JP2002030572A - High strength film material excellent in flex waterproof property - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin coated film material having a high mechanical strength and also a high flex waterproof property upon its bending. SOLUTION: This film material is constituted by forming a resin coated layer with a paste sol of a vinyl chloride resin on at least the one side surface of a base fabric obtained by weaving with a composite yarn produced by entangling a staple polyester fiber with a polyester multi-filament yarn.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high-strength membrane excellent in bending water resistance, which is useful for sports facilities, event venues, and permanent membrane structures. More specifically, the present invention relates to a high-strength film excellent in bending water resistance suitable for applications such as tents that require high strength and excellent flexibility and high water resistance.

[0002]

2. Description of the Related Art Conventionally, as a film body such as a tent fabric, a laminated film in which a resin such as soft vinyl chloride is coated on at least one surface of a base fabric made of polyester multifilament yarn or polyester spun yarn or plain weave or mat weave. The body was used a lot. These films have the following characteristics.

[0003] First, with respect to a membrane using a polyester multifilament yarn as a yarn for forming a base fabric, the membrane is roughly 150 kg class, 200 mm, due to its high mechanical strength.
Classification such as a kilo class, a 250 kilo class, and a 300 kilo class is made. One of the features of these membranes using polyester multifilament yarns is that high mechanical strength is obtained. However, when repeatedly subjected to bending and elongation deformation, peeling occurs between the base fabric and the coating resin layer, and the resin film is eventually damaged, resulting in inconvenience such as a decrease in water resistance. On the other hand, a film body in which a woven fabric base based on polyester spun yarn is coated with a resin is known. in this case,
A large number of fluffs, which are characteristics of spun yarn, exhibit an entanglement effect on the coating resin, and are less likely to cause abnormalities such as peeling between the resin layer and the base fabric layer even when subjected to bending deformation. However, when a base fabric based on polyester spun yarn is used, the mechanical strength exhibited for the basis weight is lower than that of polyester multifilament yarn,
For this reason, practical application in the field where high strength is required has not been advanced.

[0004] A soft vinyl chloride resin is often used for a film body such as a tent, and a film laminating process of heating and laminating a calender film on a base fabric is applied to many of them. In this processing method, a film is prepared by hot roll stretching using a straight vinyl chloride resin as a resin, and processing is performed in a basic process of bonding the film to a base cloth. However, there is a problem that cracks are relatively easily generated when bending deformation is given to the directionality. Therefore, measures such as increasing the degree of polymerization of the vinyl chloride resin and increasing the bending durability have been adopted.However, in this case, higher temperature processing conditions are required, and the thermal stress applied to the base cloth and the like is large. There are disadvantages such as excessive heat shrinkage of the cloth.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a film having high strength and excellent bending water resistance.

[0006]

The high-strength film of the present invention having excellent bending water resistance has a base fabric and a soft vinyl chloride resin composition covering at least one surface of the base fabric. And
The base fabric is made of a woven fabric formed of a composite yarn in which polyester staple fibers are entangled with a polyester multifilament yarn, and the soft vinyl chloride resin composition layer is formed by mixing a soft vinyl chloride paste sol with at least one of the base fabrics. It is formed by impregnating or applying to a surface and solidifying it. In the high strength membrane excellent in bending water resistance of the present invention, the weight ratio of polyester multifilament yarn / polyester staple fiber constituting the base fabric is 97/3.
It is preferably within the range of 50/50. In the high strength membrane excellent in bending water resistance of the present invention, the base fabric,
It is preferable to use a woven fabric using a composite twisted yarn obtained by twisting two or more composite yarns.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The polyester multifilament yarn used for the membrane of the present invention has a single fiber strength of 49.0.
3 × 10 ^{−3 to} 107.87 × 10 ⁻³ N / 1.1 dtex (5
１１11 g / denier). Generally, 68.65 × 10 ^{−3 to} 88.26 × 10 ⁻³ N / 1.1dt.
ex (7-9g / denier) is easy to use. The filament count of the multifilament is 555.6 dtex /
80 to 555.6 dtex / 350 (500 denier /
It is easy to use around 80-500 denier / 350).

The multifilament has a thickness of 55.6 to 1
Used in the range of 666.7 dtex (50 to 1500 denier). However, this depends on the required strength and can be arbitrarily selected. The polyester staple fiber used in the present invention has a weave of 0.56 to
7.78 dtex (0.5 to 7 denier), preferably 1.
Those having 11 to 5.56 dtex (1 to 5 denier) and a staple length of 15 mm to 200 mm can be used. Among these, those having a staple length of 70 to 120 mm have good entanglement with the multifilament, and the length of the generated fluff does not deteriorate the appearance of the obtained film.

