JP2003001767A - Polyolefinic resin high strength film material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefinic resin high strength film material having high strength, high tear strength and high frequency fusibility and especially suitable for a flexible container. SOLUTION: The polyolefinic resin high strength film material includes a substrate layer, which has two or more cloth layers each comprising fiber cloth having gaps between the yarns thereof and at least one polyolefinic resin- containing intermediate layer formed between them, and both upper and back outer surface layers comprising a polyolefinic resin formed on both upper and back surfaces of the substrate layer. The polyolefinic resin for the intermediate layer contains an ethylenic copolymer resin comprising at least one of an ethylene/vinyl acetate copolymer resin and an ethylene/(meth)acrylic acid (ester) copolymer resin and a ratio of the sum total weight of vinyl acetate and (meth) acrylic acid (ester) contained in the total weight of the polyolefinic resins as copolymer components is 10-35 wt.%, and both upper and back outer surface layers and the intermediate layer are mutually joined and continued at the gaps between the yarns of the cloth layers.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polyolefin resin high strength film material. More specifically, the present invention is suitable for applications such as flexible containers, oil fences, large tents, civil engineering sheets, and sound insulation sheets, which require particularly high strength and high tear strength, and high frequency fusion bonding. The present invention relates to a possible high-strength polyolefin resin film material.

[0002]

2. Description of the Related Art A tarpaulin, which is conventionally manufactured by laminating and compounding a soft polyvinyl chloride resin layer on both front and back surfaces of a long-fiber plain woven base cloth, is a construction curing sheet, flexible container, oil fence, eaves tent, It is an industrial material that is widely used for applications such as sound insulation sheets. Especially in these industrial material applications, if the tarpaulin requires sufficient breaking strength and sufficient tear resistance, it is possible to increase the fineness (dtex) of the yarn used for the long-fiber fabric used as the base fabric. Alternatively, it is possible to obtain a tarpaulin satisfying the above-mentioned requirements by increasing the number of warp and weft threads in the woven structure and increasing the density. Also usually
Tarpaulin uses a fibrous woven fabric with voids between yarns (blanket plain weave, etc.) as a base fabric, and coats a soft polyvinyl chloride resin layer on both sides of the fabric. By partially heat-fusing and adhering, it is possible to obtain a tarpaulin that is excellent in bending durability and sewn portion strength. That is, the performance and durability of tarpaulin means that a fiber woven fabric having an appropriate inter-yarn void space, an appropriate fineness (dtex), and an appropriate weaving density is used as the base fabric. By doing so, it can be improved.

In order to obtain a tarpaulin having higher strength and tear strength than ever before, as a base cloth used for it,
It is necessary to use a high-density woven fabric (due to yarns with high fineness), but this makes the space between yarns of the base fabric too small, and the soft polyvinyl chloride resin formed on both sides thereof is coated. The portions of the front and back layers exposed in the interfiber space of the base cloth cannot be sufficiently bonded to each other, and as a result, the resulting tarpaulin has insufficient bending durability and sewn portion strength. There was a drawback that Therefore, in high-strength / high-tear-strength tarpaulins containing soft polyvinyl chloride resin as a component of the front and back double-sided coating layers, a high-density fabric is coated with a resin composition having high adhesiveness to the soft polyvinyl chloride resin. Alternatively, a means for obtaining a sufficient adhesive effect between the soft polyvinyl chloride resin coating layer and the high-density woven fabric is provided by providing the adhesive layer by impregnation treatment. For example, as a resin composition having high adhesiveness to a soft polyvinyl chloride resin, a soft polyvinyl chloride resin paste, and a soft polyvinyl chloride resin solution dissolved in an organic solvent, or a polyurethane resin solution dissolved in an organic solvent, a polyester Known are resin solutions, and those obtained by adding a crosslinking agent such as an isocyanate compound or a carbodiimide compound thereto.

Recently, in relation to environmental problems, a resin product which is easy to dispose or recycle, does not contain any designated substance suspected of being hormone-disrupting, and has a low possibility of generating a toxic substance when burned. Development has become widely required by society. Originally, soft polyvinyl chloride resin is widely used as a synthetic resin material that is flexible and tough, and has excellent transparency, processability, cost efficiency and safety. There is a suspicion that it may be a hormone-disrupting substance for the phthalates included as plasticizers, and there is a concern that dioxin (derivative) may be generated during incineration. With respect to these anxieties, research and development of new materials that can completely dispel them are ongoing.

In particular, polyvinyl chloride resin products contain a high proportion of chlorine atoms in their molecular structure and are prone to thermal decomposition during the incineration process to generate hydrogen chloride gas. Products with a structure in which the content of halogens such as atoms has been reduced as much as possible have become desirable.
Polyolefin resin products have begun to spread widely in the daily sundries field. In addition, for large synthetic resin products that are difficult to dispose, product design that considers recycling is generally desired. In response to such social demand, there is an increasing demand to replace the conventional soft polyvinyl chloride resin tarpaulin with a halogen-free product. That is, as an alternative resin to the soft polyvinyl chloride resin, a low density polyethylene resin, ethylene-
Using a resin such as α-olefin copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene- (meth) acrylic acid (ester) copolymer resin, polypropylene resin, and polypropylene resin alloy, the surface of the base cloth Tarpaulins made of polyolefin resin with a coating layer on top of them are becoming popular, and their conversion rate is increasing especially in the field of flexible containers. The merits of converting to the above-mentioned polyolefin resin are that it is lighter than the conventional soft polyvinyl chloride resin tarpaulin and that it is registered as a polyolefin resin raw material under the self-regulation standards of the Polyolefin Hygiene Council. Products, products conforming to the food hygiene test standard of Ministry of Health and Welfare Notification No. 434, or US F.S. D. A. (§121, 2570) By using the approved product, it is possible to obtain high safety suitable for transportation of food raw materials.

In a polyolefin resin tarpaulin, an ethylene-vinyl acetate copolymer resin is used to form a coating layer,
Alternatively, a product obtained by using an ethylene-based copolymer resin such as an ethylene- (meth) acrylic acid (ester) copolymer resin is particularly easy to sew because high-frequency fusion is possible. However, in these ethylene-based copolymer resins, the higher the content of the vinyl acetate component and the polar component such as the (meth) acrylic acid (ester) component, the higher the high-frequency fusion property, but on the other hand, the resin Since the strength and abrasion resistance decrease, the practicality as an industrial material decreases. Therefore, the resin strength and abrasion resistance have been improved by blending a polyethylene resin, an ethylene-α-olefin copolymer resin, a polypropylene resin or the like with these ethylene copolymer resins. But,
By doing so, the resin strength and abrasion strength can be improved, but this time the high-frequency fusion property becomes insufficient and the sewing work becomes difficult, and the texture of the obtained tarpaulin becomes hard, making it difficult to fold. However, problems such as becoming bulky and bulky cannot be avoided. Further, at this time, there is caused a problem such as leaving crease marks that cause deterioration of resin fatigue in the bent portion due to excessive folding. Therefore, there is a problem that the practical application range of the above resin blending method is extremely narrow for a tarpaulin which requires a high degree of flexibility and durability.

The flexible container (tarpaulin) is
The larger the load capacity is, the more useful it is for physical distribution.
Therefore, in order to obtain a flexible container made of a polyolefin-based resin that is superior in strength and tear strength to the conventional one, it is necessary to use a high-density woven fabric (having a large yarn fineness) as the base fabric for the tarpaulin. An adhesive is required to laminate a polyolefin resin coating layer on both surfaces of a high-density fabric as a substrate. However, since the polyolefin resin is generally difficult to adhere to, there is a problem that it is necessary to add a treatment process such as a corona discharge treatment or a special primer treatment. Generally, as a primer, chlorinated polypropylene, modified chloroprene rubber,
Isocyanate compounds, adducts of polyhydroxypolyolefins with isocyanate compounds, and reaction products of hydrogen-terminated polybutadiene glycol with polyisocyanates are known.

However, among these primers, chlorinated polypropylene is a halogen-containing compound, and its effect is limited to the viscous adhesive effect, and it is extremely inferior in heat resistance and heat deterioration resistance. It causes peeling breakage or oxidative deterioration breakage, and therefore has a problem in its practicality when used for a flexible container. When an adduct of a polyhydroxypolyolefin and an isocyanate compound or a reaction product of a hydroxyl group-terminated polybutadiene glycol and a polyisocyanate is used as a primer, the adhesive layer has relatively good heat resistance, but the base cloth and the polyolefin. No significant improvement effect can be obtained on the adhesiveness to the resin layer. If the theoretical amount of the isocyanate compound is not accurately designed, the adhesiveness with the polyolefin resin may be decreased. Further, in the method in which the crosslinkable moisture-curable urethane prepolymer is used in combination with the above primer, it takes time to cure the primer, which causes trouble in the next step. In addition, when a two-component curing type (primary agent / curing agent) reactive primer is used, high temperature heating is required to complete the curing reaction in a short time, and the polyolefin resin base material is melted by heat during heat treatment, There is a problem of causing troubles such as deformation, and it cannot be said that it is an effective means for a polyolefin resin having a low melting point such as an ethylene copolymer resin. Further, in the method of impregnating and coating a high-density fabric with a reaction-curable primer to improve the adhesiveness with a polyolefin resin coating layer, there is a problem that the tear strength of the obtained tarpaulin is significantly reduced.

Copolymerization of a monomer having a polar functional group such as dimethylamino acid, a hydroxyl group, a carboxyl group, and / or a sulfonic acid group, for example, methacrylic acid, or an acrylic acid ester with the main chain of the polyolefin resin,
Alternatively, by using a modified polyolefin resin obtained by graft polymerization as an adhesive, it is possible to obtain some degree of adhesiveness to a polyolefin resin, but the low melting point of these adhesive olefin resins. The resulting product has poor heat resistance, and when heated,
When a shearing force or an external force in the peeling direction is applied to the adhesive olefin resin layer, there is a defect that the product is not suitable for heat resistance, such as shear failure or peeling failure easily occurring on the adhesive surface of the product. Further, for example, the above adhesive,
Also, the tarpaulin produced by including the step of applying the above-mentioned primer agent to the high-density fabric cannot be used for high-temperature transportation because the high-frequency fused portion is easily broken. That is, even if the adhesive layer or the primer layer provided between the high-density woven fabric and the polyolefin resin film layer is capable of exhibiting sufficient adhesive strength at room temperature, the high-frequency sewn portion is destroyed in a high-temperature atmosphere. Underneath, it is extremely softened and loses its adhesive effect, which rather causes thread breakage failure or peeling failure at the joint, and therefore cannot be used as a high strength flexible container for high temperature transportation. As a measure against this problem, by using an appropriate amount of a curable adhesive in the polyolefin resin,
Flexible containers that satisfy heat resistance and tear strength to some extent have also been proposed. Moreover, a flexible container (tarpaulin) made of polyolefin resin having practically sufficient high strength and high tear strength has not yet been obtained.

Therefore, in applications where a polyvinyl chloride resin tarpaulin is used, particularly in a flexible container tarpaulin, as a substitute for the polyvinyl chloride resin tarpaulin, it has high strength and high tear strength, and high frequency fusion bonding. There is a strong demand for the development of a polyolefin resin tarpaulin that is capable of high-strength, and a high-strength polyolefin resin tarpaulin that, in addition to the above characteristics, has high fracture strength at the high-frequency fusion zone and excellent heat creep resistance. .

[0011]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems of the prior art, and has a polyolefin resin film material having a sufficiently soft texture and excellent wear resistance, and capable of high frequency fusion, especially An object of the present invention is to provide a high-strength polyolefin-based resin film material excellent in fracture strength and heat-resistant creep resistance of a high-frequency fused portion.

