JP2002210894A - Water-proofing composite film material excellent in flame-proofing property and in heat-creep resistance of heat-fused part - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a soft vinyl chloride resin composite film material which can form a heat-fused part having stable flame-proofing properties and good heat-creep resistance. SOLUTION: Both side soft vinyl chloride resin substrate layers containing (1) 5-50 phr of antimony trioxide, (2) (a) 40-90 phr of di-n-alkyl phthalate at least 420 in molecular weight, an adipic acid polyester plasticizer, isodecyl adipate, or trioctyl phosphate, and (b) 50-150 phr of an ethylene-vinyl acetate or ethylene-acrylate copolymer into which CO is introduced, or (c) a mixture of 90 phr or below of the plasticizer (a) and 150 phr or below of the copolymer (b) are formed on both sides of a fiber cloth ground fabric. Both side acrylic resin intermediate layers are formed on the substrate layers, and fluororesin surface layers are formed on the intermediate layers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof composite membrane material which is excellent in flame resistance and heat creep resistance of a heat-sealed portion, and is useful for sports facilities, event venues, and permanent membrane structures. The present invention relates to a waterproof composite membrane material excellent in flame resistance and heat creep resistance of a heat-sealed portion. More specifically, the present invention relates to a waterproof composite membrane material having high antifouling properties, having stable flameproof properties, and having excellent heat creep resistance of a heat-welded portion.

[0002]

2. Description of the Related Art Conventionally, as a film material for tents and the like, a film material obtained by coating and laminating a resin such as soft vinyl chloride on a woven fabric made of synthetic fiber such as polyester, nylon, and vinylon, or glass fiber has been widely used. Was. Such a conventional film material has a stable flame resistance by adjusting the blending of a coating resin such as a soft vinyl chloride resin,
In the heat-sealed portion, since the same material is integrated by heat-sealing, the heat-resistant creep property of the heat-sealed portion has no problem at all. However, when this film material is stretched outdoors, additives such as plasticizers in the resin gradually migrate to the surface, and contaminants floating in the raindrops and in the air adhere to the film material. Had the disadvantage of impairing the

On the other hand, there is known a film material in which the surface of the above-mentioned film material is subjected to a surface treatment made of an acrylic resin or the like so as to have an improved property of preventing adhesion of dirt. Such a surface-treated film material was slightly inferior in heat-sealing property and heat-resistant creep property of the heat-sealed portion to the conventional film material in which the soft vinyl chloride resin layer was exposed. It largely cleared the required design standards for tents and permanent membrane structures.

However, in recent years, a film material with less contamination has been demanded, and in response to this demand, a film material having an outermost layer formed of a fluororesin has appeared. This film material has a high antifouling property, but on the other hand, has insufficient heat-fusing properties, poor heat-resistant creep properties of the heat-fused parts, and unstable flame resistance. And the like. The lack of the heat-fusibility is solved by removing the fluororesin layer, but there is scattering of dust such as shavings of the removed fluororesin, which is extremely high with respect to the working environment and working efficiency. Had a negative effect.

Further, a fluororesin layer is formed on at least one surface of a vinyl chloride resin film material.
Or, by applying a heat-fusible acrylic resin on other layers, the heat-sealing property is improved. It is not a level that meets the required performance of the object. Regarding flame retardancy, those with reduced plasticizers and those with large amounts of inorganic flame retardants show relatively stable flame resistance, but those with reduced plasticizers and with large amounts of inorganic flame retardants The resulting film material has insufficient flexibility and bending durability, and when a flame retardant plasticizer, which is a liquid flame retardant, is blended, no remarkable improvement in flame resistance is observed. Since the heat creep resistance of the welded portion deteriorates, the performance level has not yet reached the level that can be used for event tents, permanent membrane structures, and the like.

[0006]

SUMMARY OF THE INVENTION The present invention relates to an acrylic resin, a base material comprising a fiber base cloth and a soft vinyl chloride resin.
And a film material on which a fluororesin is laminated, whereby the film material having a high antifouling property, while maintaining its stable and high flameproofness, is provided with a good heatproof creep resistance of the heat-sealed portion. An object of the present invention is to provide a waterproof composite film material having excellent heat creep resistance of a heat-sealed portion.