The composite weight ratio of the polyester multifilament yarn and the polyester staple fiber is 97 /
It is preferably in the range of 3 to 50/50, and among them, the ratio of 70/30 to 60/40 is more preferable. When the weight ratio of the polyester staple fiber in the composite yarn is 50% or more, the generation of floating fuzz during weaving increases, and during weaving, troubles such as the entanglement of the fuzz on the reed and the fuzz are scraped off occur. It may be a base fabric with many. On the other hand, if the weight ratio of the polyester staple fiber is less than 3%, the effect of entanglement with the resin due to the fluff in the composite yarn formed by the staple fiber becomes insufficient, and the improvement in bending water resistance becomes insufficient. There is.

The composite yarn used for producing the woven fabric for the base fabric of the present invention can be produced by an appropriate method so that the polyester staple fiber is entangled with the polyester multifilament yarn. For example, the multifilament yarn may be expanded (spreading), and the staple fiber may be interposed therebetween to bind the multifilament. In this case, the staple fiber can be firmly held by wrapping the staple fiber with the filament bundle holding the staple fiber. Also, as another entanglement method, a staple fiber sliver may be wound around the multifilament yarn, or it may be further twisted, or
The multifilament yarn may be spread, staple fiber slivers may be aligned and bound, and the multifilament yarn may be wrapped.

[0011] The composite yarn produced in this manner is composed of 2
Two or more strands can be twisted to be used as a composite twisted yarn, and a film body having better bending water resistance can be obtained by using this. The effect is that by twisting two or more of the composite yarns, the distribution of fluffs extending on the surface of the composite yarn becomes more uniform; the polyester staple fibers entangled with the multifilament yarn are less likely to fall off. A small unevenness occurs in the base fabric woven by the twisted yarn, and the contact area between the base fabric and the resin increases; and, when the membrane undergoes bending deformation, the base fabric and the resin It is considered that the stress generated at the interface is dispersed, and peeling or the like hardly occurs.

The composite yarn or the composite twist yarn thus obtained is woven into a woven structure such as plain weave or mat weave to produce a base fabric of a membrane. The basis weight of the base fabric can be appropriately selected according to the strength required for the membrane, but the base fabric for a polyester high-strength membrane is generally in the range of 250 g / m ² or more. Further, depending on the characteristics of the membrane, the ratio of the number of warp yarns to the number of warp yarns is 45/55 to 55/4.
When it is set in the range of 5, the handling of the film body becomes easy and stable at the time of secondary processing performed on a large area and at the time of stretching.

The film of the present invention is characterized in that at least one surface of the base cloth is impregnated or coated with a paste sol of a vinyl chloride resin composition and solidified.
Examples of the vinyl chloride resin used in the present invention include vinyl chloride polymers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-acrylate copolymers, vinyl chloride-vinylidene chloride copolymers, and the like. Can be used alone or in combination of two or more. As the soft vinyl chloride resin composition used in the present invention, one containing at least one of a plasticizer, a stabilizer, a filler, an ultraviolet absorber, a fungicide, and a flameproofing agent is used. be able to.

As the plasticizer which can be used in the present invention, phthalate ester plasticizers include dibutyl phthalate, diethyl phthalate, diheptyl phthalate, di-2-ethylhexyl phthalate, di-n-octyl phthalate, dinonyl phthalate, di-n -Decyl phthalate, diisodecyl phthalate, ditridecyl phthalate, butylbenzyl phthalate and the like. As a polyester plasticizer, adipic acid and glycols such as 2-methyl-1,8-octanediol, 1,2-propanediol, 1,3-butanediol, 2-ethylhexanol and n-octanol were esterified. What can be used. Further, as the trimellitic acid-based plasticizer, tri-2-ethylhexyl trimellilate, triisodecyl trimellilate, or the like can be used. As other plasticizers, pyromellitic acid-based plasticizers such as 2-ethylhexyl pyromellilate, biphenyltetracarboxylic acid ester-based plasticizers, and the like can be used. These plasticizers are based on 100 parts by weight of the vinyl chloride resin.
It is preferable to use a compounding amount of 30 to 120 parts by weight.

Examples of the stabilizer for the soft vinyl chloride resin composition include stabilizers such as calcium / zinc, barium / zinc, cadmium / barium, lead, organotin laurate, organotin mercaptite, and epoxy. They can be used alone or as a mixture. The amount of the stabilizer is preferably 0.5 to 10 parts based on 100 parts of the vinyl chloride resin.