[0012]

A polyolefin resin high-strength membrane material of the present invention is formed between at least two fabric layers each made of a fiber fabric having inter-fiber voids, and between the fabric layers, and A base material layer having at least one intermediate layer containing a polyolefin-based resin, and both front and back outer surface layers each formed of a polyolefin-based resin formed on both front and back surfaces of the base-material layer, and the middle of the base material layer. The polyolefin-based resin contained in the layer contains an ethylene-vinyl acetate copolymer resin and an ethylene-copolymer resin composed of at least one selected from ethylene- (meth) acrylic acid (ester) copolymer resins. And, based on the total weight of the polyolefin resin, the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component in the polyolefin resin. Is 10 to 35% by weight, and the portions of the front and back outer surface layers made of the polyolefin resin and the polyolefin resin intermediate layer exposed in the inter-fiber voids of the fabric layer are continuously joined to each other. ing,
It is characterized by that. In the polyolefin-based resin high-strength film material of the present invention, each of the polyolefin-based resin front and back outer surface layers independently of each other (b) a linear low-density ethylene-containing α-olefin having 3 to 18 carbon atoms. At least one selected from α-olefin copolymer resin, (b) ethylene-vinyl acetate copolymer resin, and ethylene- (meth) acrylic acid (ester) copolymer resin, and its total weight is On the other hand, the proportion of the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component thereof is 6 to 30% by weight.
It is preferable that at least one member selected from the following ethylene-based copolymer resin is used. In the polyolefin resin high-strength film material of the present invention, even if at least one of the polyolefin resin front and back outer surface layers is formed of the linear low-density ethylene-α-olefin copolymer resin (a). Good. In the polyolefin resin high-strength film material of the present invention, at least one of the polyolefin resin front and back outer layers may be formed of the ethylene copolymer resin (b). In the polyolefin resin high-strength film material of the present invention, at least one of the polyolefin resin front and back outer surface layers has the linear low-density ethylene-α-olefin copolymer resin (a) and the ethylene-based copolymer. It is formed of a blended resin with a polymer resin (b), and the ratio of the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component to the total weight of the blended resin. May be 6 to 25% by weight. In the polyolefin resin high-strength film material of the present invention, the polyolefin resin contained in the intermediate layer is selected from the ethylene-vinyl acetate copolymer resin and the ethylene- (meth) acrylic acid (ester) copolymer resin. Consisting of at least one ethylene-based copolymer resin,
The ratio of the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component to the total weight of the ethylene-based copolymer resin may be 10 to 35% by weight. In the polyolefin resin high-strength film material of the present invention, the polyolefin resin contained in the intermediate layer is (a) an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer resin. At least one selected ethylene-based copolymer resin, (b) ethylene, and 3 to 18 carbon atoms.
Of a linear low-density ethylene-α-olefin copolymer resin with α-olefin, and vinyl acetate and (meth) which are contained as a copolymerization component in the total weight of the blended resin. The proportion of the total weight of acrylic acid (ester) may be 6 to 25% by weight. In the polyolefin resin high-strength film material of the present invention, at least one layer of the intermediate layer and the front and back outer surface layers may further contain 1 to 10% by weight of the weight of the synthetic amorphous silica particles. preferable. In the polyolefin resin high-strength film material of the present invention, the thickness of the intermediate layer is 0.08 mm to 1.0 mm, and the thickness ratio between the outer surface layer and the intermediate layer is 2: 1. ˜1: 4, and the thickness ratio between the front and outer surface layers and the back and outer surface layers is 2: 1 to 1: 2.
Is preferred. In the polyolefin resin high-strength membrane material of the present invention, it is preferable that the fiber cloth forming the cloth layer has a porosity between yarns of 5 to 35%. In the polyolefin resin high-strength membrane material of the present invention, the fiber cloth forming the cloth layer is selected from organic synthetic fibers and inorganic fibers, and is composed of multifilament yarns having a fineness of 250 to 2500 dtex. It is preferably selected from In the polyolefin resin high-strength membrane material of the present invention, the fiber cloth for cloth is pretreated with a silicon compound treatment agent containing at least one selected from synthetic amorphous silica, colloidal silica, and silane coupling agent. It is preferably one. In the polyolefin resin high strength membrane material of the present invention, the J
The tensile strength specified in IS L 1096 is 1,000.
It is preferably ˜10,000 N / 3 cm. In the polyolefin resin high-strength film material of the present invention, the linear low-density ethylene-α-olefin copolymer resin (a) for both front and back outer layers is ethylene and α having 3 to 18 carbon atoms.
It is preferable to be selected from those obtained by copolymerizing an olefin with a metallocene catalyst. In the polyolefin resin high-strength membrane material of the present invention, the linear low-density ethylene-α-olefin copolymer resin (b) for the intermediate layer comprises ethylene and an α-olefin having 3 to 18 carbon atoms, It is preferably selected from those obtained by copolymerization in the presence of a metallocene catalyst. In the film material of the present invention, (meth) acrylic acid (ester) includes acrylic acid, methacrylic acid, acrylic acid ester and methacrylic acid ester.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The high-strength polyolefin-based resin film material of the present invention has a base material layer, and a polyolefin resin front and back outer surface layer formed on both front and back surfaces of the base material layer. The base material layer includes at least two fabric layers each made of a fiber fabric having inter-thread spaces (mesh spaces), and at least one layer formed between the two fabric layers and containing a polyolefin resin. It is composed of an intermediate layer. Portions of the polyolefin resin front and back outer surface layers and the polyolefin resin-containing intermediate layer that are exposed in the inter-fiber voids of the fabric layer are joined and continuous.

The high-strength polyolefin resin film material of the present invention has, for example, the cross-sectional laminated structure shown in FIG. The base material layer 5 is formed of a laminate of two fabric layers 2 and 3 made of the fiber fabric and a one-layer polyolefin resin-containing intermediate layer disposed between the fabric layers 2 and 3. A polyolefin resin front and outer surface layer 6 is formed on the surface of the base material layer 5, and a polyolefin resin back and outer surface layer 7 is formed on the back surface of the base material layer 5. A part of the polyolefin-based resin of the intermediate layer 4 has entered the space 8 between the yarns of the fabric layers 2 and 3, and a part of the polyolefin-based resin of each of the front and back outer surface layers has entered and has been separated from each other. The polyolefin resin surface / outer surface layer 6 and the polyolefin resin-containing intermediate layer 4 are partially continuous, and the polyolefin resin back / outer surface layer 7 and the polyolefin resin-containing intermediate layer 4 are joined together. And are partially continuous. As described above, since the intermediate layer and the front and back outer surface layers are partially joined and continuous in the inter-fiber voids of the fabric layer, the front and back outer surface layers and the intermediate layer and the fabric layer are firmly bonded to each other. It can be integrated and can prevent delamination, and can significantly improve the mechanical strength and stability of the size and shape of the film material.

In the polyolefin resin high-strength membrane material of the present invention, the polyolefin resin front and back outer surface layers are:
Independently of each other, (a) a linear low-density ethylene-α-olefin copolymer resin containing an α-olefin having 3 to 18 carbon atoms, and (b) an ethylene-vinyl acetate copolymer resin. , And at least one selected from ethylene- (meth) acrylic acid (ester) copolymer resins, and vinyl acetate and (meth) acrylic acid (ester) contained as copolymerization components in the total weight thereof. It is preferable that at least one member selected from the ethylene-based copolymer resins having a total weight ratio of 6 to 30% by weight is formed.

That is, at least one of the outer and outer layers of the polyolefin resin is the linear low-density ethylene-containing resin.
It may be formed of an α-olefin copolymer resin (a), or may be formed of the ethylene copolymer resin (b), or the linear low-density ethylene-α- It may be formed of a blend resin of the olefin copolymer resin (a) and the ethylene copolymer resin (b), and at this time, it is contained as a copolymer component in the total weight of the blend resin. It is preferable that the total weight ratio of the vinyl acetate and the (meth) acrylic acid (ester) is 6 to 25% by weight.

The polyolefin resin contained in the intermediate layer of the base material layer is at least one selected from ethylene-vinyl acetate copolymer resins and ethylene- (meth) acrylic acid (ester) copolymer resins. And a total weight of the vinyl acetate and the (meth) acrylic acid (ester) contained as a copolymerization component in the total weight of the polyolefin resin is 10 to 10%. 35% by weight.

That is, the polyolefin resin contained in the intermediate layer is ethylene comprising at least one selected from the ethylene-vinyl acetate copolymer resin and the ethylene- (meth) acrylic acid (ester) copolymer resin. It may be composed of only a copolymer resin, in which case vinyl acetate and (meth) contained as a copolymer component in the total weight of the ethylene copolymer resin.
The ratio of the total weight of acrylic acid (ester) is 10 to 3
It is 5% by weight.

The polyolefin resin contained in the intermediate layer may be a blend of the ethylene copolymer resin with another polyolefin resin. In this case, the polyolefin resin contained in the intermediate layer is ethylene composed of at least one selected from (a) ethylene-vinyl acetate copolymer resin and ethylene- (meth) acrylic acid (ester) copolymer resin. -Based copolymer resin,
(B) It is preferable that it is made of a blend resin of ethylene and a linear low-density ethylene-α-olefin copolymer resin of α-olefin having 3 to 18 carbon atoms, and at this time, a blend It is preferable that the ratio of the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component to the total weight of the resin is 6 to 25% by weight.

The linear low density ethylene-α-olefin copolymer resin is obtained by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms. In the production of this ethylene-α-olefin copolymer resin, an ethylene monomer and an α-olefin monomer having 3 to 18 carbon atoms are used in the presence of a Ziegler-Natta catalyst or a metallocene catalyst in a gas phase method or a slurry liquid phase method. Or a method of polymerizing by a high pressure method is known. Examples of the α-olefin monomer include propylene, butene-1,4-methylpentene-1, hexene-1, heptene-1, octene-
1, nonene-1, decene-1, tetradecene-1, hexadecene-1, heptadecene-1, octadecene-1 and the like are used, but it is particularly preferable to use an α-olefin monomer having 4 to 10 carbon atoms. Also, these α
-The olefin monomers may be used alone or in combination of two or more. These linear low-density ethylene-α-olefin copolymer resins may be not only one type of copolymer but also a blend of two or more types.

Of ethylene-α-olefin copolymer resin
The Ziegler-Natta catalyst used in the production is periodic
Compounds of Group IV-VI transition metals and Periodic Tables I-II
A metal-carbon bond composed of a group I metal compound
A transition metal compound catalyst having
It is composed of salt and metal alkyl compound.
It As the halogenated transition metal salt, for example, MgCl 2
₂ , AlCl₃ , TiCl ₃ , TiCl_Four Is used
Examples of the metal alkyl compound include triethyl
Used with aluminum, triisobutylaluminum, etc.
To be

As the metallocene catalyst, an organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative can be preferably used. The transition metal of the organic transition metal compound containing a cyclopentadienyl derivative or an indenyl derivative is selected from Group IVB of the periodic table of atoms. For example, zirconium, titanium and hafnium are preferable. Specific examples of the organic transition metal compound containing a cyclopentadienyl derivative include bis (n-propylcyclopentadienyl) zirconium dichloride and bis (1-methyl-3).
-N-propylcyclopentadienyl) zirconium dichloride, 1-methyl-1 ethylidene (cyclopentadienyl-1-fluorenyl) zirconium dichloride, bis (cyclopentadienyl) hafnium dichloride, dimethylsilanediylbis (2,4,4) 5-trimethylcyclopentadienyl) hafnium dichloride and the like. Specific examples of the organic transition metal compound containing an indenyl derivative include ethylenebis (indenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, 1,2-ethylenebis (tetrahydroindenyl) zirconium dichloride, bis (indenyl) titanium. Dichloride, dimethylsilanediylbis (indenyl) hafnium dichloride, and the like. The former metallocene-based catalyst containing a cyclopentadienyl derivative has a high syndiotacticity, and the latter metallocene-based catalyst containing an indenyl derivative has a high isotacticity, and ethylene-α can be obtained by properly using these metallocene-based catalysts. It can be obtained by controlling the stereoregularity of the olefin copolymer resin.