[0007]

SUMMARY OF THE INVENTION The waterproof composite membrane material of the present invention, which is excellent in flame resistance and heat creep resistance of a heat-sealed portion, is provided on a base cloth made of fiber cloth and on both front and back surfaces of the base cloth. Having a soft vinyl chloride resin base layer formed, an acrylic resin intermediate layer formed on the two base layers, and a fluororesin surface layer formed on the two intermediate layers,
In the soft vinyl chloride resin base layer, (1) 5 to 50 phr of antimony trioxide and (2) (a) 40 to 90 phr of a di-n-alkyl having a molecular weight of 420 or more are added to the soft vinyl chloride resin. (B) 50-150 phr of an ethylene-vinyl acetate copolymer and an ethylene-acrylate ester of at least one selected from phthalate, adipic acid-based polyester plasticizer, diisodecyl adipate, and trioctyl phosphate A polymer obtained by introducing carbon monoxide into at least one copolymer selected from copolymers, or (c) the plasticizer (a) of 90 phr or less and the polymer (b) of 150 phr or less And a mixture thereof. In the waterproof composite membrane material of the present invention, the base fabric is:
The fiber fabric may further include an adhesive resin applied, adhered, or impregnated. In the waterproof composite membrane material of the present invention, the fluororesin surface layer preferably contains at least one selected from polyvinylidene fluoride and a copolymer of vinylidene fluoride and tetrafluoroethylene. In the waterproof composite membrane material of the present invention, it is preferable that the fluororesin surface layer is formed of a mixed resin of a fluororesin and an acrylic resin. The waterproof composite membrane material of the present invention may further include an acrylic resin layer formed on at least one of the fluororesin surface layers.

[0008]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The waterproof composite membrane material of the present invention can have, for example, a laminated structure shown in FIGS. 1- (1) and (2). Fiber fabrics included in the base fabric of the waterproof composite membrane material of the present invention include natural fibers (eg, cotton, hemp, etc.), synthetic fibers (eg, polyester, polyamide, polyvinyl alcohol fibers, etc.), and inorganic fibers (eg, glass, carbon, etc.). Fiber, etc.), or a plain weave formed from a spun yarn, a monofilament yarn, a multifilament yarn, a tape yarn, or the like containing two or more types.
Woven fabrics such as twill weave, Oxford weave, and entangled weave are used. In general, the base fabric for membrane materials used for event tents, permanent membrane structures, etc. is made of synthetic fiber woven fabric using polyester multifilament yarn, polyamide yarn, polyvinyl alcohol yarn, glass fiber, carbon fiber, etc. It is preferable to use a woven inorganic fiber fabric. The basis weight of the fiber fabric for the base fabric is 80 to 450 g / m ^2.
And it can be arbitrarily selected from the required strength of a structure such as a tent. The fiber fabric for the base cloth may be subjected to a water-repellent treatment or an adhesive treatment as required. Further, an adhesive resin may be applied to the fiber cloth included in the base cloth to form an undercoat layer,
Alternatively, the fiber fabric may be impregnated with an adhesive resin.
As the adhesive resin, a vinyl chloride resin, an acrylic resin, a urethane resin, or any other appropriate resin having an effect can be used. When the adhesive resin uses a composition containing (paste) vinyl chloride resin, as a plasticizer,
It is further preferable to use a plasticizer comprising at least one selected from di-n-alkyl phthalate having a molecular weight of 420 or more, an adipic acid-based polyester plasticizer, diisodecyl adipate and trioctyl phosphate.

The soft vinyl chloride resin referred to in the present invention is:
It is obtained by blending a vinyl chloride polymer with a plasticizer or a polymer having a plasticizing action and antimony trioxide as an inorganic flameproofing agent, and preferably further comprises a stabilizer, a filler, an ultraviolet absorber, a light stabilizer, and a colorant. , And a fungicide.

