blend was 20% by mass. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 4
A polyolefin-based resin tarpaulin was produced in the same manner as in Example 1. However, in the polyolefin resin blend for the polyolefin resin layer of Example 1, 80 parts by mass of ethylene-vinyl acetate copolymer resin (trademark: Evaate K2010, manufactured by Sumitomo Chemical Co., Ltd.) It changed to 80 mass parts of polymer resin (trademark: ACRIFTH WH206, MFR 2.0, density 0.940, MMA content 20 mass%, manufactured by Sumitomo Chemical Co., Ltd.). The MMA-containing mass in the obtained resin blend was 16% by mass. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 5
A polyolefin-based resin tarpaulin was produced in the same manner as in Example 1. However, in the polyolefin resin blend for the polyolefin resin layer of Example 1, 40 parts by mass of 80 parts by mass of an ethylene-vinyl acetate copolymer resin (trademark: Evaate K2010, manufactured by Sumitomo Chemical Co., Ltd.) Replacement with 40 parts by mass of an ethylene-methyl methacrylate copolymer resin (trademark: ACRIFTH WH206, manufactured by Sumitomo Chemical Co., Ltd.) described in Example 4 was performed. VA and MMA containing mass in the obtained resin blend were 18 mass%. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 6
A polyolefin-based resin tarpaulin was produced in the same manner as in Example 1. However, in the polyolefin resin blend for the polyolefin-based resin layer of Example 1, the amount of ethylene-vinyl acetate copolymer resin (trademark: Evertate K2010, manufactured by Sumitomo Chemical Co., Ltd.) was reduced to 40 parts by mass, The amount of metallocene linear low-density polyethylene resin (trademark: Kernel KF270, manufactured by Nippon Polychem Co., Ltd.) was increased to 60 parts by mass. The VA-containing mass in the obtained resin blend was 10% by mass. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 7
A polyolefin-based resin tarpaulin was produced in the same manner as in Example 1. However, instead of the polyolefin resin blend for the polyolefin resin layer of Example 1, 50 parts by mass of an ethylene-vinyl acetate copolymer resin (trademark: Evertate K2010, manufactured by Sumitomo Chemical Co., Ltd.), a metallocene linear chain 30 parts by mass of low-density polyethylene resin (trademark: Kernel KF270, manufactured by Nippon Polychem Co., Ltd.) and the styrene copolymer resin described in Example 3 (trademark: Hybler 7125 (HVS-3), manufactured by Kuraray Co., Ltd.) ) A polyolefin resin blend consisting of 20 parts by mass was used. The VA-containing mass in this resin blend was 12.5% by mass. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 8
A polyolefin-based resin tarpaulin was produced in the same manner as in Example 1. However, instead of the polyolefin resin blend for the polyolefin resin layer of Example 1, 50 parts by mass of an ethylene-vinyl acetate copolymer resin (trademark: Evertate K2010, manufactured by Sumitomo Chemical Co., Ltd.), described in Example 2 30 parts by mass of a polypropylene resin (trademark: Catalloy KS-353P: manufactured by Sun Allomer Co., Ltd.), which is an EPR-PP reactor resin, and a styrene copolymer resin (trademark: Hibler 7125 (HVS- 3) A blend consisting of 20 parts by mass (manufactured by Kuraray Co., Ltd.) was used. The VA-containing mass in the obtained resin blend was 12.5% by mass. Further, instead of 2 parts by mass of the basic hindered amine compound of Example 1, 2 parts by mass of basic hindered amine compound (trademark: FLAMESTTAB NOR 116FF) manufactured by Ciba Specialty Chemicals Co., Ltd. was used. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 9
A polyolefin-based resin tarpaulin was produced in the same manner as in Example 1. However, instead of the polyolefin resin blend for the polyolefin resin layer of Example 1, 30 parts by mass of an ethylene-vinyl acetate copolymer resin (trademark: Evertate K2010, manufactured by Sumitomo Chemical Co., Ltd.), described in Example 4 20 parts by mass of an ethylene-methyl methacrylate copolymer resin (trade name: ACRIFTH WH206, manufactured by Sumitomo Chemical Co., Ltd.), a polypropylene resin (trade name: Catalloy KS-) which is an EPR-PP reactor resin described in Example 2 353P (manufactured by Sun Allomer Co., Ltd.) and a resin blend comprising 20 parts by mass of the styrene copolymer resin described in Example 3 (trademark: Hibler 7125 (HVS-3) manufactured by Kuraray Co., Ltd.) are used. It was. The MMA and VA-containing mass in this resin blend was 11.5% by mass. In addition, 2 parts by mass of the basic hindered amine compound used in Example 1 was changed to 2 parts by mass of basic hindered amine compound (trademark: FLAMESTTAB NOR 116FF) manufactured by Ciba Specialty Chemicals. A halogen-free flame-retardant polyolefin-based resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained.