In the polymerization of the linear low-density ethylene-α-olefin copolymer resin used in the present invention, the use of alkylaluminoxane as a cocatalyst for the metallocene catalyst can improve the activation efficiency of the polymerization. it can. Examples of the alkylaluminoxane include methylaluminoxane, ethylaluminoxane and isobutylaluminoxane. As alkylaluminoxane, for example, trimethyl aluminum, obtained by condensation of an organic aluminum with water, such as triethyl aluminum _{- (Al (CH 3) -O-} ) n - condensates can be used. The alkylaluminoxane preferably has a metal atom number ratio (aluminum atom / transition metal atom of the metallocene catalyst) of 100 to 1000 with respect to the metallocene catalyst, and the metallocene catalyst used in the polymerization system is polymerized. 1 × 10 ^-8 for a volume of 1 liter
It is preferably used in an amount of ˜1 × 10 ⁻³ gram atom. Further, if necessary, a conventionally known proton acid, Lewis acid or Lewis acidic compound may be used in combination with the metallocene catalyst for the purpose of enhancing the polymerization activity.

The linear low-density ethylene-α-olefin copolymer resin used for both the front and back outer layers of the polyolefin resin and / or the intermediate layer containing the polyolefin resin is a Ziegler-Natta catalyst or a metallocene catalyst. It may be any copolymer resin polymerized by using,
In the present invention, it is preferable to use a linear low-density ethylene-α-olefin copolymer resin polymerized using a metallocene catalyst. In addition, at least one selected from linear low-density ethylene-α-olefin copolymer resins polymerized using a Ziegler-Natta catalyst and linear low-density ethylene-polymerized using a metallocene catalyst. α-
It is also possible to use by blending with one or more kinds selected from olefin copolymer resins. The linear low density ethylene-α-olefin copolymer resin and the blend resin have a melt index of 0.3 to 20 g / 10 mi.
n is preferable for the membrane material of the present invention. If the melt index is less than 0.3 g / 10 min, the molding process of the obtained polyolefin resin film material becomes extremely difficult, which is not preferable, and if it exceeds 20 g / 10 min, the polyolefin resin film material is obtained. In some cases, the abrasion resistance strength and the heat-resistant creep resistance are insufficient, and the adhesiveness is further increased to block the film material.

The ethylene-vinyl acetate copolymer resin used for both the front and back outer layers of the polyolefin resin and / or the intermediate layer containing the polyolefin resin is produced by radical copolymerizing ethylene monomer and vinyl acetate monomer. The ethylene-based copolymer resin containing 6 to 35% by weight, preferably 15 to 30% by weight of a vinyl acetate component can be used. The ethylene- (meth) acrylic acid (ester) copolymer resin is a (meth) acrylic acid (ester) component produced by radical copolymerization of an ethylene monomer and a (meth) acrylic acid (ester) monomer. An ethylene- (meth) acrylic acid (ester) copolymer resin containing 6 to 35% by weight, preferably 15 to 30% by weight is used. Specific examples of the (meth) acrylate ester include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Glycidyl (meth) acrylate or the like is used. Further, as the ethylene-based copolymer resin, a blend of an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer resin, further an ethylene-vinyl acetate copolymer resin, and / Or a blend of an ethylene- (meth) acrylic acid (ester) copolymer resin and a linear low-density ethylene-α-olefin copolymer resin, and the like. ) The total amount of acrylic acid (ester) components is 6 to 35% by weight, preferably 15% by weight based on the blend weight.
~ 30% by weight. The above vinyl acetate component, (meth)
When the total amount of the acrylic acid (ester) component is less than 6 parts by weight, the high frequency fusion property of the obtained polyolefin resin film material may be insufficient, and the total amount is 35 or less.
When the content is more than 5% by weight, the heat resistance creep resistance of the obtained polyolefin resin film material may be insufficient.

The melt index of the polyolefin-based copolymer resin for the front and back outer layers and the intermediate layer, and the polyolefin-based copolymer resin blend is 0.3 to 20 g /
It is preferably 10 min. When the melt index is less than 0.3 g / 10 min, it is difficult to process the obtained polyolefin resin sheet, and when it is higher than 20 g / 10 min, the abrasion resistance and heat resistance of the obtained polyolefin resin film material are high. Not only is it inferior in creep property, but it also increases tackiness and causes blocking, which is not preferable. At the same time, the tensile yield value (JIS K 7113) of the polyolefin-based copolymer resin used for both the front and back outer layers of the polyolefin-based resin and the blend of the polyolefin-based copolymer resin is 500 N / cm ² (51 kg
f / cm ² ) or more, preferably 500 to 900
More preferably, it is N / cm ² (91.8 kgf / cm ² ). If the tensile yield value is less than 500 N / cm ² , the abrasion resistance of the obtained polyolefin resin film material is insufficient, which is not preferable, and if it exceeds 900 N / cm ² , the abrasion resistance of the obtained polyolefin resin film material is not sufficient. The strength is sufficient, the texture is hardened, and at the same time, the high frequency fusion property may be insufficient. Further, the polyolefin resin high-strength membrane material of the present invention, the polyolefin resin front and back outer surface layer, in the presence of a metallocene catalyst or Ziegler-Natta catalyst, for the purpose of improving surface wear strength and heat creep resistance. Isotactic polypropylene resin obtained by self-polymerization of propylene monomer, syndiotactic polypropylene resin, or the like, the total amount of the vinyl acetate component and the (meth) acrylic acid (ester) component, the melt index, and the tensile yield value. Within the range, about 5 to 20% by weight may be blended.

At least one of the polyolefin resin front and back outer layers and the polyolefin resin-containing intermediate layer of the polyolefin resin high-strength film material of the present invention contains 1 to 10% by weight of synthetic amorphous silica. It is preferable. As the synthetic amorphous silica (silicon dioxide), it is preferable to use synthetic amorphous silica obtained by a wet method in which sodium silicate, mineral acid (sulfuric acid) and salts are reacted in an aqueous solution. This synthetic amorphous silica is a hydrous silica that contains, as bound water, water bound to the silanol group (Si-OH group) on the silica surface by hydrogen bond and water present as a hydroxyl group contained in the silanol group itself. is there. This hydrous silica is distinguished from other anhydrous silica having an extremely low water content obtained by other dry synthesis method or airgel synthesis method.

In the present invention, there is no particular limitation on the average agglomerated particle size of the synthetic amorphous silica used in the outer and outer layers of the polyolefin resin and / or the intermediate layer containing the polyolefin resin. It is preferable to use synthetic amorphous silica having an aggregate particle size (Cole counter method) of 1 to 20 μm, preferably 2 to 10 μm. The water content of the synthetic amorphous silica is preferably 3 to 15% by weight, more preferably 5 to 10% by weight.

If the blending amount of the synthetic amorphous silica is less than 1% by weight, the high-frequency fusion property of the obtained polyolefin resin film material and the heat-resistant creep strength of the fusion-bonded body may be insufficient, Further, the compounding amount of synthetic amorphous silica is 10
When the content exceeds 5% by weight, not only the molding of the polyolefin resin front and back outer surface layers and / or the polyolefin resin-containing intermediate layer is hindered, but the molding itself becomes difficult, and sufficient durability cannot be obtained. Sometimes. The synthetic amorphous silica is blended in the polyolefin resin high strength film material of the present invention in both the front and back outer layers of the polyolefin resin and / or the intermediate layer containing the polyolefin resin in an amount of 1 to 10% by weight based on the mass thereof. Thereby, the high-frequency fusion property can be further improved, and at the same time, the heat-resistant creep property of the fusion-bonded body can be improved.

The polyolefin resin high strength film material of the present invention has a polyolefin resin front and back outer surface layer and / or a polyolefin resin-containing intermediate layer which is colored (including white) with an organic pigment and / or an inorganic pigment. May be. Examples of organic pigments include azo pigments, phthalocyanine pigments, dyeing lake pigments, anthraquinone pigments, thioindigo pigments, perinone pigments, perylene pigments, quinacridone pigments, dioxazine pigments, isoindolinone pigments, In addition to quinophthalone pigments, other nitroso pigments, alizarin lake pigments, metal complex salt azomethine pigments, aniline pigments and the like can be used. Examples of the inorganic pigments include metal oxides such as zinc oxide, titanium oxide (rutile type, anatase type), antimony trioxide, iron oxide, lead oxide, chromium oxide, zirconium oxide, and metals such as calcium sulfide and zinc sulfide. Sulfides, metal sulfates such as barium sulfate, calcium sulfate and lead sulfate, metal carbonates such as barium carbonate, calcium carbonate and magnesium carbonate, metal hydroxides such as magnesium hydroxide and aluminum hydroxide, lead chromate and chromium Chromate metal salts such as barium acid salt, other carbon black, white carbon, diatomaceous earth, talc, clay, aluminum powder, colored aluminum powder, crushed metal vapor deposition film, silver white mica titanium, colored mica titanium, dichroic Interference mica titanium etc. can be illustrated. These pigments can be used in combination of two or more kinds. There is no limit to the amount added. Further, the combination of the polyolefin resin-containing intermediate layer and the polyolefin resin front and back outer layers may be different from each other.

If desired, other additives may be added to the outer and outer layers of the polyolefin resin and / or the polyolefin resin-containing intermediate layer. Particularly, for the purpose of improving the durability of the polyolefin resin, it is preferable to add an appropriate amount of an ultraviolet absorber, an antioxidant, a light stabilizer and the like. Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, salicylic acid compounds, and anilide compound ultraviolet absorbers.
Examples of antioxidants include hindered phenol compounds, amine compounds, and phosphite compound antioxidants. Examples of the light stabilizer include light stabilizers of hindered amine compounds. In addition, it is preferable to add a lubricant such as a phosphoric acid ester-based compound, an aliphatic amide-based compound, a montanic acid-based compound, etc. for the purpose of improving the processability during film forming.

The polyolefin resin high-strength film material of the present invention has a polyolefin resin front and back outer surface layer and / or a polyolefin resin-containing intermediate layer, which are conventionally known molding methods such as T-die extrusion method and inflation method. It can be processed by a calendar method or the like. The resin compound for forming the polyolefin resin front and back outer surface layers, and / or the polyolefin resin-containing intermediate layer is a known method, for example, using a Banbury mixer, a kneader, a twin-screw kneader, etc. It can be obtained by a method of applying and compounding, or a method of pelletizing into pellets by a single-screw extrusion pelletizer, a twin-screw extrusion pelletizer or the like after melt-kneading. The polyolefin resin front and back both outer surface layer of the present invention, and / or polyolefin resin-containing intermediate layer can be formed by a processing technique such as T-die extrusion method, inflation method, calender method using the above compound, In particular, the calendar method is simple and has little loss and is suitable for the production of a film colored with an organic pigment, an inorganic pigment, or the like, or for a process involving many color changing operations. The polyolefin resin front and back outer surface layers and / or the polyolefin resin-containing intermediate layer film of the present invention is 10
It is preferably formed by molding a film in a temperature range of 0 to 200 ° C. The thickness of the polyolefin resin front and back outer surface layers obtained by calendering and / or the polyolefin resin-containing intermediate layer is 0.08 to 0.5.
mm is preferable, and 0.1 to 0.35 mm is more preferable. When the thickness is thinner than 0.08 mm, not only the molding process is difficult, but also when laminated on the fiber cloth, the film is cut off at the intersection of the weaves of the fiber cloth, and not only the waterproof property is impaired, but also It deteriorates the durability of the membrane material. There is no limitation on the thickness of the polyolefin resin high-strength membrane material of the present invention, but a thickness of 0.
It is preferable that a total of three or more polyolefin resin front and back outer layer films having a thickness of 08 to 0.5 mm and / or a polyolefin resin-containing intermediate layer film are laminated on the fiber cloth. In particular, in a laminated structure of polyolefin resin front / back surface film / fiber cloth / polyolefin resin intermediate layer film / fiber cloth / polyolefin resin back / outer surface film using two fiber cloths, polyolefin resin front / back outer surface layers Each of these is partially joined to the polyolefin-based resin-containing intermediate layer at the inter-fiber voids of the fabric layer and is partially continuous, and a polyolefin-based resin film material having such a five-layer structure is most preferred in the present invention. It is a mode.