As the ultraviolet absorber for the soft vinyl chloride resin composition, ultraviolet absorbers such as triazole, benzophenone, cyanoacrylate, salicylic acid and hydroquinone can be used. From these two
(5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2-ethylhexyl-2-cyano-3,3-diphenylacrylate alone Alternatively, it is particularly preferable to use a mixture,
For example, when 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate are selected and used in a blending amount of 0.5 to 1 part by weight, It is effective for preventing deterioration and coloring of the soft vinyl chloride resin.

Examples of the filler for the soft vinyl chloride resin composition include calcium carbonate, magnesium carbonate, barium sulfate, aluminum hydroxide and magnesium hydroxide.
It is preferable to use more than one kind in a blending amount of up to 50 parts with respect to 100 parts of the vinyl chloride resin. However, it is advantageous to keep the amount of the filler added as small as possible to maintain the bending water resistance of the obtained film.

The film of the present invention preferably has flame retardancy, but the flame retardant imparted to the soft vinyl chloride resin of the film of the present invention is typically antimony trioxide. Inorganic flameproofing agents, bromo-based flameproofing agents, phosphate-based flameproofing agents, halogen-containing phosphoric esters, chlorinated paraffins, and the like can be used. The inorganic flameproofing agent such as antimony trioxide is preferably used in an amount of up to 50 parts with respect to 100 parts of the vinyl chloride resin.
If the number of added parts exceeds 50 parts, the bending resistance of the obtained resin composition is reduced, and the resin composition may be separated from the base fabric due to bending or a crack may be generated in the resin layer. May reduce the performance. Therefore, as in the case of the filler, the addition amount of the inorganic flameproofing agent should be as small as possible.

As the bromo flame retardant, decabromodiphenyl ether, pentabromomethylbenzene, hexabromobenzene and the like can be used. As the phosphoric ester flame retardant, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate and the like can be used. The above flame retardants can be used alone or in combination of two or more.

An adhesive can be added to the paste sol for the purpose of enhancing the adhesiveness between the soft vinyl chloride resin composition layer formed therefrom and the base fabric. As the adhesive used for this purpose, a compound obtained by mixing an isocyanate group-containing compound and a polyol, a polyfunctional isocyanate compound, and the like are used.

The vinyl chloride-based resin composition layer is formed by applying a predetermined amount of a paste sol of the vinyl chloride-based resin composition by a method such as dipping, knife coating, casting, screen coating, or gravure coating. Impregnate or apply on one or both sides of the fabric and solidify. The paste sol may be applied in a desired amount in a single operation, or may be applied in two or more divided operations. In this case, a difference in the composition or a difference in the amount of the composition may be provided between the layer close to the base cloth and the layer further outside.

[0022] If the membrane material of the present invention is used as a permanent film material, the adhesion amount of the coating resin layer is preferably 400 g / m ² or more, and more preferably 450~600g / m ^2. After impregnating or applying the paste sol, the paste sol layer is subjected to a heat treatment under a predetermined temperature condition to be solidified. If necessary, the surface of the soft vinyl chloride resin composition layer may be embossed, or may be subjected to a surface treatment for the purpose of preventing contamination.

[0023]

The present invention is further described by the following examples.

[0024] Description of the test method 1. The mass measurement of the film was performed according to JIS-L-1096 method. 2. Measurement of Base Weight of Membrane of Resin The resin of the sample used for measuring the mass of the membrane was dissolved and removed with THF, dried at 100 ° C. for 1 hour, and the mass was measured. 3. Tensile strength of membrane The tensile strength of the membrane in the warp and weft directions was measured by the JIS-L-1096 strip method. The average tensile strength measured in the warp and weft directions was used to indicate the tensile strength of the membrane. 4. Tensile strength of membrane / base fabric weight The value obtained by dividing the tensile strength of the membrane by the fabric weight. A higher value means that a higher strength can be obtained with a smaller basis weight.

[0025] 5. Bending test “Y. S. S. Type Repeated Permanent Fatigue Tester ”, the length shown in FIG.
The film sample 1 cut into cm was folded in two at right angles in the width direction and mounted, and was bent so as to reciprocate between the shapes (A) and (B) shown in FIG. .
The number of bending was 50,000 times. Test environment temperature is 20 ℃
Alternatively, the temperature was set to 0 ° C. The appearance was checked for abnormalities using a loupe, and evaluated and displayed according to the following criteria. ◎: no abnormality, ：: slight peeling was observed between the base fabric and the resin, Δ:
Cracking was observed in the resin layer. ×: Peeling and cracking of the resin layer were observed. 6. With respect to the sample after performing the water pressure resistance bending test, JIS-L-10
92 Hydrostatic pressure was measured by the hydrostatic pressure method.