Example 10
Polyester plain woven fabric described in Example 1 (555.5 dtex (500 denier) polyester multifilament yarn density warp 21 yarns / 2.54 cm × weft yarn 21 yarns / 2.54 cm porosity 18% mass 80 g / m ² ) Adhesion treatment was performed.
<Adhesive treatment agent>
Ionomer resin dispersion (Trademark: Chemipearl S-3
00: Zinc salt of ethylene-methacrylic acid copolymer, solid content 35% by mass: manufactured by Mitsui Chemicals Co., Ltd. 100 parts by mass Oxazoline-based cross-linking agent (trademark: Epocross WS-500: solid content 40% by mass: Nippon Shokubai) (Made by Co., Ltd.) 20 parts by mass The polyester plain woven fabric is immersed in the above-mentioned adhesive treatment agent bath, and the woven fabric is pulled up and simultaneously squeezed with a nip roll (wet adhesion mass 80 g / m ² ). Drying was performed for 2 minutes in a hot stove. The mass of the polyester fiber plain fabric after the adhesion treatment was 108.0 g / m ² . A polyolefin resin layer was formed in the same manner as in Example 1 on both the front and back surfaces of this base fabric. A polyolefin resin tarpaulin having a thickness of 0.44 mm and a mass of 510 g / m ² was obtained.

Comparative Example 1
Tarpaulin was produced in the same manner as in Example 1. However, 2 parts by mass of the basic hindered amine compound, 25 parts by mass of melamine-coated ammonium polyphosphate, 25 parts by mass of melamine cyanurate, and 5 parts by mass of the oxazoline side chain group-containing resin were omitted from the composition of the polyolefin resin layer of Example 1. . A polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 320 g / m ² was obtained. This tarpaulin has poor flameproofness and inferior heat resistant creep resistance at the joint.

Comparative Example 2
Tarpaulin was produced in the same manner as in Example 1. However, 2 parts by mass of the basic hindered amine compound, 25 parts by mass of melamine-coated ammonium polyphosphate, and 25 parts by mass of melamine cyanurate were omitted from the composition of the polyolefin resin layer of Example 1. A polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 340 g / m ² was obtained. This tarpaulin was inferior in flame resistance.

Comparative Example 3
Tarpaulin was produced in the same manner as in Example 1. However, from the composition of the polyolefin-based resin layer of Example 1, 2 parts by mass of the basic hindered amine compound and 5 parts by mass of the oxazoline side chain group-containing resin are omitted, and the blending amounts of melamine-coated ammonium polyphosphate and melamine cyanurate are respectively set. The amount was changed to 40 parts by mass. A polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 560 g / m ² was obtained. This tarpaulin had poor processability, poor flameproofness, and inferior heat resistant creep resistance at the joint.