A polyolefin resin film material of the present invention obtained by arranging a polyolefin resin-containing intermediate layer between two fiber cloths and arranging a polyolefin resin outer surface layer on the front and back surfaces of the obtained base material. In the above, the thickness ratio of the polyolefin resin surface / outer surface layer to the polyolefin resin-containing intermediate layer is preferably 2: 1 to 1: 4,
More preferably, it is 1: 1 to 1: 3. The minimum thickness of these layers is 0.08mm and the maximum thickness is 1.0mm.
For example, the thickness (mm) ratio between the outer surface layer of the polyolefin-based resin and the intermediate layer containing the polyolefin-based resin is 0.16 mm when they are the thinnest:
0.08 mm, with the thickest being 1.0 mm: 4.0
mm. In the above thickness ratio, the thickness ratio of the polyolefin-based resin-containing intermediate layer is, for example, 3: 1.
When it is larger than 2: 1, the relative thickness of the intermediate layer becomes excessively thin, and therefore, the lamination interval between the two fiber cloths becomes small, and the high-frequency fusion property and the flexibility of the obtained film material are improved. There is a problem that it becomes insufficient and that delamination is likely to occur due to bending. Further, in the above thickness ratio, it becomes smaller than 1: 4, such as 1: 5,
Therefore, if the thickness of the polyolefin-based resin-containing intermediate layer film is excessively large, the flexural resilience of the obtained film material becomes large, and not only the handling becomes inconvenient but also the abrasion resistance of the film material is reduced. Sometimes.

The thickness ratio of the polyolefin resin surface / outer surface layer of the polyolefin resin high strength membrane material of the present invention to the polyolefin resin back / outer surface layer is preferably 2: 1 to 1: 2, It is more preferably 3: 2 to 2: 3. Also, the minimum thickness of these layers is 0.08 mm,
The maximum thickness is preferably 1.0 mm. For example, in the case where the thickness (mm) of the polyolefin-based resin outer surface layer and the polyolefin-based resin back outer surface layer is the thinnest, the maximum thickness is 0.
16 mm: 0.08 mm, or 0.08 mm: 0.16 mm, and 2.0 mm: 1.0 mm or 1.0 mm: 2.0 mm in the thickest case. In the above thickness ratio, if it is, for example, 1: 3 and is smaller than 1: 2, the thickness of the polyolefin resin surface / external surface layer becomes thin and the abrasion resistance of the obtained film material becomes low. Further, in the above thickness ratio, when it is larger than 2: 1 such as 3: 1, the thickness of the polyolefin resin back outer surface layer becomes thin, and the back surface abrasion resistance of the obtained film material becomes insufficient. May be sufficient. Further, the present invention may be a multi-layered polyolefin resin high-strength membrane material using three or more fiber cloths. In this case, two or more polyolefin-based resin-containing intermediate layers contained in the multi-layer structure are used. Each thickness is 0.
It is preferably in the range of 08 to 1.0 mm, and the thickness ratio of each of the polyolefin resin front and back outer surface layers to each of the polyolefin resin-containing intermediate layers is preferably in the same range as described above.

As the fiber cloth which can be used for the cloth layer of the base material of the high strength polyolefin resin film material of the present invention, woven cloth,
Any of knitted fabrics may be used, and examples of the structure of the woven fabric include plain weave, twill weave, satin weave and the like. Among these, the plain weave fabric is preferable because the polyolefin resin film material from which it is obtained has an excellent balance of warp and weft physical properties. The warp and weft fibers used for the fiber cloth may be synthetic fibers, natural fibers, semi-synthetic fibers, inorganic fibers or mixed fibers composed of two or more of these, but in view of processability and versatility. Synthetic fiber yarns such as polypropylene fiber, polyethylene fiber, vinylon fiber, acrylic fiber, polyurethane fiber, polyester fiber, nylon fiber, aromatic polyamide (aramid) fiber, aromatic polyester fiber, and heterocyclic polymer fiber can be preferably used. Further, as the inorganic fiber, a multifilament yarn such as glass fiber, ceramic fiber, carbon fiber or the like can be used. Alternatively, the yarn for fiber cloth may have any shape such as a multifilament yarn, a short fiber spun yarn, a monofilament yarn, a split yarn, a tape yarn and the like.

As the fiber yarn used in the high strength film of the polyolefin resin of the present invention, polyester fiber (polyethylene terephthalate, polybutylene terephthalate, polynaphthylene terephthalate), nylon fiber (nylon-6, nylon-6, nylon-6, etc.) can be used. 6), aromatic polyamide fiber (poly-p-phenylene terephthalamide, poly-p-benzamide, p-phenylene-3,4 oxydiphenylene terephthalamide copolymerization), aromatic polyester fiber (p-hydroxybenzoic acid or p , Polycondensation products of p-dioxydiphenyl and aromatic dicarboxylic acid), heterocyclic polymer fibers (poly-p-phenylenebenzbisthiazole, poly-p-phenylenebenzbisoxazole), glass fibers, ceramic fibers ( Silica, alumina, potassium titanate Beam, titania), carbon fiber (P
Most preferred are multifilament yarns such as AN-based, pitch-based), and polyetheretherketone fibers and polyphenylene sulfide fibers. These fiber yarns are spun into single fiber diameters in the range of 1-10 μm,
Strand obtained by converging 500 strands 1 to 5 times / 2
5.4mm twisted single yarn or strand 2
A multifilament yarn such as a plied yarn in which three or three twists are twisted at 1 to 5 times / 25.4 mm is preferable. The fiber cloth is most preferably a plain woven woven fabric obtained by mixing these yarns and these yarns. As a mixed example, one of the above-mentioned fiber threads is used for the warp and the weft.
A woven structure in which the above-mentioned seeds and other fiber yarns are used in combination, and the respective fiber yarns are arranged at a fixed driving interval, for example, poly-p-phenylene terephthalamide (PPTA) fiber yarns which are aramid fibers. A fiber cloth having a woven structure having {PPTA-PET-PET -...} as a repeating unit, which is a mixture of polyester (PET) fiber yarns, is used.

As the multifilament yarn used in the present invention, it is preferable to use a yarn having a fineness of 250 to 2500 dtex, and more preferably, a multifilament yarn having a fineness of 500 to 1500 dtex is excellent in tensile strength and tear strength. Fiber fabric can be obtained. Tensile strength of the polyolefin resin high strength membrane material of the present invention is 1000
It is preferably from 1 to 10,000 N / 3 cm, more preferably from 2000 to 5000 N / 3 cm (JIS L 10
96), and the tear strength is preferably 100 to 800 N, more preferably 300 to 800 N (J
IS L 1096). All yarns are all 250
When a fiber cloth having a fineness of less than dtex is used, its tensile strength and tear strength are insufficient, so that the resulting film material also has insufficient tensile strength and tear strength. Further, in order to obtain a film material satisfying tensile strength and tear strength by using a fiber cloth in which all yarns have a fineness of less than 250 dtex, a large number of these fiber cloths are laminated to form a base material. This makes the manufacturing process complicated and expensive. Further, a fiber cloth having yarns having a fineness of less than 250 dtex and a fiber cloth made of yarns having a fineness of 250 dtex or more may be used in combination, but if a fiber fabric having a fineness of less than 250 dtex is used, the combined effect is obtained. Is sparse. When the fineness of the yarn exceeds 2500 dtex, the tensile strength and tear strength of the obtained membrane material are improved, but the yarn diameter becomes thicker and the obtained membrane material becomes thicker, and at the same time, due to the interwoven points of the yarn of the fiber cloth. Since the unevenness is increased, the surface smoothness of the laminated front and back outer layers of the polyolefin-based resin becomes uneven, and the abrasion resistance of the obtained film material becomes insufficient, which is not preferable.

The striking density of the warp and the weft in the fiber cloth varies depending on the fineness of the fiber yarn used and is not particularly limited, but a multifilament yarn having a fineness of 250 to 2500 dtex is used as the warp and the weft of 25.4 mm. (1
Woven fabric obtained by driving 8 to 45 yarns per inch, for example, in the case of a multifilament yarn having a yarn fineness of 555 dtex, a plain woven fabric obtained by driving 16 to 24 yarns per 1 inch. , And the yarn fineness is 111
25.4 mm for 1 dtex multifilament yarn
A plain woven woven fabric obtained by driving about 12 to 20 fibers per (1 inch) can be exemplified as a fiber fabric suitable for the base material of the membrane material of the present invention. These fiber cloths have voids between yarns, and the outer and outer layers of the polyolefin-based resin of the obtained film material are joined to the intermediate layer of the polyolefin-based resin and are partially continuous in the voids between the yarns.

The inter-yarn porosity of fiber cloth (percentage of total area of voids to surface area of cloth) is 5 to 35.
%, Particularly preferably 10 to 25%. If the inter-yarn porosity is less than 5%, the fiber threads come too close to each other and the bridge fusion property between the two layers of the polyolefin resin front and back outer surface layers formed on the front and back surfaces of the fiber cloth is reduced, This may cause a problem that the dynamic durability of the obtained membrane material is insufficient. Further, if the inter-yarn porosity exceeds 35%, the dynamic durability of the obtained membrane material is improved, but the amount of fiber threads becomes too small, so that the tensile strength and tear strength of the membrane material are sufficient. Not only can it not be obtained, but the dimensional stability of the film material may be insufficient, resulting in a lack of practicality. The inter-yarn porosity can be obtained as a value obtained by subtracting 100 from the area of the fiber thread occupying in the unit area of the fiber cloth as a percentage. For measuring the inter-yarn porosity, it is preferable to obtain 100 cm ² of 10 cm in the warp direction × 10 cm in the weft direction as a unit area.

Further, the two or more fiber cloths used in the base material of the film material of the present invention may be the same fiber cloth as each other or different fiber cloths as each other. The same fiber cloth means fiber type, yarn, fineness, twist,
Elements such as weave, weave, thread density, voids are all the same, and different means that at least one of the elements is different. As a combination of different kinds of fiber cloth, for example, a polyester fiber woven fabric and an aromatic polyamide fiber woven fabric are used together, a polyester fiber woven fabric and a glass fiber woven fabric are used together, and an aromatic polyamide fiber woven fabric and a glass fiber woven fabric are used together. Is mentioned.

The fiber cloth used in the high strength membrane material of polyolefin resin of the present invention may be pretreated with a treating agent containing a silicon compound. By this silicon compound treatment, the heat-resistant creep property of the obtained film material can be improved. In order to improve the heat-resistant creep resistance of the film material, it is also effective to impregnate and coat the fiber cloth with a reaction curable resin to improve the adhesiveness between the outer surface layer of the polyolefin resin and the intermediate layer containing the polyolefin resin. However, in this case, the texture of the obtained membrane material becomes hard,
There is the disadvantage that the tear strength of the film material is significantly reduced. In the membrane material of the present invention, by using the fiber cloth pretreated with the silicon compound-containing treatment agent, the heat creep resistance can be improved while maintaining the tear strength and the flexibility at appropriate levels.