Example 1 A fineness of 1.56 dtex (1.25 dene (250 denier) / 48 polyester multifilament yarns) was obtained.
A polyester staple fiber having a staple length of 100 mm and a staple length of 100 mm was entangled at a weight ratio of 65/35 to prepare a composite yarn. The number of strands of this thread is 6
t / 25.4 mm. A composite twisted yarn obtained by twisting these two yarns at a number of 220 t / m was used as 40 warp yarns / 25.
Weaving was performed with a sluser loom so as to be 4 mm and 40 wefts / 25.4 mm. The obtained woven fabric for base cloth is 305 g /
It had a basis weight of m ² .

As a pretreatment for resin coating, the base fabric was subjected to heat setting at 180 ° C. for 2 minutes, and then immersed in a 3% bath of a fluorine-based water repellent to obtain a pickup rate of 40%.
The mixture was squeezed with a rubber mangle so as to obtain a film, and further dried at 180 ° C. for 2 minutes. A vinyl chloride resin paste sol having a composition shown in Table 1 was impregnated and adhered to the pretreated base fabric by dipping, and heat-treated at 185 ° C. for 2 minutes. The mass of the obtained film was as shown in Table 3. Table 3 shows the test results.

Example 2 Using the composite twisted yarn prepared in Example 1, 43 warp yarns /
The fabric was woven so as to have a width of 25.4 mm and a width of 42 wefts / 25.4 mm to prepare a woven fabric for a base fabric. This base cloth is 325 g / m
It had a basis weight of ² . This base fabric was subjected to a vinyl chloride resin paste sol process under the same pretreatment and composition and conditions (Table 1) as in Example 1. Table 3 shows the test results.

Example 3 The composite yarn and the composite twist yarn prepared in Example 1 were alternately arranged to produce a plain woven fabric having the same weaving structure as in Example 1.
The base fabric made of this woven fabric had a basis weight of 295 g / m ² . This base fabric was subjected to a vinyl chloride resin paste sol process of the same pretreatment and the same composition and conditions as in Example 1. Table 3 shows the test results.

Example 4 The same three composite yarns as those produced in Example 1
The composite twisted yarn twisted at 50 t / m is used for 33 warp yarns /
The fabric was woven with a structure of 25.4 mm and 32 wefts / 25.4 mm. The basis weight of the obtained woven fabric is 340 g / m.
^{Was 2} . The same pretreatment as in Example 1 is applied to this base fabric,
A vinyl chloride paste sol process having the same composition and conditions was performed. Table 3 shows the test results.

Example 5 A polyester staple fiber having a fineness of 1.33 dtex (1.2 denier) and a staple length of 80 mm was added to 166.7 dtex (150 d) polyester multifilament yarn so as to have a weight ratio of 70/30. To form a composite yarn. Three hundred composite yarns
The composite twisted yarn twisted at t / m is 48 warp yarns / 25.
It was woven with a sluser loom so as to be 4 mm and 50 wefts / 25.4 mm. The obtained woven fabric had a basis weight of 360 g / m ² . Table 3 shows the test results. As pretreatment of resin coating on the base cloth made of this woven cloth, 195
After heat setting at 2 ° C. for 2 minutes, the film was further immersed in a 5% bath of a fluorine-based water repellent, squeezed with a rubber mangle so that the pickup ratio became 45%, and further dried at 180 ° C. for 2 minutes. A vinyl chloride resin paste sol having the composition shown in Table 1 was impregnated and adhered to the pretreated base fabric by a dipping method, and was subjected to a heat treatment at 185 ° C. for 2 minutes. The mass of the obtained film was as shown in Table 3. Table 3 shows test results
Shown in

Example 6 A composite twisted yarn obtained by twisting four identical yarns produced in Example 5 at several 150 t / m was used in a mat weave structure in which each of a warp yarn and a weft yarn was two by two. The weave tissue
Weaving was performed so that the length became 8 warp yarns / 25.4 mm and the width of 39 weft yarns / 25.4 mm. The base cloth made of this woven cloth is 370
g / m ² . Example 5 was added to this base cloth.
The same pretreatment as described above was performed, and then a dipping process of a vinyl chloride paste sol having the same composition as that used in Example 1 was performed. Table 3 shows the test results.