Comparative Example 4
Tarpaulin was produced in the same manner as in Example 1. However, 5 parts by mass of the oxazoline side chain group-containing resin was omitted from the composition of the polyolefin resin layer of Example 1. A polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 470 g / m ² was obtained. This tarpaulin has flame resistance but is inferior in heat-resistant creep resistance at the joint.

Comparative Example 5
Tarpaulin was produced in the same manner as in Example 1. However, the polyolefin resin of the polyolefin resin layer described in Example 1 was changed to 100 parts by mass of the metallocene linear low density polyethylene resin of Example 1, and the composition of Example 1 contained an oxazoline side chain group. The blending of 5 parts by mass of resin was omitted. A polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 480 g / m ² was obtained. Since this tarpaulin cannot be fused at high frequency, a joining piece was prepared by simple heat sealing, but the heat resistance creep resistance of the joining portion was inferior.

Comparative Example 6
In the same manner as in Example 8, a polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 560 g / m ² was produced. However, from the composition of the polyolefin-based resin layer of Example 8, 2 parts by mass of the basic hindered amine compound and 5 parts by mass of the oxazoline side chain group-containing resin were omitted, and the blending amounts of melamine-coated ammonium polyphosphate and melamine cyanurate were The amount was changed to 40 parts by mass. This tarpaulin has poor workability, flame resistance, and heat resistance creep resistance at the joint.

Comparative Example 7
In the same manner as in Example 8, a polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 470 g / m ² was produced. However, 5 parts by mass of the oxazoline side chain group-containing resin was omitted from the composition of the polyolefin resin layer of Example 8. This tarpaulin had poor heat resistance creep resistance at the joint.

Comparative Example 8
In the same manner as in Example 4, a polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 560 g / m ² was produced. However, from the composition of the polyolefin-based resin layer of Example 4, 2 parts by mass of the basic hindered amine compound and 5 parts by mass of the oxazoline side chain group-containing resin were omitted, and the compounding amounts of melamine-coated ammonium polyphosphate and melamine cyanurate were The amount was changed to 40 parts by mass. This tarpaulin had poor workability, poor flameproofness, and unsatisfactory heat resistance creep resistance at the joint.

Comparative Example 9
In the same manner as in Example 4, a polyolefin resin tarpaulin having a thickness of 0.43 mm and a mass of 470 g / m ² was produced. However, 5 parts by mass of the oxazoline side chain group-containing resin was omitted from the composition of the polyolefin resin layer of Example 4. This tarpaulin had poor heat resistance creep resistance at the joint.

Comparative Example 10
A tarpaulin was produced in the same manner as in Example 1. However, in the composition of the polyolefin resin layer of Example 1, the amount of the oxazoline side chain group-containing resin was increased to 50 parts by mass. Although the film was rolled with a test roll, the film adhered to the surface of the hot roll and a film could not be obtained, and a tarpaulin could not be obtained.

Comparative Example 11
A tarpaulin was produced in the same manner as in Example 1. However, in the composition of the polyolefin resin layer of Example 8, the amount of the oxazoline side chain group-containing resin was increased to 50 parts by mass. Although the film was rolled with a test roll, the film adhered to the surface of the hot roll and a film could not be obtained, and a tarpaulin could not be obtained.

Comparative Example 12
Tarpaulin was produced in the same manner as in Example 1. However, in the composition of the polyolefin resin layer of Example 1, 5 parts by mass of the oxazoline side chain group-containing resin was changed to 5 parts by mass of a carbodiimide resin (trademark: Carbodilite HMV-8CA, Nisshinbo Co., Ltd.). Although the film was formed with a test roll, the carbodiimide resin was agglomerated and solidified, and the film adhered to the surface of the hot roll, resulting in poor workability. The obtained tarpaulin (thickness 0.43 mm, mass 480 g / m ² ) had poor heat-resistant creep properties at the joint, and partially did not meet the flameproof standard.