As the silicon compound-containing treatment agent, at least one selected from synthetic amorphous silica, colloidal silica and silane coupling agent, and synthetic amorphous silica,
A composition of at least one selected from colloidal silica and a silane coupling agent and a thermoplastic resin is used. Among these silicon compounds, as the synthetic amorphous silica, water adsorbed on the surface of silica particles, anhydrous silica having a small amount of hydroxyl groups, airgel method silica, wet method silica and the like can be used. These silicas have an average particle size of 1 to 20 μm.
The thing of a grade can be used preferably. For the pretreatment of the fiber cloth, the silicon compound-containing treatment agent is uniformly dispersed in water, and the fiber cloth is immersed in a treatment agent aqueous solution bath having a SiO ₂ content concentration of 1 to 15% by weight, and the fiber cloth is pulled up from the bath. At the same time, it can be carried out by passing through a nip roll to remove an excessive aqueous solution of the treating agent and drying the water. The adhesion of the treatment agent to the fiber cloth is not particularly limited, but the adhesion is preferably 1 to 5% by weight. At this time, it is preferable to use the synthetic amorphous silica and a silane coupling agent together.

As colloidal silica, BET obtained by cation exchange of sodium silicate solution
An aqueous dispersion medium colloidal silica sol having an average particle diameter of 10 to 50 nm or a BET colloidal silica sol having an organic solvent as a dispersion medium and having an average particle diameter of 10 to 50 nm can be used.
For the pretreatment of the fiber cloth, the fiber cloth is immersed in a colloidal silica bath having a SiO ₂ content concentration of 5 to 30% by weight, pulled up from the bath and passed through a nip roll at the same time to remove excess colloidal silica to remove water or moisture. It can be performed by drying the organic solvent. The adherence rate to the fiber cloth is not particularly limited, but the adherence rate is 1 to 15% by weight, especially 3
It is preferably from 10 to 10% by weight. At this time, it is preferable to use colloidal silica and a silane coupling agent together.

The silane coupling agent has a general formula:
A compound having two or more different reactive groups in the molecule represented by XR-Si (Y) ₃ , for example, X = amino group,
A compound having a vinyl group, an epoxy group, a chloro group, a mercapto group or the like (R = alkyl chain), Y = methoxy group, ethoxy group or the like is used. Further, a hydrolyzate of the above compound, a co-hydrolyzed compound with an alkoxysilane compound, and the like can also be used. Specifically, as the silane coupling agent, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, β- (3,4
Epoxycyclohexyl) ethyltrimethoxysilane,
γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane Methoxysilane, N-β
(Aminoethyl) γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like, but particularly It is preferable to use an epoxy silane coupling agent. The silane coupling agent is used at a concentration of 1 to 5% by weight, and it is preferable to adjust the pH to 3 to 5 using an acid such as formic acid or acetic acid. The pretreatment of the fiber cloth is performed by immersing the fiber cloth in a bath of an aqueous silane coupling agent solution, pulling it up from the bath and passing it through a nip roll to remove excess aqueous solution of the silane coupling agent and drying the water. be able to. At this time, it is preferable to use synthetic amorphous silica or colloidal silica together with the silane coupling agent. The adhesion ratio of the silane coupling agent to the fiber cloth is not particularly limited, but the adhesion ratio is preferably 1 to 15% by weight, particularly 3 to 10% by weight.

As the thermoplastic resin used together with the silicon compound in the above treatment agent, an emulsion of the thermoplastic resin, an aqueous dispersion such as a dispersion, or a form solubilized in an organic solvent is used. it can. The thermoplastic resin is, for example, an ionomer resin, an acrylic resin, a vinyl acetate resin, a polyvinyl alcohol resin, an ethylene-vinyl acetate copolymer resin, a polyurethane resin, a polystyrene resin, a saturated polyester resin, a polyamide resin. Resins and modified resins thereof, and the like, in particular glycidyl methacrylate, dimethylaminoethyl methacrylate, itaconic anhydride, maleic anhydride,
It includes an ethylene-based copolymer resin modified with N-methylmaleimide and the like, and an acrylic-based copolymer resin. If necessary, a thermosetting resin such as a phenolic resin, a melamine resin, a urea resin, an unsaturated polyester resin, an epoxy resin, a thermosetting polyurethane resin, or an allyl phthalate resin may be added to the above thermoplastic resin. It can also be used by blending with a resin. For the pretreatment of the fiber cloth, the fiber cloth is immersed in an aqueous treatment liquid bath in which a silicon compound is mixed in these thermoplastic resin emulsions or dispersions, and the fiber cloth is pulled up from the bath and simultaneously passed through a nip roll to remove excess silicon. It can be performed by removing the compound-containing composition and drying the water. Also in the case of a solvent-based thermoplastic resin, pretreatment can be carried out by the same method. The weight ratio of the solid content of the thermoplastic resin to the solid content of the silicon compound is not particularly limited, but the ratio of the thermoplastic resin: silicon compound (synthetic amorphous silica) is 5:95 to 40: 6.
It is preferably about 0, particularly 10:90 to 30:
It is more preferably 70.

In the base material of the membrane material of the present invention, the above-mentioned fiber cloth is laminated with a film for polyolefin resin front or back outer surface layer, or a polyolefin resin-containing intermediate layer, and both front and back outer surface layers of polyolefin resin are In the space between yarns of the fiber cloth, it is joined to the polyolefin resin-containing intermediate layer and is partially continuous. As a method for laminating these, bridge fusion between two polyolefin resin layers formed on each of the front and back surfaces of the fiber cloth is the most simple and preferable, but a polyolefin resin front and back outer surface layer film or a polyolefin resin An adhesive layer may be provided between the resin-containing intermediate layer film and the fiber cloth for laminating and bonding. The lamination method suitable for forming the film material of the present invention is a calender topping method or a T-die extrusion laminating method and the like, and the polyolefin resin front or back outer surface layer film and the polyolefin resin-containing intermediate layer film are molded and processed. At the same time, a polyolefin resin front or back outer layer film and a polyolefin resin-containing intermediate layer film are molded by a method of heat lamination to a fiber cloth, a calendering method, a T-die extrusion method, an inflation method, etc. Examples include a method in which a film is thermocompression-bonded to a fiber cloth using a laminator to perform lamination. In the production of the polyolefin-based resin high-strength film material of the present invention, a polyolefin-based resin front or back outer layer film molded by a calendar method, and a polyolefin-based resin-containing intermediate layer film,
The method of thermocompression-bonding and laminating to a fiber cloth is preferable because it is efficient and economically excellent. At this time, in the space between the yarns of the fiber cloth, the polyolefin-based resin front and back outer surface layer film directly heat-melt bridges to the polyolefin-based resin-containing intermediate layer film, so that application of an adhesive is not required, and therefore, A film material having sufficient dynamic durability can be obtained without lowering tear strength and hand hardening.

The polyolefin resin high strength film material of the present invention can be easily joined by high frequency fusion using a high frequency welder. As a high frequency fusion method,
Specifically, two or more sheets of the polyolefin-based resin high-strength film material of the present invention or a part of another thermoplastic resin molded product that can be heat-sealed with the polyolefin-based resin high-strength film material of the present invention are overlapped. It is placed between two electrodes (one electrode is a weld bar), and the potential difference that oscillates at a high frequency (1 to 200 MHz) is applied while applying pressure to the welded part with the weld bar. The high-frequency fusing property, which allows the resin of the system to be melted by molecular frictional heat and thereby adhere and seal, is the dielectric loss factor of the resin, that is, the product amount (ε) of the dielectric constant (ε) and the dielectric loss tangent (tan δ). .Tan δ) and is therefore related to the magnitude of internal molecular frictional heat oscillating at high frequencies. The dissipation factor is
It is a function of the portion of the high-frequency electromagnetic radiation energy absorbed by the resin that is converted into heat, and this dielectric loss factor is preferably at least 0.01 or more. As a high-frequency welder machine, a commercially available model such as YC-7000FT or YF-7000 manufactured by Yamamoto Vinitter Co., Ltd.
Seidensha Electronics Co., Ltd. KM-5000TA, KA-7
000TE, LW- from Quinlite Electronic Seiko Co., Ltd.
4000W, LW-4060S, etc. can be used.

In addition, as a method for joining the high strength polyolefin resin film material of the present invention, the ultrasonic energy (16 to 30 KHz) generated from the ultrasonic vibrator is amplified through the tip of the tool horn to increase the amplitude of the boundary surface of the film material. 20-700 by the ultrasonic welder fusion method that performs instant fusion using the frictional heat generated in the
Hot air that is continuously set to ℃ is blown between the film materials through a nozzle to instantly melt the surface of the film material, and immediately after that the film material is pressure-bonded and bonded, or the melting temperature of the thermoplastic resin. As described above, fusion bonding can be performed by any method such as a hot plate fusion method in which an adherend is pressure-bonded and sealed using a heated mold (trowel) with a built-in heater, but especially a flexible container with complicated sewing For this, high-frequency fusion using a dedicated mold is excellent in work efficiency.

[0049]

The present invention will be described in more detail with reference to the following examples, but the technical scope of the present invention is not limited to the scope of these examples. In the following Examples, and Comparative Examples, the strength evaluation of the polyolefin resin high-strength film material of the present invention, tear strength evaluation, flexibility evaluation, abrasion resistance evaluation, high-frequency fusion bond evaluation, heat creep resistance evaluation test method is It is as follows.

(I) Tensile strength evaluation General textile test method (JIS L 1096) Tensile strength A
According to the method, using a universal tensile tester (Strograph V10: manufactured by Toyo Seiki Seisaku-sho, Ltd.), a 3 cm × 30 cm test piece was held at a test piece gripping interval of 20 cm and a tensile strength of 20 cm / min.
Under the conditions described above, the test piece was pulled until it broke, and the stress load at the time of rupture was determined to obtain the tensile strength.

(II) Tear strength evaluation General textile test method (JIS L 1096) Tear strength A
According to the -1, method, a 10 cm × 25 cm long test piece was used with a universal tensile tester (Strograph V10: manufactured by Toyo Seiki Seisaku-sho, Ltd.) to hold the test piece at a gripping interval of 10 cm and a tensile strength of 20.
The test piece was torn under the condition of cm / min until it broke, and the maximum load was calculated as the tear strength.

(III) Flexibility evaluation A small piece sampled 160 mm wide x 50 mm long is rounded to a diameter of 50 m.
A cylinder of size m x 50 mm was prepared (the margin is fixed with a cyanoacrylate-based instant adhesive), and the compression test of JIS K6382 is performed. After ascertaining and comparing, it was judged that the smaller the value, the better the flexibility of the canvas. A loop stiffness tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) was used as a tester for evaluating flexibility. ◯: Good flexibility (200 g or less) Δ: Slightly inferior flexibility (201 to 299 g) X: Inferior flexibility (300 g or more)

(IV) Evaluation of Abrasion Resistance The abrasion resistance of the canvas surface was evaluated by the abrasion strength test C method (taper method) specified in the general woven fabric test method (JIS L 1096). A rotary appraisal tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) is used as a tester to evaluate the wear strength, and wears under the condition of a wear wheel (H-18), a wear load of 1 kg, and a wear count of 1000 times. A test was conducted, and the difference in mass (loss of wear) between the samples before and after the test was determined and compared, and it was judged that the smaller the value, the better the abrasion resistance of the canvas.

(V) Evaluation of high-frequency fusion property Two polyolefin resin film material ends were linearly overlapped with a width of 4 cm, and a weld bar (tooth profile: tooth profile: 4 cm × 30 cm) was used.
Convex parts are 4 cm wide linear imprints at regular intervals of 9 / 25.4 mm, convex part height is 0.5 mm: concave parts are evenly spaced 4 cm wide linear imprints at 9/2
The high frequency welding of the polyolefin resin film material was performed using a high frequency welder machine (YF-7000 type manufactured by Yamamoto Vinita Co., Ltd .: output 7 KW) equipped with 5.4 mm and a recess depth of 0.5 mm. In addition, a sample with a width of 3 cm including the fusion-bonded portion was sampled and subjected to a shear test of the fusion-bonded portion (JIS L 1096).
Then, the fractured state of the joint was evaluated according to the following criteria. <High-frequency fusion (welder) property> O: Fusion is easy. * High-frequency fusion conditions: fusion time 5 seconds, cooling time 5 seconds anode current 0.8A, weld bar temperature 40 to 50 ° C △: fusion can be performed by making the fusion conditions strong and long. * High frequency fusion conditions: fusion time 10 seconds, cooling time 5 seconds, anode current 1.0A, weld bar temperature 40 to 60 ° C x: No fusion occurs even if the fusion conditions are set to be strong and long. * High frequency fusion conditions: fusion time 10 seconds, cooling time 5 seconds, anode current 1.3A, weld bar temperature 40 to 60 ° C <destruction state of joint part due to shearing> ◯: main body fracture. Δ: The joint is destroyed. X: The yarn loss at the bonded portion is destroyed.