The vinyl chloride resin of the present invention includes vinyl chloride polymers, vinyl chloride / vinyl acetate copolymers, vinyl chloride / acrylate copolymers, vinyl chloride / vinylidene chloride copolymers, and the like. They can be used alone or in combination of two or more. In the present invention, the plasticizer (a) that can be blended with the vinyl chloride resin includes:
At least one selected from di-n-alkyl phthalate having a molecular weight of 420 or more, adipic acid-based polyester plasticizer, diisodecyl adipate, and trioctyl phosphate;
Types can be used. Di-molecular having a molecular weight of 420 or more
Examples of the n-alkyl phthalate include di-n-nonyl phthalate, di-n-decyl phthalate, di-n-undecyl phthalate, di-n-dodecyl phthalate, and di-n-tridecyl phthalate. As the agent, adipic acid and 2-methyl-1,8-octanediol, 1,2-propanediol, 1,3-
It is obtained by esterifying glycols such as butanediol, 2-ethylhexanol and n-octanol. The molecular weight of the adipic acid-based polyester plasticizer is 16
It is preferably in the range of 00 to 2200. These plasticizers (a) can be used alone or in combination of two or more. Isodecyl adipate does not easily migrate to the acrylic resin intermediate layer and does not reduce the heat creep resistance of the heat-sealed portion. Further, the phosphate ester plasticizer used as a flame retardant plasticizer has good compatibility with the acrylic resin, and when blended into the soft vinyl chloride resin base layer, gradually migrates to the acrylic resin layer. However, there is a property that the adhesiveness between the soft vinyl chloride resin base layer and the fluororesin surface layer is reduced, and the heat creep resistance is also significantly reduced.
Trioctyl phosphate as a flameproof plasticizer used in the present invention hardly migrates to an acrylic resin intermediate layer, and can maintain good heat creep resistance even when blended in a soft vinyl chloride resin base layer. The amount of the plasticizer (a) to be added to the vinyl chloride resin base layer is 40 to 90 phr.
When the added amount of the plasticizer (a) is less than 40 phr, the obtained soft vinyl chloride resin base layer becomes hard, the texture of the film material is hard, the handleability is reduced, and the cold resistance may be poor. . If the added amount of the plasticizer (a) exceeds 90 phr, the resulting composite membrane material tends to have reduced heat creep resistance and may have unstable flame resistance.

Further, an ethylene-vinyl acetate copolymer which is generally used as a so-called non-plasticizer in place of the plasticizer (a) is provided on the soft vinyl chloride resin base layer of the composite membrane material of the present invention, and / or A polymer (b) in which carbon monoxide is introduced into an ethylene-acrylate copolymer may be contained. In this case, 50 to vinyl chloride resin
~ 150phr can be used. As these polymers, Elvaloy 742 (trademark) manufactured by Du Pont-Mitsui Chemicals Co., Ltd. can be used. If the amount of the polymer (b) is less than 50 phr, the resulting film material has a hard feel, resulting in poor handling properties and poor cold resistance. If the amount of the polymer (b) exceeds 150 phr, the heat-resistant creep resistance of the obtained film material tends to decrease, and the flame resistance becomes unstable. Alternatively, a mixture of the plasticizer (a) at 90 phr or less and the polymer (b) at 150 phr or less may be used in place of the plasticizer (a) or the polymer (b).

As the flame retardant added to the soft vinyl chloride resin base layer of the composite film material of the present invention, antimony trioxide is used as an inorganic flame retardant. The addition amount is 5 to 50 phr with respect to the vinyl chloride resin. This added amount is 5phr
If it is less than 3, the flame retardancy of the obtained composite membrane material becomes unstable. On the other hand, if the addition amount exceeds 50 phr, the resin strength of the vinyl chloride resin base layer of the obtained composite film material is reduced, so that cracks occur during handling and the cold resistance becomes poor.

As the stabilizer, calcium-zinc-based, barium-zinc-based, cadmium-barium-based, lead-based, organic tin laurate, organic tin mercaptite, epoxy-based, and the like can be added alone or in combination. The addition amount is preferably 0.5 to 10 phr with respect to the vinyl chloride resin.

As the ultraviolet absorber, triazoles,
Benzophenone-based, acrylate-based, and salicylic acid-based ultraviolet absorbers can be used. These UV absorbers may be used alone or as a mixture with respect to the vinyl chloride resin, preferably at least 0.3 phr, more preferably at least 0.1 phr.
Used in the range of 5 to 2 phr. 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2
It is particularly preferable to use -ethylhexyl-2-cyano-3,3-diphenylacrylate alone or as a mixture. For example, 2- (5-methyl-2-)
The use of (hydroxyphenyl) benzotriazole and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate in amounts of 0.5 to 1 part by weight is effective for preventing deterioration and coloring of the resin.