Comparative Example 13
Tarpaulin was produced in the same manner as in Example 8. However, in the composition of the polyolefin resin layer of Example 8, 5 parts by mass of the oxazoline side chain group-containing resin was changed to 5 parts by mass of a carbodiimide resin (trademark: Carbodilite HMV-8CA, Nisshinbo Co., Ltd.). Although the film was formed with a test roll, the carbodiimide resin was agglomerated and solidified, and the film adhered to the surface of the hot roll, resulting in poor workability. The obtained tarpaulin (thickness 0.43 mm, mass 480 g / m ² ) was poor in heat-resistant creep resistance at the joint, and partially did not meet the flameproof standard.

Comparative Example 14
Tarpaulin was produced in the same manner as in Example 8. However, in the composition of the polyolefin-based resin layer of Example 8, 5 parts by mass of the oxazoline side chain group-containing resin was a synthetic adsorbent containing crystallization water mainly composed of Mg and Al (Kyoward 500, Kyowa Chemical Industry ( Co.)) changed to 10 parts by mass. The obtained tarpaulin (thickness 0.43 mm, mass 480 g / m ² ) had poor heat resistance creep resistance at the joint and did not meet the flameproof standard.

Comparative Example 15
Tarpaulin was produced in the same manner as in Example 1. However, in the composition of the polyolefin resin layer of Example 1, 5 parts by mass of the oxazoline side chain group-containing resin was omitted, and a polyester fiber plain fabric subjected to the following adhesion treatment was used instead. A polyolefin resin tarpaulin having a thickness of 0.44 mm and a mass of 510 g / m ² was obtained. This tarpaulin was poor in heat-resistant creep resistance at the joint and partially did not meet the flameproof standard.
<Adhesive treatment agent>
Ionomer resin dispersion (Trademark: Chemipearl S-300: Zinc salt of ethylene-methacrylic acid copolymer, solid content 35% by mass: manufactured by Mitsui Chemicals, Inc.) 100 parts by mass Isocyanate-based crosslinking agent (Trademark: Aquanate AQ10)
0: 100% by mass of solid content: manufactured by Nippon Polyurethane Industry Co., Ltd.) 5 parts by mass

Comparative Example 16
Tarpaulin was produced in the same manner as in Example 8. However, in the composition of the polyolefin resin layer of Example 8, 5 parts by mass of the oxazoline side chain group-containing resin was omitted, and the bonded polyester fiber plain fabric described in Comparative Example 15 was used. A polyolefin resin tarpaulin having a thickness of 0.44 mm and a mass of 510 g / m ² was obtained. This tarpaulin had poor heat-resistant creep resistance at the joint, and partially did not meet the flameproof standard.

Comparative Example 17
Tarpaulin was produced in the same manner as in Example 1. However, in the composition of the polyolefin resin layer of Example 1, 5 parts by mass of the oxazoline side chain group-containing resin was omitted, and a polyester fiber plain fabric subjected to the following adhesion treatment was used. A polyolefin resin tarpaulin having a thickness of 0.44 mm and a mass of 510 g / m ² was obtained. This tarpaulin had poor heat-resistant creep resistance at the joint, and partially did not meet the flameproof standard.
<Adhesive treatment agent>
Ionomer resin dispersion (Trademark: Chemipearl S-
300: Zinc salt of ethylene-methacrylic acid copolymer, solid content 35
100% by mass Carbodiimide-based crosslinking agent (trademark: Carbodilite V-02, manufactured by Mitsui Chemicals, Inc.)
Solid content 40 wt%, Nisshinbo Co., Ltd.) 10 parts by mass

Comparative Example 18
Tarpaulin was produced in the same manner as in Example 8. However, in the composition of the polyolefin resin layer of Example 8, 5 parts by mass of the oxazoline side chain group-containing resin was omitted, and the bonded polyester fiber plain fabric described in Comparative Example 17 was used. A polyolefin resin tarpaulin having a thickness of 0.44 mm and a mass of 510 g / m ² was obtained. This tarpaulin had poor heat-resistant creep resistance at the joint, and partially did not meet the flameproof standard.