(VI) Evaluation of heat-resistant creep resistance In the heat-resistant creep resistance test, a test piece of 3 cm × 30 cm including 4 cm of the joint portion was taken from the high frequency fusion sheet of (V), and this was used as a heat-resistant creep test piece. Machine (100L
DR type: 50 ° C x using Toyo Seiki Seisakusho Co., Ltd.
A thermal creep resistance test of 25 kgf load × 24 hours was evaluated. ◯: After 24 hours, the joint was not broken and the load of 25 kgf was withstood. X: The joint part was sheared and broken within 24 hours.

Example 1 1) Film for polyolefin resin front and outer surface layer Linear low density ethylene-α-olefin copolymer resin (trademark: kernel KF270) obtained by copolymerizing ethylene and hexene in the presence of a metallocene catalyst. : 3 parts by weight of synthetic amorphous silica (trademark: Nipseal E200: Nippon Silica Industry Co., Ltd .: water content 6% by weight: average particle diameter 3 μm), phosphoric acid ester, per 100 parts by weight of Japan Polychem Co., Ltd. -Based lubricant (trademark: LTP-2: Kawaken Fine Chemical Co., Ltd.) 1.0 part by weight, benzotriazole-based ultraviolet absorber (trademark: Biosorb 510: Kyodo Yakuhin Co., Ltd.) 0.3 part by weight, hindered amine-based lubricant 0.2 parts by weight of light stabilizer (trademark: TINUVIN 770: Ciba Specialty Chemicals Co., Ltd.) and 3 parts by weight of coloring pigment [(organic pigment Lard pellet: Trademark: HCM161
7 Blue: Cyanine blue (α type) content 20% by weight:
Dainichiseika Kogyo Co., Ltd.) 2 parts by weight + inorganic pigment colored pellets: Trademark: HCM2060 White: Titanium dioxide (rutile type) 60% by weight: Dainichiseika Kogyo Co., Ltd.] 2
Parts by weight] and melt-kneaded in a Banbury mixer for 3 minutes, and then uniformly kneaded in 2 rolls set at 140 ° C. for 3 minutes.
A 6 mm thick blue polyolefin resin front and outer surface layer film was calender-rolled and molded.

2) Polyolefin resin back outer layer
The same film as the above-mentioned film for polyolefin resin front and outer surfaces was used as a film for polyolefin resin back and outer surface layers. (Polyolefin resin front / outer surface layer: polyolefin resin back / outer surface weight ratio layer = 1: 1)

3) Polyolefin resin-containing intermediate layer film
Irumu the polyolefin resin sheet external layer linear low density ethylene -α- olefin copolymer resin film (trademark: Kernel KF270: Nippon Polychem Co.) All the 100 parts by weight of ethylene - vinyl acetate copolymer resin ( 2) (Trademark: EvaTate K2010: MFR3.0: VA content 25% by weight: Sumitomo Chemical Co., Ltd.) Vinyl acetate is the same as the above-mentioned polyolefin resin surface / external surface layer film except that the content is changed to 100 parts by weight. A 0.16 mm-thick blue film containing 25% by weight of the components was used as a polyolefin resin-containing intermediate layer film. (Polyolefin resin surface / outer surface layer: polyolefin resin-containing intermediate layer weight ratio = 1: 1)

4) Production of Membrane Material Polyester fiber plain fabric (1) (833 dtex polyester multifilament: yarn density warp 19 / 2.54 cm
× 20 wefts / 2.54 cm: void ratio between yarns 18%: mass 140 g / m ² ) and polyester fiber plain weave (2)
(1111dtex polyester multifilament: yarn density warp 18 / 2.54 cm x weft 19 / 2.54 cm:
The following pretreatment was applied to each of the inter-filament porosity 15%: mass 180 g / m ² ) and the above polyolefin resin-containing intermediate layer film was provided between the polyester fiber plain woven fabric (1) and the polyester fiber plain woven fabric (2). The polyolefin resin front and outer surface layer film is disposed on the surface of the polyester fiber plain woven fabric (1), and the polyolefin resin back and outer surface layer film is disposed on the back surface of the polyester fiber plain woven fabric (2). The laminates are laminated by thermocompression bonding with a laminator set at 140 ° C. in sequence, and the polyolefin resin surface / outer surface layer / polyester fiber plain fabric (1) / polyolefin resin-containing intermediate layer / polyester fiber plain fabric (2) / polyolefin system A polyolefin resin film material having a thickness of 1.0 mm and a mass of 780 g / m ^{2 having} a five-layer structure of the resin back outer surface layer was obtained. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Pretreatment agent composition for polyester fiber plain weaves (1) and (2) Trademark: Nipseal E200: Nippon Silica Industry Co., Ltd .: Synthetic amorphous silica: Moisture content 6% by weight: Average particle diameter 3 μm 10 parts by weight Trademark: KBM303: Shin-Etsu Chemical Co., Ltd .: Epoxy silane coupling agent (100% by weight of active ingredient) 2 parts by weight Trademark: Aquatex E-1800: Chuo Rika Co., Ltd .: Ethylene-vinyl acetate copolymer Resin emulsion (solid content 40% by weight) 10 parts by weight Diluent: distilled water 100 parts by weight Polyester fiber plain woven fabric (1) is dipped in the above treatment agent bath, the woven fabric is pulled up, and immediately squeezed with a nip roll, (w
Et adhesion mass 75 g / m ² ) Then, drying was performed in a hot air oven at 100 ° C. for 2 minutes. The mass of the pretreated polyester fiber plain woven fabric (1) thus obtained was 148 g / m ² . (Synthetic amorphous silica: silane coupling agent: thermoplastic resin mass ratio = 5: 1: 2) The polyester fiber plain woven fabric (2) is also subjected to the same pretreatment as the polyester fiber plain woven fabric (1). Pretreated polyester fiber plain weave (2) with a weight of (wet adhesion mass of 85 g / m ² ) and mass of 189 g / m ^2.
Got

Example 2 Ethylene-vinyl acetate copolymer resin (2) for the intermediate layer containing the polyolefin resin of Example 1 (trademark: Evatate K)
2010: 100 parts by weight of Sumitomo Chemical Co., Ltd., ethylene-methyl methacrylate copolymer resin (trademark: Acryft WH-206: MMA content 20% by weight: MFR
2.0: Density 0.940: Sumitomo Chemical Co., Ltd. 100
The same as Example 1 except that the weight part was changed to
Polyolefin resin surface / outer surface layer / polyester fiber plain woven fabric (1) / polyolefin resin-containing intermediate layer / polyester fiber plain woven fabric (2) / polyolefin resin back outer surface layer having a five-layer structure, thickness 1.0 mm, mass 780 g / m
To obtain a ^second polyolefin-based resin layer material. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Example 3 1000 parts by weight of a linear low-density ethylene-α-olefin copolymer resin (trade name: Kernel KF270: Nippon Polychem Co., Ltd.) for the outer surface layer of the polyolefin-based resin of Example 1 was mixed with ethylene- Vinyl acetate copolymer resin (1) (trademark:
Everflex P-1905: VA content 19% by weight:
MFR2.5: Mitsui DuPont Polychemical Co., Ltd. 1
Same as Example 1 except that the amount was changed to 00 parts by weight, the same as Example 1 except that the polyolefin resin surface / outer surface layer / polyester fiber plain fabric (1) / polyolefin resin-containing intermediate layer / polyester fiber plain fabric (2) / polyolefin resin. The back and outer layers have a five-layer structure and a thickness of 1.0 mm and a weight of 780 g.
A polyolefin-based resin film material having a thickness of / m ² was obtained. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Example 4 Linear low-density ethylene-α-of the polyolefin resin front and outer surface layers and the polyolefin resin back outer surface layer of Example 2
Olefin Copolymer Resin (Trademark: Kernel KF270:
100 parts by weight of Nippon Polychem Co., Ltd. was added to ethylene-vinyl acetate copolymer resin (1) (trademark: Evaflex P-1905: VA content 19% by weight: MFR2.
5: Mitsui DuPont Polychemical Co., Ltd. The same as in Example 2 except that the amount was changed to 100 parts by weight, and the polyolefin resin surface / outer surface layer / polyester fiber plain fabric (1) / polyolefin resin-containing intermediate layer / Polyester fiber plain weave (2) / polyolefin resin back outer layer consisting of 5 layers, thickness 1.0 mm, mass 780 g / m
To obtain a ^second polyolefin-based resin layer material. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Example 5 Linear low-density ethylene-α-of the polyolefin resin front and outer surface layers and the polyolefin resin back outer surface layer of Example 1
Olefin Copolymer Resin (Trademark: Kernel KF270:
40 parts by weight of 100 parts by weight of Nippon Polychem Co., Ltd. are used as ethylene-vinyl acetate copolymer resin (1) (trademark:
Everflex P-1905: VA content 19% by weight:
MFR2.5: Same as in Example 1 except that it was replaced with Mitsui DuPont Polychemical Co., Ltd., and the polyolefin resin surface / outer surface layer / polyester fiber plain weave (1)
A polyolefin resin film material having a thickness of 1.0 mm and a mass of 780 g / m ^{2 having} a five-layer structure of / polyolefin resin-containing intermediate layer / polyester fiber plain weave (2) / polyolefin resin back outer layer was obtained. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

[0065]Example 6 Ethylene for the polyolefin resin-containing intermediate layer of Example 5
-Vinyl acetate copolymer resin (2) (trademark: EvaTate K
2010: Out of 100 parts by weight of Sumitomo Chemical Co., Ltd.
20 parts by weight of linear low-density ethylene-α-olefin
Copolymer resin (Trademark: Kernel KF270: Nippon Poly
Same as Example 5 except that it was replaced with Chem.
Polyolefin resin surface / outer surface layer / polyester fiber
Plain woven fabric (1) / Polyolefin resin-containing intermediate layer / Poly
Ester fiber plain weave (2) / polyolefin resin back outside
Face layer consisting of 5 layers, thickness 1.0mm, mass 780g
/ M ² To obtain a polyolefin resin film material. (Outermost surface
Layer thickness: Middle layer thickness: Backside outermost layer thickness = 1: 1: 1)

Example 7 The outer surface layer of the polyolefin resin of Example 1 and Example 5
Example 1 except that the polyolefin resin back outer layer of Example 1 and the polyolefin resin-containing intermediate layer of Example 6 were used.
Same as the above, a thickness of 1 layer consisting of a five-layer structure of polyolefin resin surface / outer surface layer / polyester fiber plain weave (1) / polyolefin resin-containing intermediate layer / polyester fiber plain weave (2) / polyolefin resin back outer layer A polyolefin resin film material having a weight of 0.0 mm and a mass of 780 g / m ² was obtained.
(Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1:
1)

Example 8 The same procedure as in Example 1 was repeated except that the polyolefin-based resin-containing intermediate layer of Example 1 was changed to the polyolefin-based resin intermediate layer used in Example 6, and the polyolefin-based resin outer / surface layer / polyester was used. Fiber plain fabric (1) / polyolefin resin-containing intermediate layer / polyester fiber plain fabric (2) /
A polyolefin resin film material having a thickness of 1.0 mm and a mass of 780 g / m ^{2 having} a five-layer structure of the polyolefin resin back outer surface layer was obtained. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

The composition of the polyolefin resin front and outer surface layers of Examples 1 to 8 is shown in Table 1, the composition of the polyolefin resin back and outer surface layers is shown in Table 2, and the composition of the polyolefin resin-containing intermediate layer is shown. 3 shows. Table 4 shows the composition of the fiber cloth of each of the membrane materials of Examples 1 to 8 and the test results of the membrane material.
Shown in.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

[Table 3]

[0072]

[Table 4]

Performance of Membrane Materials of Examples 1 to 8 Polyolefin resin high strength membrane materials of Examples 1 to 8 have two (or more) polyester fiber cloths (plain fabrics).
And, each of the polyolefin-based resin surface outer surface layer and the polyolefin-based resin back outer surface layer, in the inter-thread space of the fiber cloth, joined with the polyolefin-based resin-containing intermediate layer, by partially continuous, It has excellent bending durability and heat-resistant creep resistance at the joint part, which could not be achieved by a film material obtained by applying a polyolefin resin coating on a conventional high-density fiber woven fabric, and at the same time, has a tensile strength of 2500 to 3500N.
It was / 3 cm (JIS L 1096), and a high strength film material having a tear strength of about 300 to 500 N (JIS L 1096) could be obtained. Further, the polyolefin resin film material of the present invention can be easily fusion bonded under the conditions of an anode current value of 0.8 A, a fusion time of 5 seconds, a cooling time of 5 seconds and a weld bar temperature of 40 to 50 ° C. It was possible and had a joint shear strength comparable to the strength of the film body. Further, the polyolefin resin film materials of Examples 1 to 8 retain the flexibility of the film materials obtained by using the fiber cloth pretreated with the silicon compound, and are accompanied by a decrease in tear strength. However, the thermal creep resistance of the fusion-bonded portion was improved.