As the light stabilizer, tetrakis (1,2,2,3)
2,6,6-pentamethyl-4-piperidyl) -1,
2,3,4-butanetetracarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl)
Hindered amine compounds such as -1,2,3,4-butanetetracarboxylate are preferably used, and these have an effect of capturing radicals and preventing deterioration of the resin. Such a light stabilizer is preferably 0.1 phr or more, more preferably 0.2 to
It is contained in the range of 0.5 phr.

As the filler, at least one of calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide, magnesium hydroxide and the like may be used.
0 to 30 phr is contained per part by weight.

The vinyl chloride resin base layer may be formed by dipping, knife coating, casting, or the like on a paste sol-like vinyl chloride resin base fabric, or by forming a soft vinyl chloride resin previously formed into a film.
It is formed by a method of heat laminating on a base fabric, an extrusion coating while extruding from a T-die, or a method combining these.

In the present invention, the acrylic resin for forming the intermediate layer outside the soft vinyl chloride resin base layer is:
It is preferably selected from a polymer containing an ester of a C1 to C4 alcohol of acrylic acid or methacrylic acid as a main constituent monomer, or a resin containing a copolymer as a main component. Specific examples of the main constituent monomer of such an acrylate-based resin include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, and butyl methacrylate. Methyl methacrylate is preferred. Examples of comonomers to be copolymerized with these main constituent monomers include, for example, esters of C1 to C12 alcohols of acrylic acid or methacrylic acid, vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, acrylonitrile, There are monomers such as butadiene.

These acrylic resin intermediate layer copolymers may be random copolymers or graft copolymers. For example, a copolymer in which vinylidene fluoride is graft-polymerized to a methyl methacrylate polymer may be used. An acrylate containing an amino group, an imino group, an ethyleneimine residue, or an alkylenediamine residue can also be used.

The thickness of the acrylic resin intermediate layer is from 0.1 μm
The thickness is preferably 10 μm. If the thickness is smaller than 10 μm, the adhesion between the soft vinyl chloride resin base layer and the fluororesin surface layer may be insufficient. May be enough. This acrylic resin intermediate layer is formed by applying a predetermined amount of a liquid acrylic resin paint on a vinyl chloride resin base layer by a method such as gravure coating, knife coating, dipping, or the like, and then drying, or topping a resin melt. A method and a method of thermally laminating an acrylic resin in a film form can be used, but are not particularly limited. A coloring agent may be added to the acrylic resin intermediate layer as needed.

In the composite film material of the present invention, the fluororesin for the fluororesin surface layer formed on the two acrylic resin intermediate layers includes vinylidene fluoride and vinylidene fluoride / tetrafluoroethylene copolymer. Or a mixture of two or more thereof, and the fluororesin may further be mixed with an acrylic resin. It is preferable that the content of tetrafluoroethylene in the fluororesin is 0 to 30% by weight, and when the content exceeds 30% by weight, the heat fusion property between the acrylic resin intermediate layer and the fluororesin surface layer is reduced. And heat creep resistance may deteriorate. Also, the mixing ratio of the acrylic resin is preferably 30% by weight or less,
If the mixing ratio exceeds 30% by weight, the flame retardancy of the fluororesin surface layer may decrease, and the flame resistance of the film material may become unstable.

In the fluororesin surface layer of the composite film material of the present invention, as the acrylic resin which can be mixed with the fluororesin, a polymer having at least one of C1 to C4 alcohol esters of acrylic acid and methacrylic acid as a main constituent monomer Alternatively, a resin containing a copolymer as a main component is preferable. As the main constituent monomer of such an acrylate resin, specifically, it is preferable to use methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, Particularly, methyl acrylate and methyl methacrylate are preferred. Examples of comonomers to be copolymerized with these main constituent monomers include, for example, esters of C1 to C12 alcohols of acrylic acid or methacrylic acid, vinyl fluoride, vinylidene fluoride, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, acrylonitrile, Butadiene and the like can be used.

These acrylic copolymers may be random copolymers or graft copolymers. For example, a copolymer in which vinylidene fluoride is graft-polymerized to a methyl methacrylate polymer may be used. An acrylate containing an amino group, an imino group, an ethyleneimine residue, or an alkylenediamine residue can also be used.

The fluororesin surface layer is formed by applying a predetermined amount of a paint in a resin solution onto an acrylic resin intermediate layer by a method such as gravure coating, knife coating, dipping or the like, and drying the resin melt. Although a method of topping, and a method of heat laminating a film-like fluororesin can be used,
There is no particular limitation to these.