Comparative Example 19
Tarpaulin was produced in the same manner as in Example 1. However, in the blending of the polyolefin-based resin layer of Example 1, 5 parts by mass of the oxazoline side chain group-containing resin was omitted, and the bonded polyester fiber plain fabric described in Example 10 was used. A polyolefin resin tarpaulin having a thickness of 0.44 mm and a mass of 510 g / m ² was obtained. This tarpaulin has poor heat-resistant creep resistance at the joint, and partially does not meet the flameproof standard.

Comparative Example 20
Tarpaulin was produced in the same manner as in Example 8. However, in the composition of the polyolefin resin layer of Example 8, 5 parts by mass of the oxazoline side chain group-containing resin was omitted, and the bonded polyester fiber plain fabric described in Example 10 was used. A polyolefin resin tarpaulin having a thickness of 0.44 mm and a mass of 510 g / m ² was obtained. This tarpaulin had poor heat-resistant creep resistance at the joint, and partially did not meet the flameproof standard.

Example 11
An antifouling layer having the following composition was formed on one surface of the tarpaulin of Example 8. That is, the surface of the tarpaulin of Example 8 was coated on the surface of the polyolefin-based resin layer with a primer layer treatment solution shown in Formula 1 below at a coating amount of 15 g / m ² with a gravure coater, dried at 100 ° C. for 1 minute, and then cooled. Then, a primer layer of 1.5 g / m ² is formed, and then a treatment solution for the adhesion / protection layer having the composition shown in Formula 2 below is applied onto the primer layer with a gravure coater at a coating amount of 15 g / m ^2. Then, after drying at 100 ° C. for 1 minute and cooling, a 1.5 g / m ² adhesion / protection layer is formed, and then a photocatalyst substance-containing layer having the composition shown in Formula 3 below is formed on this adhesion / protection layer. The coating solution was applied with a gravure coater at a coating amount of 15 g / m ² , dried at 100 ° C. for 1 minute and then cooled to form an antifouling layer with a photocatalytic substance of 1.5 g / m ² .
<Formulation 1> Primer layer treatment solution composition
Styrene copolymer resin (Trademark: Hibler 7125
(HVS-3): Styrene-hydrogenated vinylisoprene-styrene copolymer resin: MFR 6.0 g / 10 min / 230 ° C .: Styrene content 20% by mass: Kuraray Co., Ltd.) 10 parts by mass
Toluene-methyl ethyl ketone (50/50 mass ratio)
100 parts by mass of solution
<Formulation 2> Adhesive / protective layer treatment solution composition
8 acrylic silicon resins with a silicon content of 3 mol%
Ethanol-ethyl acetate containing mass% (solid content)
(50/50 mass ratio) Solution 100 parts by mass
Methyl silicate MS51 (copolysiloxane)
8 parts by mass of 20% ethanol solution of Le Coat
Γ-Glycidoxypropylene as silane coupling agent
1 part by weight of rutrimethoxysilane
<Formulation 3> Photocatalyst antifouling layer treatment solution composition
Nitric acid acidic oxidation equivalent to 10% by mass of titanium oxide
Water-ethanol (50/50) in which titanium sol is dispersed
(Mass ratio) Solution 50 parts by mass
Nitric acid acidic silica corresponding to silicon oxide content of 10% by weight
Sol-dispersed water-ethanol (50/50 mass ratio)
50 parts by mass of solution