Example 9 The polyester fiber plain weave (1) of Example 1 was replaced with a glass fiber plain weave (1350 dtex glass multifilament: yarn density warp 20 / 2.54 cm × weft 21 / 2.54c).
m: inter-filament porosity 12%: mass 240 g / m ² ) The same as in Example 1, except that the polyolefin resin surface / outer surface layer / glass fiber plain weave / polyolefin resin-containing intermediate layer / polyester A polyolefin resin membrane material having a thickness of 1.1 mm and a mass of 880 g / m ^{2 having} a five-layer structure of a fiber plain fabric (2) / a polyolefin resin back outer surface layer was prepared. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Example 10 The polyester fiber plain weave (2) of Example 1 was replaced with a carbon fiber plain weave (660 dtex carbon multifilament:
Thread density Warp 15 / 2.54 cm x Weft 15 / 2.54
cm: inter-filament void ratio 19%: mass 185 g / m ² ) The same as in Example 1, except that the polyolefin resin surface / outer surface layer / polyester fiber plain weave (1) / polyolefin resin-containing intermediate Layer / Carbon fiber plain weave /
A polyolefin resin back outer surface layer has a five-layer structure,
A polyolefin resin film material having a thickness of 0.95 mm and a mass of 825 g / m ² was produced. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Example 11 The polyester fiber plain weave (2) of Example 1 was replaced with an aramid fiber plain weave (1111 dtex aramid multifilament: yarn density warp 15 / 2.54 cm × weft 15/2.
54 cm: 15% porosity between yarns: mass 145 g / m ² ) The same as in Example 1, except that the polyolefin resin surface / outer surface layer / polyester fiber plain weave (1) /
A polyolefin resin film material having a thickness of 0.95 mm and a mass of 785 g / m ^{2 having} a five-layer structure of a polyolefin resin-containing intermediate layer / aramid fiber plain weave / polyolefin resin back outer layer was prepared. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Example 12 The polyester fiber plain weave (1) of Example 1 was used in Example 9
Glass fiber plain fabric (1350 dtex glass multifilament: yarn density 20 warps / 2.54 cm × weft 21 /
2.54 cm: Porosity between yarns 12%: Mass 240 g / m
² ), and the polyester fiber plain weave (2) of Example 1 was replaced with the aramid fiber plain weave (1111) of Example 11.
dtex aramid multifilament: yarn density 15 warps /
2.54 cm x 15 wefts / 2.54 cm: inter-thread void ratio 1
5%: mass 145 g / m ² ) The same as in Example 1 except that the polyolefin resin surface / outer surface layer /
Glass fiber plain woven fabric / intermediate layer containing polyolefin resin /
Aramid fiber plain weave / polyolefin resin back outer layer consisting of 5 layers, thickness 1.0 mm, mass 890 g /
An m ² polyolefin resin film material was produced. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Example 13 The polyester fiber plain weave (1) and the polyester fiber plain weave (2) of Example 1 were used together with the aramid fiber plain weave (1111 dtex aramid multifilament: yarn density warp 15/2) of Example 11. 0.54 cm x 15 wefts / 2.
54 cm: porosity between yarns 15%: mass 145 g / m ² ) The same as in Example 1, except that the polyolefin resin surface / outer surface layer / aramid fiber plain fabric / polyolefin resin-containing intermediate layer / aramid was used. A polyolefin resin film material having a thickness of 0.9 mm and a mass of 790 g / m ^{2 having} a five-layer structure of a fiber plain woven fabric / a polyolefin resin back outer surface layer was produced. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

[0079]Example 14 The polyester fiber plain weave (1) of Example 1 was used in Example 9
Glass fiber plain weave (1350 dtex glass multifiller
Mento: 20 yarns / 2.54cm × 21 wefts /
2.54 cm: Porosity between yarns 12%: Mass 240 g / m
² ), And the polyester fiber plain weave of Example 1
The item (2) was replaced with the carbon fiber plain weave (660
dtex carbon multifilament: yarn density 15 warps /
2.54 cm x 15 wefts / 2.54 cm: inter-thread void ratio 1
9%: mass 185 g / m² ) Except that
In the same manner as in Example 1, the polyolefin resin surface / outer surface layer /
Glass fiber plain woven fabric / intermediate layer containing polyolefin resin /
Carbon fiber plain woven fabric / polyolefin resin back outer layer
Of a 5-layer structure, thickness 1.0 mm, mass 930 g / m
² A polyolefin resin film material was manufactured. (Outermost surface
Layer thickness: Middle layer thickness: Backside outermost layer thickness = 1: 1: 1)

Example 15 The polyester fiber plain weave (1) and the polyester fiber plain weave (2) of Example 1 were used together with the carbon fiber plain weave of Example 10 (660 dtex carbon multifilament: yarn density 15 warps / 2. 54 cm x 15 wefts / 2.54c
m: interfiber porosity 19%: mass 185 g / m ² ) The same as in Example 1 except that the polyolefin resin outer / outer surface layer / carbon fiber plain weave / polyolefin resin-containing intermediate layer / carbon Fiber flat woven fabric / polyolefin resin back outer layer having a five-layer structure, thickness 0.9
A polyolefin resin film material having a mass of 770 g / m ² was prepared. (Front outermost layer thickness: Middle layer thickness: Backside outermost layer thickness =
1: 1: 1)

Example 16 The polyester fiber plain weave (1) of Example 1 was used in Example 1
0 carbon fiber plain weave (660dtex carbon multifilament: yarn density 15 warps / 2.54cm x weft 15
Book / 2.54 cm: Porosity between yarns 19%: Mass 185 g /
m ² ), and the polyester fiber plain weave (2) of Example 1 was replaced with the aramid fiber plain weave (11) of Example 11.
11dtex aramid multifilament: yarn density warp 15
Book / 2.54 cm x weft 15 / 2.54 cm: porosity between yarns 15%: mass 145 g / m ² ) The same as in Example 1 except that the polyolefin resin surface / outer surface layer / carbon Fiber flat woven fabric / polyolefin resin-containing intermediate layer / aramid fiber plain woven fabric / polyolefin resin back outer layer having a five-layer structure, thickness 0.9 mm, mass 820
A polyolefin resin film material having a g / m ² was obtained. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1)

Table 5 shows the composition and test results of the fiber cloth of the membrane material obtained in each of Examples 9 to 16.

[0083]

[Table 5]

Properties of Membrane Materials of Examples 9 to 16 The polyolefin resin membrane materials of Examples 9 to 16 include two (or more) fiber cloths (plain fabrics), and at least one of the fiber cloths is glass. A fiber cloth, a carbon fiber cloth, or an aramid fiber cloth, and each of the polyolefin-based resin outer surface layer and the polyolefin-based resin back outer surface layer is bonded to the polyolefin-based resin-containing intermediate layer in the interfiber space of the fiber cloth. Partly continuous, resulting in excellent bending durability and heat-resistant creep resistance at the joints, which could not be achieved with conventional high-density fiber woven membranes coated with polyolefin resin. At the same time, the tensile strength is 2500 to 8500 N / 3 cm (JIS L 109
6) and a tear strength of 300 to 800 N (JIS
It was possible to obtain a polyolefin resin high-strength membrane material of L 1096) level. Further, the polyolefin resin film material of the present invention has an anode current value of 0.8 A and a fusion time of 5
Seconds, a cooling time of 5 seconds, and a weld bar temperature of 40 to 50 ° C. can be easily used for fusion bonding, and
It had a joint shear strength comparable to the strength of the membrane material body. Further, the polyolefin resin film materials of Examples 9 to 16 retain the flexibility of the film materials obtained by using the fiber cloth pretreated with the silicon compound, and are accompanied by a decrease in tear strength. However, the thermal creep resistance of the joint was improved.

Comparative Example 1 Polyester fiber plain weave (1) used in the film material of Example 1
And 2 pieces of (2), polyester fiber plain weave (5)
(1666dtex polyester multifilament: yarn density warp 19 / 2.54 cm x weft 20 / 2.54 cm:
Porosity between yarns 0%: mass 245 g / m ² ) Same as Example 1 except that the polyolefin resin-containing intermediate layer was omitted and the polyolefin resin surface / outer surface layer / polyester A polyolefin resin film material having a thickness of 0.65 mm and a mass of 535 g / m ² and having a three-layer structure of a fiber plain woven fabric (5) / a polyolefin resin back outer layer was prepared. (Outermost layer thickness on front surface: Outermost layer thickness on back surface =
1: 1)

Comparative Example 2 Polyester fiber plain woven fabric (1) used in the membrane material of Example 1
And 2 pieces of (2), polyester fiber plain weave (5)
(1666dtex polyester multifilament: yarn density warp 19 / 2.54 cm x weft 20 / 2.54 cm:
The porosity between yarns was 0%: the mass was 245 g / m ² ) Only one sheet was used, and the polyolefin resin-containing intermediate layer was omitted. In addition, pretreatment of the fiber cloth of Example 1 (synthetic amorphous silica: silane coupling agent: thermoplastic resin / 5: 1:
Same as in Example 1 except that 2) was changed to the following pretreatment, and the thickness was made of a three-layer structure of polyolefin resin front / outer surface layer / polyester fiber plain weave (5) / polyolefin resin back / outer surface layer. 0.66 mm, mass 545 g
A polyolefin resin film material having a thickness of / m ² was produced. (Outermost layer thickness on the front surface: Outermost layer thickness on the back surface = 1: 1) <Pretreatment composition of polyester fiber plain weave (5)> Trademark: Takelac E-350: Takeda Pharmaceutical Co., Ltd .: Polyester polyurethane (solid content 26 % By weight) 100 parts by weight Trademark: Coronate L: Nippon Polyurethane Industry Co., Ltd .: Isocyanate compound (solid content 75% by weight) 4 parts by weight Diluting solvent: Toluene 100 parts by weight Polyester fiber plain fabric (5 ), Pull up the woven cloth, immediately squeeze with a nip roll,
(Wet adhesion mass 125 g / m ² ) Then, drying was performed in a hot air oven at 90 ° C. for 3 minutes. The mass of the obtained pretreated polyester fiber plain weave (5) was 263 g / m ² .
(Polyurethane resin: isocyanate compound / 26:
3)