The thickness of the fluororesin surface layer is 0.5 μm to 1 μm.
If the thickness is smaller than 0 μm, the fluororesin surface layer of the obtained composite membrane material is easily damaged by abrasion or the like during handling, and the damaged portion is easily stained. The flame resistance and antifouling properties of that part may be reduced. Thicker layers may have wrinkles on the folded portion of the obtained composite membrane material. Another feature of the waterproof composite membrane material of the present invention is that stable flame resistance can be obtained by forming a fluororesin surface layer on both surfaces. A coloring agent may be added to the fluororesin surface layer as needed.

In the composite film material of the present invention, the formation of the acrylic resin intermediate layer on the soft vinyl chloride resin base layer and the formation of the laminated resin layer of the fluororesin surface layer on the acrylic resin intermediate layer are performed in advance. After laminating and integrating the fluororesin surface layer and the acrylic resin intermediate layer, it is also possible to form the lamination and integration by a method such as thermocompression bonding to the soft vinyl chloride resin base layer, further emphasizing workability, After previously laminating and integrating a fluororesin surface layer, an acrylic resin intermediate layer, and a soft vinyl chloride resin base layer by a three-layer extrusion method, etc., a base cloth or
It can also be formed on the soft vinyl chloride resin base layer by a method such as thermocompression bonding.

In the composite film material of the present invention, it is also possible to form an acrylic resin layer on the outermost fluororesin layer formed on both sides. At the site where the composite membrane material of the present invention is used, the sheets are joined and sewn by various heat-sealing methods.
It is inferior to the heat sealability between acrylic resins, and this defect can be improved by forming an acrylic resin layer on one side or both sides of the outermost layer. that time,
As the acrylic resin, those used for forming the intermediate layer on the soft vinyl chloride resin base layer can be used, and the thickness of the acrylic resin outermost layer is 0.1.
It is preferably from 10 μm to 10 μm. Even if this acrylic resin outermost layer is provided, the flame resistance of the composite film material of the present invention and the heat creep resistance of the heat-sealed portion are not impaired.

The composite film material of the present invention obtained in this manner has good heat creep resistance of the heat-sealed portion, and all surfaces are uniformly imparted with good flameproofing performance.

[0029]

EXAMPLES The structure and effects of the present invention will be further described with reference to the following examples.

[0030] (Description of the test method) 1. Using a heat-resistant creep-resistant variant Leister hot-air fusing machine, width 3c in the weft direction having a heat-sealed part with a welding width of 4cm in the warp direction
A test piece having a length of 30 cm and a length of 30 m was prepared. 6
294 in an atmosphere at a temperature of 5 ° C., 70 ° C., or 75 ° C.
The state after applying a load of N and left for 24 hours was evaluated according to the following criteria. ：: No abnormality △: Peeling occurred at the heat-sealed part
×: Fracture due to peeling of the heat-sealed part Further, using a YF-7000 type high frequency welder manufactured by Yamamoto Vinita Co., Ltd., a width of 3 cm in a weft direction having a heat-sealed part having a welding width of 4 cm in the sewn part warp direction. A test piece having a length of 30 cm was prepared. A 294 N load was applied to this test piece in an atmosphere at a temperature of 65 ° C., 70 ° C., or 75 ° C., and the state after standing for 24 hours was evaluated according to the following criteria. ：: No abnormality △: Peeling occurred at the heat-sealed part
×: breakage by thermal fusion portion peeling 2. Flameproofing Measure carbonization length, carbonization area, residual flame time, residual dust time by JIS A 1322 method and JIS L 1091 method, and based on the result, pass / fail of JIS A 13222 class and JIS L 1091 Category 3 Pass / Fail was determined. 3. Texture (handling properties) based on the generic polyvinyl chloride resin sheet was evaluated hand feeling test sample. ：: Soft and good handling ×: Hard and poor handling 4. Cold resistance The cold resistance of the test sample was measured and evaluated according to the cold resistance test method of JIS L 6328.