Example 12
An acrylic resin layer having the following composition was formed on both the front and back surfaces of the tarpaulin of Example 8. One of the front and back surfaces was an antifouling layer, and the other surface was a back surface layer for lap bonding. First, a primer layer treatment solution (same as Formulation 1 in Example 11) was applied to both sides of the polyolefin resin layer with a gravure coater at a coating amount of 15 g / m ² , dried at 100 ° C. for 1 minute, and then cooled. Then, a 1.5 g / m ² primer layer is formed, and then a solvent dilution of a resin composition of the following formulation 4 is used as an acrylic resin on the front and back primer layers using a gravure coater. ^Then , the coating was dried at 120 ° C. for 1 minute and then cooled to form an antifouling layer and a back surface layer for lap bonding with an acrylic resin of 5 g / m ^{2 on} each side.
<Formulation 4> Acrylic resin composition Acrylic resin (manufactured by Mitsubishi Rayon Co., Ltd., trademark: Acryprene Pellet HBS001) 20 parts by mass high molecular weight ultraviolet absorber (on the other hand, manufactured by Yushi Kogyo Co., Ltd., product number: UCI-635
L, [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone]) and methyl methacrylate 50 wt%: 50 wt% copolymer resin 1 part by mass

Example 13
An antifouling layer having the following composition was formed on one surface of the tarpaulin described in Example 8. That is, the primer layer treatment liquid (same as Formulation 1 in Example 11) was applied to both surfaces of the polyolefin resin layer with a gravure coater at a coating amount of 15 g / m ² , dried at 100 ° C. for 1 minute, and then cooled. A front and back primer layer of 1.5 g / m ² each was formed, and then a solvent of a resin composition of the following formulation 5 as a fluororesin (vinylidene fluoride-tetrafluoroethylene copolymer resin) on the surface of the surface primer layer The diluted solution is applied with a gravure coater at an application amount of 25 g / m ² , dried at 120 ° C. for 1 minute and then cooled to form an antifouling layer with a fluorine resin of 5 g / m ^2. the solvent dilution of acrylic resin composition of the formulation 4 is on the layer, using a gravure coater, was coated at a coverage of 25 g / m ^2, and cooled after drying 1 minute at 120 ° C., acrylic 3 g / m ² To form a rear surface treatment layer by the resin.
<Formulation 5> Fluorine-based resin composition Vinylidene fluoride-tetrafluoroethylene copolymer resin (manufactured by Elf Atchem Japan Co., Ltd., trademark: Kyner 7201) 20 parts by mass Diluting solvent (methyl ethyl ketone) 80 parts by mass

Example 14
An antifouling layer having the following composition was formed on one surface of the tarpaulin described in Example 8. That is, the primer layer treatment liquid (same as Formulation 1 in Example 11) was applied to both surfaces of the polyolefin resin layer with a gravure coater at a coating amount of 15 g / m ² , dried at 100 ° C. for 1 minute, and then cooled. A front and back primer layer of 1.5 g / m ² each is formed, and then a blend of fluorine resin and acrylic resin containing 25% by mass of silica fine particles on the surface primer layer (fluorine resin: acrylic resin) The solvent ratio of the resin composition of the following formulation 6 was applied at a coating amount of 25 g / m ² using a gravure coater, dried at 120 ° C. for 1 minute, cooled, and 5 g / m ^2. An antifouling layer containing silica fine particles was formed, and a solvent dilution of the acrylic resin composition of Formula 4 was applied onto the backside polyolefin resin layer at a coating amount of 25 g / m ² using a gravure coater. Apply, It cooled after drying 1 minute at 20 ° C., to form the backside treatment layer by acrylic resins 3 g / m ^2.
<Formulation 6> Blend composition of fluororesin and acrylic resin containing silica fine particles Acrylic resin (Made by Mitsubishi Rayon Co., Ltd., trademark: acrylprene pellet HBS001) 4 parts by mass of fluororesin (vinylidene fluoride) -Tetrafluoroethylene copolymer resin (manufactured by Elf Atchem Japan Co., Ltd., trademark: Kyner 7201) 12 parts by mass high molecular weight UV absorber (manufactured by Yushi Kogyo Co., Ltd., product number: UCI-635L)
) 50 wt%: 50 wt% copolymer resin of [2-hydroxy-4- (methacryloyloxyethoxy) benzophenone] and methyl methacrylate 1 part by mass silica fine particles (wet process amorphous silica, manufactured by Nippon Silica Kogyo Co., Ltd.) , Trademark: Nip seal E-220, average particle diameter 2 μm, BET specific surface area 130 m ² / g) 4 parts by weight diluent solvent (toluene-methyl ethyl ketone 50/50 parts by weight) 80 parts by weight