Comparative Example 1 A urethane-based adhesive was applied to the same base fabric as that used in Example 1 using a gravure coater so that the amount of the adhesive applied was 50%.
g / m ² . A calender film (thickness: 0.18 mm) having the composition shown in Table 2 was heated at 180 ° C.
Was laminated on both sides of the base fabric by using a hot roll of No. 1. The mass of the obtained film was as shown in Table 3. Table 3 shows the test results.

Comparative Example 2 A polyester multifilament yarn of 555.6 dtex (500 denier) was woven into a structure of 40 warp yarns / 25.4 mm and 41 weft yarns / 25.4 mm. The basis weight of the obtained base fabric was 180 g / m ² . The same pretreatment as that used in Examples 1 to 4 was applied to this base fabric, a vinyl chloride paste sol having the composition shown in Table 1 was adhered by a dipping method, and a heat treatment was performed at 185 ° C. for 2 minutes. The mass of the film was as shown in Table 3. Table 3 shows the test results.

Comparative Example 3 Polyester spun yarn 2 of 590.6 dtex (10th count)
The twisted yarn was twisted at several 150 t / m and woven into a structure of 38 warp yarns / 25.4 mm and 35 weft yarns / 25.4 mm. The basis weight of the obtained woven fabric is 37
It was 0 g / m ² . The same pretreatment as in Example 1 was applied to this base fabric, and a vinyl chloride resin paste sol having the composition shown in Table 1 was impregnated and adhered by dipping, followed by heat treatment at 185 ° C. for 2 minutes. The mass of the film was as shown in Table 3. Table 3 shows the test results.

Comparative Example 4 295.3 dtex (20th count) polyester spun yarn 3
Strands obtained by twisting the books at several 150 t / m were woven into a structure of 43 warp yarns / 25.4 mm and 41 wefts / 25.4 mm. The basis weight of the obtained woven fabric is 3
It was 10 g / m ² . This base cloth was subjected to the same pretreatment as in Example 1, and further impregnated with a polyvinyl chloride resin paste sol having the composition shown in Table 1 by dipping, and then subjected to 185 ° C.
For 2 minutes. The mass of the film was as shown in Table 3. Table 3 shows the test results.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

In Tables 1 to 3, as can be seen from Examples 1 to 6, in the film body according to the present invention, as a result of the water pressure resistance test after the bending test, cracking of the coating resin layer leading to a decrease in the water pressure resistance was observed. I couldn't see it. For these,
In the membranes of Comparative Examples 1 and 2, a decrease in water pressure was caused by the occurrence of resin cracks in the bending test, and in the membranes of Comparative Examples 3 and 4, there was no decrease in the water resistance, but with respect to the basis weight of the base fabric. The strength appearance rate was low, and a high-strength film was not obtained with a limited basis fabric weight. According to the good test results seen in the membranes of Examples 1 to 6, the polyester multifilaments constituting the base fabric maintain the strength of the membrane at a high level, and the polyester staple fibers entangled with the polyester multifilament yarn. It was confirmed that the entanglement with the resin coating layer formed by impregnation or application of the soft vinyl chloride paste sol significantly improved the bending resistance of the film body.

[0041]

The film of the present invention has both high strength and high flexural water resistance, and can be used as a large foldable membrane-structured roof, large openable tent warehouse, large tent for leasing, etc. It could be widely applied to applications such as large-scale membrane structures with bending.

[Brief description of the drawings]

FIG. 1 is an explanatory view showing a change in shape of a film sample in a film bending test of the present invention.

[Explanation of symbols]

 1: membrane sample 2: fold A: shape when membrane sample is bent B: shape when membrane sample is extended

Claims (3)

[Claims] 1. A composite comprising a base fabric and a soft vinyl chloride resin composition covering at least one surface of the base fabric, wherein the base fabric is formed by entanglement of polyester staple fibers with a polyester multifilament yarn. A soft vinyl chloride resin composition layer formed of a yarn, formed of a woven fabric, and formed by impregnating or applying a soft vinyl chloride paste sol to at least one surface of the base fabric and solidifying the soft vinyl chloride paste sol; A high-strength film having excellent bending water resistance. 2. The high flexural water resistant high according to claim 1, wherein the weight ratio of the polyester multifilament yarn / polyester staple fiber constituting the base fabric is in the range of 97/3 to 50/50. Strength membrane. 3. The high-strength film body excellent in bending water resistance according to claim 1, wherein the base fabric is made of a woven fabric using a composite twisted yarn obtained by twisting two or more of the composite yarns.