Comparative Example 3 Polyester fiber plain woven fabric (1) used in the film material of Example 1
The polyester fiber plain weave without inter-thread voids (6)
(833 dtex polyester multifilament: yarn density warp 25 / 2.54 cm × weft 26 / 2.54 cm: void ratio between yarns 0%: mass 175 g / m ² ) and polyester fiber plain fabric (2 ) Is a polyester fiber plain weave (7) (1111 dtex polyester multifilament: yarn density warp 23 / 2.5
4 cm × 24 wefts / 2.54 cm: porosity between yarns 0%: mass 210 g / m ² ) The same as in Example 1, except that the polyolefin resin surface / outer surface layer / polyester fiber plain weave (6 ) / Polyolefin resin-containing intermediate layer / Polyester fiber plain weave (7) / Polyolefin resin back outer surface layer having a five-layer structure, thickness 1.1 mm, mass 8
A polyolefin resin film material of 45 g / m ² was produced.
(Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1:
1)

Comparative Example 4 Polyester fiber plain woven fabric (1) used in the film material of Example 1
The polyester fiber plain weave without inter-thread voids (6)
(833 dtex polyester multi-filament: yarn density warp 25 / 2.54 cm x weft 26 / 2.54 cm: void ratio between yarns 0%: mass 175 g / m ² ) , Polyester fiber plain fabric without inter-thread voids (7) (1111 dtex polyester multifilament: yarn density warp 23 / 2.54 cm x weft 24 / 2.54 cm: inter-thread void ratio 0%: mass 210
g / m ² ), and the pretreatment agent (synthetic amorphous silica: silane coupling agent: thermoplastic resin / 5: 1: 2) for the fiber cloth of Example 1 was changed to the following pretreatment agent. Same as Example 1 except that the polyolefin resin surface / outer surface layer / polyester fiber plain fabric (6) / polyolefin resin-containing intermediate layer / polyester fiber plain fabric (7) / polyolefin resin back outer layer A polyolefin resin film material having a five-layer structure and a thickness of 1.1 mm and a mass of 870 g / m ² was produced. (Outermost layer thickness on front surface: Middle layer thickness: Outermost layer thickness on back surface = 1: 1: 1) <Pretreatment composition of polyester fiber plain weave (6) and (7)> Trademark: Takelac E-350: Takeda Yakuhin Kogyo ( Co., Ltd .: Polyester polyurethane (solid content 26% by weight) 100 parts by weight Trademark: Coronate L: Nippon Polyurethane Industry Co., Ltd .: Isocyanate compound (solid content 75% by weight) 4 parts by weight Diluting solvent: Toluene 100 parts by weight The above pretreatment Dip the polyester fiber plain weave (6) in the bath of the agent, pull up the woven fabric, immediately squeeze with a nip roll,
(Wet adhesion mass 80 g / m ² ) Then, drying was performed in a hot air oven at 90 ° C. for 3 minutes. The mass of the obtained pretreated polyester fiber plain weave (6) was 186 g / m ² . Polyester fiber plain woven fabric (7) has a mass of 223 in the same manner.
A pretreated polyester fiber plain weave (7) with g / m ² was obtained. (Polyurethane resin: isocyanate compound / 2
6: 3)

Table 6 shows the composition of the fiber cloth used in each of Comparative Examples 1 to 4 and the test results of the film material.

[0090]

[Table 6]

Performance of Film Materials of Comparative Examples 1 to 4 Since the film materials obtained in Comparative Examples 1 and 2 could not be subjected to high frequency fusion, the adherends were pressure-bonded with a heated hot plate containing a heater. Heat plate type heat fusion machine of heat fusion type (heat seal machine LHP-W703 manufactured by Quinlite Electronics Co., Ltd.)
Was used to evaluate the shear strength. In the film material of Comparative Example 1, the bonded portion was peeled off on the fabric surface, and the strength of the main body was about 1
Only 6% strength was obtained. Further, in Comparative Example 2, the use of the polyurethane resin-treated fiber cloth improved the shear strength of the joint to some extent, and the shear strength of about 44% of the main body strength was obtained. The destruction could not be prevented. In addition, the fiber cloth is treated with polyurethane resin, resulting in a tear strength of 6
The defect of 0% reduction was also revealed. Further, the film materials obtained in Comparative Examples 3 and 4 had high strength and were capable of high frequency fusion, but the joint strength was insufficient as in Comparative Examples 1 and 2,
In particular, the film material of Comparative Example 4 had an insufficient tear strength. Further, the heat creep resistance of the film materials of Comparative Examples 1 to 4 was evaluated. However, since the adhesion between the fiber cloth and the polyolefin resin outermost layer and the polyolefin resin intermediate layer was insufficient, all the film materials were evaluated. It was revealed that the joint part peeled and was destroyed.

[0092]

As is apparent from the above Examples and Comparative Examples, the polyolefin resin film material obtained according to the present invention is a film material obtained by applying a polyolefin resin coating to a conventional high density fiber woven fabric. It is a high-strength film material having excellent flexural durability that could not be achieved and heat-resistant creep resistance at the joint portion, and at the same time, having a tensile strength of 2500 to 8500 N / 3 cm and a tear strength of 300 to 800 N. Further, the polyolefin-based resin film material of the present invention is capable of high-frequency fusion bonding, and since it has a joint shear strength comparable to the strength of the film material body, particularly high strength and high tear strength are required. It is a very useful sheet that can be suitably used for flexible containers, oil fences, large tents, civil engineering sheets, etc.

[Brief description of drawings]

FIG. 1 is an explanatory cross-sectional view showing the configuration of an example of a polyolefin resin high strength film material of the present invention.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Polyolefin-based resin high-strength membrane material 2, 3 ... Fabric layer 4 having voids between yarns 4 ... Polyolefin-based resin-containing intermediate layer 5 ... Base material layer 6 ... Polyolefin-based resin outer / outer surface layer 7 ... Polyolefin-based resin back / outer surface layer 8 ... Inter-thread voids of fabric layer 9 ... Partial joining continuous part between polyolefin resin front and outer surface layer and polyolefin resin-containing intermediate layer 10 ... Partial bonding between polyolefin resin back outer surface layer and polyolefin resin-containing intermediate layer Joined continuous part

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F055 AA07 AA09 AA23 AA26 BA12                       BA14 CA17 EA04 EA22 FA06                       GA34 GA35 GA36                 4F100 AA20C AA20D AA20E AH06A                       AH06B AK03C AK03D AK03E                       AK63D AK63E AK68C AK68D                       AK68E AK70C AK70D AK70E                       AL05D AL05E BA04 BA10D                       BA10E BA25C CA23C CA23D                       CA23E DG11A DG11B EJ67A                       EJ67B GB16 JA12C JA12D                       JA12E YY00C                 4L031 AA18 AB32 BA20 DA21                 4L033 AA07 AB05 AC11 AC15 BA96                       DA06

Claims (15)

[Claims] 1. At least two fabric layers each made of a fiber fabric having inter-fiber voids, and at least one formed between the fabric layers and containing a polyolefin resin.
A base material layer having an intermediate layer and a front and back outer surface layer made of a polyolefin-based resin formed on both front and back surfaces of the base material layer, and a polyolefin-based resin included in the intermediate layer of the base material layer. Is an ethylene-vinyl acetate copolymer resin and an ethylene- (meth) acrylic acid (ester) copolymer resin containing at least one ethylene copolymer resin, and the polyolefin resin The ratio of the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component to the total weight is 1
0 to 35% by weight, the portions of the front and back outer surface layers made of the polyolefin resin and the polyolefin resin intermediate layer exposed in the inter-fiber voids of the fabric layer are continuously joined to each other. A high-strength polyolefin resin film material characterized by the following. 2. Each of the front and back outer layers of the polyolefin-based resin, independently of each other, is (a) having 3 to 1 carbon atoms.
Linear low-density ethylene-α-containing 8 α-olefins
Olefin copolymer resin, and (b) ethylene-vinyl acetate copolymer resin, and at least one selected from ethylene- (meth) acrylic acid (ester) copolymer resin, based on the total weight thereof, It is formed by at least one member selected from an ethylene-based copolymer resin in which the total weight ratio of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component is 6 to 30% by weight. The polyolefin-based resin high-strength film material according to claim 1. 3. The linear low-density ethylene-α-
Formed of an olefin copolymer resin (a),
The polyolefin resin high strength film material according to claim 2. 4. The polyolefin resin high-strength film material according to claim 2, wherein at least one of the front and back outer layers of the polyolefin resin is formed of the ethylene copolymer resin (b). 5. The linear low density ethylene-α-
It is formed of a blend resin of an olefin copolymer resin (a) and the ethylene copolymer resin (b), and vinyl acetate contained as a copolymer component in the total weight of the blend resin. The polyolefin resin high-strength film material according to claim 2, wherein the total weight ratio of (meth) acrylic acid (ester) is 6 to 25% by weight. 6. The polyolefin resin contained in the intermediate layer is ethylene comprising at least one selected from the ethylene-vinyl acetate copolymer resin and the ethylene- (meth) acrylic acid (ester) copolymer resin. The total weight of the ethylene-based copolymer resin is 10 to 35, and the total weight of vinyl acetate and (meth) acrylic acid (ester) contained as a copolymerization component in the ethylene-based copolymer resin is 10 to 35. The polyolefin resin high-strength membrane material according to claim 1, wherein the polyolefin resin high-strength membrane material is wt%. 7. The polyolefin resin contained in the intermediate layer is at least one selected from (a) ethylene-vinyl acetate copolymer resin and ethylene- (meth) acrylic acid (ester) copolymer resin. And a linear low density ethylene-α-olefin copolymer resin of (b) ethylene and an α-olefin having 3 to 18 carbon atoms. Vinyl acetate and (meth) acrylic acid (ester) contained as copolymerization components in the total weight of the blended resin
The percentage of the total weight of is 6 to 25% by weight.
The high-strength polyolefin resin film material as described in 1. 8. The synthetic amorphous silica particles in an amount of 1 to 10% by weight based on the weight of the intermediate layer and at least one of the front and back outer surface layers are further contained in at least one layer. The polyolefin resin high-strength film material according to item 1. 9. The intermediate layer has a thickness of 0.08 mm to 1.
0 mm, the thickness ratio between the front and outer surface layers and the intermediate layer is 2: 1 to 1: 4, and the thickness ratio between the front and outer surface layers and the back outer surface layer is 2: It is 1-1: 2, It is 1-8.
The polyolefin resin high-strength membrane material according to any one of 1. 10. The polyolefin resin high-strength membrane material according to claim 1, wherein the fiber cloth forming the cloth layer has a void ratio between yarns of 5 to 35%. 11. The fiber cloth forming the cloth layer is selected from organic synthetic fibers and inorganic fibers, and is 250 to 25.
The polyolefin resin high-strength membrane material according to any one of claims 1 to 10, which is selected from knitted fabrics composed of multifilament yarns having a fineness of 00 dtex. 12. The fiber fabric for a fabric layer is pretreated with a silicon compound treating agent containing at least one selected from synthetic amorphous silica, colloidal silica and a silane coupling agent. The polyolefin resin high-strength membrane material according to any one of 1 to 11. 13. The polyolefin resin high-strength membrane material according to claim 1, which has a tensile strength defined by JIS L 1096 of 1,000 to 10,000 N / 3 cm. 14. The linear low-density ethylene-α-olefin copolymer resin (a) for both front and back outer layers comprises ethylene and an α-olefin having 3 to 18 carbon atoms in the presence of a metallocene catalyst. The polyolefin resin high-strength film material according to claim 2, 3 or 5, which is selected from those obtained by copolymerization with. 15. A linear low density ethylene for the intermediate layer
The α-olefin copolymer resin (b) is selected from those obtained by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms in the presence of a metallocene catalyst. High strength film material of polyolefin resin.