Example 1 (1) Preparation of Sheet Substrate (Formation of Undercoat Layer and Vinyl Chloride Resin Underlayer) As a base cloth, a polyester filament plain woven fabric having the following structure was used. This base cloth was dipped in a 2% water bath of a fluorine-based water repellent, squeezed with a rubber mangle so that the pickup rate became 45%, and dried at 180 ° C. for 3 minutes. This is immersed in a solvent diluent of a resin composition containing the paste vinyl chloride resin of the following formulation 1, so that the base fabric is impregnated with the adhesive resin liquid,
After drying at 50 ° C. for 1 minute, heat treatment was performed at 185 ° C. for 1 minute, and an adhesive resin was adhered to the base fabric at 90 g / m ² to form an adhesive resin undercoat layer. <Formulation 1> Paste vinyl chloride resin 100 parts by weight Di-n-decyl phthalate 65 parts by weight Epoxidized soybean oil 4 parts by weight Ba-Zn-based stabilizer 2 parts by weight Antimony trioxide 20 parts by weight Pigment (TiO ₂ ) 5 parts by weight Isocyanate adhesive 5 parts by weight Toluene (solvent) 20 parts by weight

Next, a film made of a resin composition containing the straight vinyl chloride resin of Formulation 2 in Table 1 (0.16
mm thickness) was prepared on a calendar, and this was adhered to both sides of the undercoat layer-impregnated base fabric to form a vinyl chloride resin base layer of 200 g / m ² per side, and a total weight of 710 g / m ^2.
Was prepared.

(2) Formation of Acrylic Resin Intermediate Layer On both sides of the soft vinyl chloride resin underlayer of the sheet substrate,
Using a gravure coater, a coating amount of a solvent diluted solution of the resin composition of the following Formulation 3 was used as an acrylic resin at a coating amount of 25 g / m 2.
² and dried at 120 ° C. for 1 minute and then cooled to form a 5 g / m ² acrylic resin intermediate layer. <Formulation 3> Acryprene (registered trademark) pellets HBS001 (manufactured by Mitsubishi Rayon Co., Ltd.) 20 parts by weight Toluene-MEK (50/50 weight ratio) (solvent) 80 parts by weight

(3) Formation of Fluororesin Surface Layer On the acrylic resin intermediate layer on both the front and back surfaces formed above, a solvent diluent of a resin composition of the following Formulation 4 as a fluororesin (polyvinylidene fluoride resin) was coated with a gravure coater. Is applied so that the application amount becomes 25 g / m ² , and 12
After drying at 0 ° C. for 1 minute and cooling, a 5 g / m ² fluororesin surface layer (polyvinylidene fluoride resin layer) was formed. <Formulation 4> KYNAR (registered trademark) 710 (manufactured by Elf Atochem Japan KK) 20 parts by weight MEK-toluene-DMF (40/30/30 weight ratio) (solvent) 80 parts by weight This waterproof composite membrane material is And the laminated structure of FIG. 1- (1). This waterproof composite material was subjected to the test. Table 1 shows the test results.

Example 2 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to Formulation 5 in Table 1. This waterproof composite membrane material was subjected to the test. Table 1 shows the test results.

Example 3 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to Formulation 6 in Table 1. This waterproof composite membrane material was subjected to the test. Table 1 shows the test results.

Example 4 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to Formulation 7 in Table 1. This waterproof composite membrane material was subjected to the test. Table 1 shows the test results.

Example 5 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to Formulation 8 in Table 1. This waterproof composite membrane material was subjected to the test. Table 1 shows the test results.

Example 6 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to Formulation 9 in Table 1. This waterproof composite membrane material was subjected to the test. Table 1 shows the test results.

[0040] was prepared waterproof composite film layer in Example 7 Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 10 in Table 1.
Changed to This waterproof composite membrane material was subjected to the test.
Table 1 shows the test results.

Example 8 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 11 in Table 1.
Changed to This waterproof composite membrane material was subjected to the test.
Table 1 shows the test results.

Example 9 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 12 in Table 1.
Changed to This waterproof composite membrane material was subjected to the test.
Table 1 shows the test results.

Example 10 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the process of forming the fluororesin surface layer in Example 1 was changed as follows. Using a gravure coater, a solvent diluent of a resin composition having the following formulation 13 as a vinylidene fluoride-tetrafluoroethylene copolymer resin (tetrafluoroethylene content: 25%) was formed on an acrylic resin intermediate layer on both front and back surfaces. , So that the coating amount is 25 g / m ² ,
After drying at 120 ° C. for 1 minute and cooling, a 5 g / m ² vinylidene fluoride-tetrafluoroethylene copolymer resin (tetrafluoroethylene content: 25%) layer was formed. <Blend 13> Vinylidene fluoride-tetrafluoroethylene copolymer resin (tetrafluoroethylene content 25%) 20 parts by weight MEK-toluene-DMF (40/30/30 weight ratio) (solvent) 80 parts by weight Waterproof The composite membrane material was subjected to the test. Table 1 shows the test results.