Example 15
An antifouling layer having the following composition was provided on one surface of the tarpaulin described in Example 8. That is, the primer layer treatment liquid (same as Formulation 1 in Example 11) was applied to both surfaces of the polyolefin resin layer with a gravure coater at a coating amount of 15 g / m ² , dried at 100 ° C. for 1 minute, and then cooled. A front and back primer layer of 1.5 g / m ² each was formed, and then a multilayer film composed of polyvinylidene fluoride (PVdF) resin / acrylic resin on the surface primer layer (manufactured by Kureha Chemical Co., Ltd., product number: KFC film ST-50Y (thickness 50 μm) is heat-laminated at 160 ° C. to form a 50 g / m ² film antifouling layer having a fluororesin layer as the outermost layer. the solvent dilution of 4 identical acrylic resin composition and, by using a gravure coater, was coated at a coverage of 25 g / m ^2, and cooled after drying 1 minute at 120 ° C., of 3 g / m ² acrylate To form a rear surface treatment layer by the system resin.

  From the evaluation results in Tables 4 to 7, obtained by blending a specific amount of cyclic iminoether side chain group-containing resin into a polyolefin resin composition containing a halogen-free flame retardant (preferably a specific basic hindered amine compound). The tarpaulins (Examples 1 to 10) obtained by laminating the polyolefin resin film on the fibrous base fabric have excellent heat resistance and creep resistance while having flame resistance comparable to that of polyvinyl chloride resin. In addition, it was confirmed that the high frequency fusion processing is easy. Moreover, from the evaluation results of Table 8, the antifouling layer containing the photocatalytic substance on the surface of the tarpaulin, the antifouling layer made of acrylic resin, acrylic-silicon resin, fluorine resin, or the like, or antifouling containing silica fine particles therein It was confirmed that the appearance of the tent film structure can be maintained by forming the layers (Examples 11 to 15).

The polyolefin resin tarpaulin obtained by the present invention enables the flame resistance comparable to that of a vinyl chloride resin tarpaulin with a chlorine- and bromine-free design, and also has the heat resistant creep resistance of the polyolefin resin tarpaulin, which has been considered difficult in the past. Since it is improved and has excellent high-frequency fusion properties, it can be handled in the same way as tarpaulin made of vinyl chloride resin. Further, the antifouling layer containing a photocatalytic substance in the outermost layer of the polyolefin resin tarpaulin of the present invention, or the antifouling layer made of an acrylic resin, an acrylic-silicon resin, a fluorine resin, or the like, or an antifouling layer containing silica fine particles therein. By providing the layer, it is possible to maintain the aesthetics of the tent membrane structure.
Therefore, the polyolefin-based resin tarpaulin of the present invention can be used as a substitute for polyvinyl chloride for uses such as large tents (pavilions), tent warehouses, awning tents, building curing sheets, internally illuminated signboards, etc. It exhibits high flameproofing properties and does not emit chlorine, hydrogen bromide gas or other toxic substances even when burned, and it does not contain plasticizers. And easy.

Claims (9)

A fibrous base fabric and a membrane material including a polyolefin-based resin layer laminated on both front and back surfaces,
The polyolefin resin layer includes a kneaded product of (1) a resin component, (2) a halogen-free flame retardant imparting component, and (3) a heat-resistant creep resistance improving component,
As the main resin element (a), the resin component (1) is one or more ethylene-based resins selected from ethylene-vinyl acetate copolymer resins and ethylene- (meth) acrylic acid (ester) copolymers. Including a copolymer resin,
The heat resistant creep resistance improving component (3) is represented by the following formula (I):

[In the formula (I), R ¹ and R ² each independently represent a hydrogen atom or an inert hydrocarbon group containing 18 carbon atoms, and n is a positive number of 1-5. Represents an integer of
And the content of the heat-resistant creep resistance improving component (3) is 0.5 with respect to 100 parts by mass of the resin component (1). A flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep, characterized by being in the range of ˜30 parts by mass.   The heat resistance according to claim 1, wherein the resin component (1) further includes at least one selected from polyethylene resin, ethylene-α-olefin copolymer resin, and soft polypropylene resin as the blend resin element (b). A flame-retardant polyolefin resin tarpaulin with excellent creep properties.   The resin component (1) is an ABA type styrene block copolymer resin (where A represents a styrene polymer block, B represents a butadiene polymer block, isoprene polymer) as an additional blend resin element (c). Block or vinyl isoprene polymer block), AB type styrene block copolymer resin (A and B are as defined above), styrene random copolymer resin, and styrene copolymer resin. The flame retardant polyolefin-based resin tarpaulin excellent in heat-resistant creep property according to claim 1 or 2, comprising at least one selected from hydrogenated resins.   The total mass of the vinyl acetate component and / or the (meth) acrylic acid (ester) component contained in the main resin element (a) contained in the resin component (1) is the total mass of the polyolefin resin layer (provided that The flame-retardant polyolefin-based resin tarpaulin excellent in heat-resistant creep property according to any one of claims 1 to 3, which is 5 to 30% by mass relative to a halogen-free flame retardant imparting component.   The crosslinked structure by ring-opening of the cyclic iminoether side chain group in the said heat-resistant creep resistance improving component (3) is formed in the lamination | stacking interface of the said polyolefin resin layer and the said fibrous base fabric. The flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property according to any one of -4.   The flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property according to any one of claims 1 to 5, wherein the cyclic imino ether side chain group-containing resin is an oxazoline group-containing copolymer resin. The halogen-free flame retardant imparting component (2) contains at least one basic hindered amine compound, and the basic hindered amine compound is represented by the following formula (II):

[However, in the formula (II), R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a). A hydrogen atom, b). A linear or branched alkyl group having 1 to 20 carbon atoms, c). Including one or more selected from -O-, -S-, -SO-, -SO _2- , -CO-, -COO-, -OCO-, -CONR-, -NRCO- and -NR- An alkyl group having 1 to 20 carbon atoms, d). An alkenyl group having 3 to 20 carbon atoms, e). An unsubstituted aryl group having 6 to 10 carbon atoms, f). An aryl group having 1 to 3 substituents selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, and a phenylalkyl group having 7 to 15 carbon atoms; R ⁷ represents an alkyl group having 2 to 18 carbon atoms, or a cycloalkyl group having 5 to 12 carbon atoms.
The flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property according to any one of claims 1 to 6, which has a hindered amine structure represented by: One or more types selected from titanium oxide (TiO ₂ ), titanium peroxide (peroxotitanic acid), zinc oxide (ZnO), and tin oxide (SnO ₂ ) on at least one surface of the front and back double-sided polyolefin resin layers. The flame-retardant polyolefin resin tarpaulin excellent in heat-resistant creep property according to any one of claims 1 to 7, wherein an antifouling layer containing the photocatalytic substance is formed.   One or more antifouling resins selected from acrylic resins, acrylic-silicon resins, and fluororesins, or one or more of the antifouling resins and silica on at least one surface of the front and back double-sided polyolefin resin layers The flame-retardant polyolefin-based resin tarpaulin excellent in heat-resistant creep property according to any one of claims 1 to 7, wherein an antifouling layer comprising a mixture containing fine particles is provided.