Example 11 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the process of forming the fluororesin surface layer in Example 1 was changed as follows. Using a gravure coater, a coating amount of a solvent diluent of a resin composition having the following formulation 14 as a mixed resin of a fluorine resin and an acrylic resin (mixing ratio of acrylic resin: 20%) was formed on the acrylic resin intermediate layer on both front and back surfaces. 25g /
m ² , dried at 120 ° C. for 1 minute, and then cooled to form a 5 g / m ² mixed resin layer of a fluorine resin and an acrylic resin (mixing ratio of acrylic resin: 20%). <Formulation 14> KYNAR (registered trademark) 710 (manufactured by Elf Atochem Japan Co., Ltd.) 16 parts by weight Acryprene (registered trademark) pellets HBS001 (manufactured by Mitsubishi Rayon Co., Ltd.) 4 parts by weight MEK-toluene-DMF (40 / 30/30 weight ratio) (solvent) 80 parts by weight (mixing ratio of acrylic resin: 20%) This waterproof composite membrane material was subjected to the test. Table 1 shows the test results.

Example 12 A waterproof composite membrane material was produced in the same manner as in Example 1. However, after forming the fluororesin surface layer of Example 1, the same layer as the acrylic resin intermediate layer of Formulation 3 was further formed on one side of the fluororesin surface layer. This waterproof composite membrane material is
1 (2). This waterproof composite membrane material was subjected to the test. Table 1 shows the test results.

[0046]

[Table 1]

Table 1 shows the film materials obtained in Examples 1 to 12.
Shows excellent heat creep resistance and flame resistance as shown in
The texture was soft and the handleability was good, and the cold resistance was also good.

Comparative Example 1 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 15 in Table 2.
As a plasticizer and a di-2-mer having a molecular weight of 390 as a plasticizer.
Ethylhexyl phthalate was used at 65 phr. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. The obtained film material had poor heat creep resistance as compared with the film material obtained in Example 1, and was not suitable for practical use.

Comparative Example 2 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 16 in Table 2.
The amount of di-n-decyl phthalate used as a plasticizer was reduced to 30 phr. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. The obtained film material was hard to handle and had poor cold resistance as compared with the film material obtained in Example 1, and was not suitable for practical use.

Comparative Example 3 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 17 in Table 2.
The amount of di-n-decyl phthalate used as a plasticizer was increased to 100 phr. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. The obtained film material is inferior to the film material obtained in Example 1 in heat creep resistance (70 ° C., 75 ° C.) and unstable in flame resistance, so that it is suitable for practical use. There was no film material.

Comparative Example 4 A waterproof composite membrane material was produced in the same manner as in Example 5. However, the composition of the vinyl chloride resin in Example 5 was changed to the composition 18 in Table 2.
The amount of the ethylene-vinyl acetate-carbon monoxide terpolymer (Elvaloy (registered trademark) 712, DuPont Mitsui Polychemicals Inc.) used as a plasticizer was reduced to 40 phr. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. The obtained film material was hard to handle and had poor cold resistance as compared with the film material obtained in Example 5, and was not suitable for practical use.

Comparative Example 5 A waterproof composite membrane material was produced in the same manner as in Example 5. However, the composition of the vinyl chloride resin in Example 5 was changed to the composition 19 in Table 2.
The amount of the ethylene-vinyl acetate-carbon monoxide terpolymer (Elvaloy (registered trademark) 712, Mitsui DuPont Polychemicals Co., Ltd.) used as a plasticizer was increased to 160 phr. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. The obtained film material has a slightly poorer heat creep resistance (75 ° C.) than the film material obtained in Example 5, and is unstable in flame resistance, and is not suitable for practical use. Material.

Comparative Example 6 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 20 in Table 2.
The amount of antimony trioxide used as a flame retardant was reduced to 3 phr. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. The obtained film material was unstable in flame resistance as compared with the film material obtained in Example 1, and was not suitable for practical use.

Comparative Example 7 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the composition of the vinyl chloride resin in Example 1 was changed to the composition 21 in Table 2.
The amount of antimony trioxide used as a flame retardant was increased to 60 phr. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. Compared with the film material obtained in Example 1, the obtained film material had a lower resin strength of the vinyl chloride resin base layer, caused cracks during handling, and had poor cold resistance. The film material was not suitable for practical use.

Comparative Example 8 A waterproof composite membrane material was produced in the same manner as in Example 1. However, the fluororesin surface layer of Example 1 was formed only on the surface. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. Compared with the film material obtained in Example 1, the obtained film material has a lower flame retardancy on the back surface and a difference in flame retardancy on the front and back surfaces. The film material was not suitable for practical use.

Comparative Example 9 A waterproof composite membrane material was produced in the same manner as in Example 2. However, the fluororesin surface layer of Example 2 was formed only on the surface. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. Compared with the film material obtained in Example 2, the obtained film material has a lower flame retardancy on the back surface and a difference in flame retardancy on the front and back surfaces. The film material was not suitable for practical use.

Comparative Example 10 A waterproof composite membrane material was produced in the same manner as in Example 5. However, the fluororesin surface layer of Example 5 was formed only on the surface. This waterproof composite membrane material was subjected to the test. Table 2 shows the test results. Compared with the film material obtained in Example 5, the obtained film material has lower flame retardancy on the back surface and a difference in flame retardancy on the front and back surfaces. The film material was not suitable for practical use.

[0058]

[Table 2]

[0059]

The waterproof composite membrane material of the present invention has a stable flameproof property by selecting a plasticizer to be blended in the soft vinyl chloride resin base layer and forming a fluororesin layer forming the surface layer on both sides. And good heat creep resistance of the heat-sealed portion. The composite membrane material of the present invention can be widely used for event tents such as expositions, permanent membrane structures such as sports facilities, large tent warehouses, etc. without adding special operations such as removing surface resin. It is sewn using a conventional Leister hot air fusion method or a high frequency welder method and can be used widely.

[Brief description of the drawings]

FIGS. 1A and 1B are explanatory views showing a laminated structure of a waterproof composite membrane material of the present invention, respectively.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/10 C08K 5/10 5/521 5/521 C08L 27/06 C08L 27/06 // (C08L 27 / 06 (C08L 27/06 23:08) 23:08) F term (reference) 4F100 AA21 AA29C AH08C AK15C AK17A AK17E AK18A AK18E AK19A AK19E AK25A AK25B AK25D AK25E AK41 AK51 CA05C05A05 AL05BA05 CB00 DG11C DG12 EH46 EJ19 EJ42 EJ82 GB07 JA07C JD05 JJ03 JJ04 JJ07 JL05 YY00C 4J002 BB062 BB072 BD041 BD081 BD091 BD101 DE127 EH096 EH146 EW046 FD010 FD022 FD026 FD030 FD040 FD040

Claims (5)

[Claims] 1. A base cloth made of a fiber cloth, a soft vinyl chloride resin base layer formed on each of the front and back surfaces of the base cloth, an acrylic resin intermediate layer formed on the two base layers, And a fluororesin surface layer formed on the two intermediate layers. In the soft vinyl chloride resin base layer, the soft vinyl chloride resin includes: (1) 5 to 50 phr of antimony trioxide; 2) (a) 40 to 90 phr of a plasticizer of at least one selected from di-n-alkyl phthalates having a molecular weight of 420 or more, adipic acid-based polyester plasticizer, diisodecyl adipate, and trioctyl phosphate; b) 50 to 150 phr of at least one copolymer selected from ethylene-vinyl acetate copolymer and ethylene-acrylate copolymer, and carbon monoxide A polymer obtained by introducing, or (c) 90 phr or less of the plasticizer (a), 150 phr
The following mixture with the polymer (b) is mixed,
A waterproof composite film material having excellent flame resistance and heat creep resistance of a heat-sealed portion. 2. The waterproof composite membrane material according to claim 1, wherein the base fabric further includes an adhesive resin applied, adhered, or impregnated to the fiber fabric. 3. The waterproof composite membrane according to claim 1, wherein the fluororesin surface layer contains at least one selected from polyvinylidene fluoride and a copolymer of vinylidene fluoride and tetrafluoroethylene. material. 4. The fluororesin surface layer is formed of a mixed resin of a fluororesin and an acrylic resin.
The waterproof composite membrane material according to claim 1. 5. The waterproof composite membrane material according to claim 1, further comprising an acrylic resin layer formed on at least one of the fluororesin surface layers.