JPH0155100B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is directed to a laminated structure made of a specific fully aromatic polyamide fiber characterized by high strength as a base material, a fiber base layer obtained by impregnating or coating the base material with a resin, and a film layer. Regarding. More specifically, it is a highly weather resistant, highly strong composite membrane type laminated structure that uses one or more types of films, including a film with good weather resistance and a film with good gas barrier properties, as the film layer. It is related to. BACKGROUND ART Conventionally, so-called rubberized woven fabrics, which are fabrics made of nylon or polyester fibers coated with rubber, have been used as membrane materials for balloons or awnings. However, when using these processed woven fabrics for the above-mentioned uses and purposes, it is important to note that the fibers used in the woven fabrics themselves have a high elongation and lack dimensional stability when stress is applied. However, there have been problems such as limited gas barrier properties and insufficient strength as the size increases. Increasing the thickness or basis weight in order to increase strength or improve gas barrier properties is undesirable because it increases the weight of the material itself and leads to a reduction in performance. New, stronger materials and combinations thereof are desired. was. The present inventors have accomplished the present invention as a result of extensive research into developing membrane materials that are lightweight and capable of exhibiting high strength by overcoming these problems. That is, the present invention provides (a) substantially the following general formula (A)
, a fiber base layer formed by impregnating or coating with a resin a fiber obtained from a wholly aromatic polyamide having a structural unit represented by the general formula (B) or/and (C), and (b) a film layer. The present invention relates to a laminated structure consisting of. [However, in the above general formulas (A), (B), and (C), Ar ₁ , Ar ₂ , and Ar ₃ are the same or different, and are biaxial with bond chains extending along coaxes and/or parallel axes. Represents aromatic hydrocarbon ring residues, aromatic heterocyclic residues bonded by the ring atoms representing the maximum spacing, and combinations thereof, where X is the same or different halogen group, alkyl group, aralkyl group , aryl group, and alkoxy group, n represents an integer of 1 to 3, and Y represents -O-, CH ₂ -, -SO ₂ -, -CO −，−
S-,

[Formula] -NH-,

[Formula] (R is an alkyl group having 5 or less carbon atoms) represents a divalent residue selected from the group consisting of: ] The wholly aromatic polyamide fiber used as the high-strength material component of the laminated structure according to the present invention has a smaller dimensional change than conventionally used organic fibers such as polyethylene terephthalate fiber and nylon, and has extremely high strength. It is strong and has the potential to have high reliability in terms of mechanical properties under stress. That is, by using the wholly aromatic polyamide fibers according to the present invention, it becomes possible to provide a membrane material that is lighter in weight as a layered structure and is also extremely strong. It is essential that the wholly aromatic polyamide used in the present invention has a structural unit represented by the general formula (A) and (B) and/or (C). As specific examples of structural units represented by these general formulas, for example, for general formula (A), etc., and for general formula (B), For general formula (C) etc. can be given. Further, the wholly aromatic polyamide used in the present invention has a structural unit represented by the general formula (A) and the general formula (B) or/and the general formula (C),
The usage ratio can be arbitrarily selected within the range of (A): 5 to 95 mol%, (B): 0 to 95 mol%, and (C): 0 to 95 mol%. Examples of specific usage forms include (A): 50 mol% + (B): 50 mol%, (A): 40 mol% + (C): 60 mol%, (A): 30 mol% + Examples include (B): 30 mol% + (C) 40 mol%. The wholly aromatic polyamide fiber used as the fiber base material in the present invention is usually used in the form of long fibers, but it can also be used in the form of cut fibers. In addition, it is usually preferably used in the form of a long fiber woven fabric for the purpose of dimensional stability and high strength, but it can also be used in the form of a woven fabric made of spun yarn, a nonwoven fabric made of long fibers, or a nonwoven fabric made of short fibers. It is possible. The resin used in the present invention may be a thermosetting resin or a thermoplastic resin, and can be selected depending on the intended use. Specific examples of thermosetting resins include epoxy resins, modified phenolic resins, and modified polyurethane resins, and specific examples of thermoplastic resins include polyester resins, ethylene/vinyl alcohol copolymers, and polyurethane resins. resin,
Examples include chlorosulfonated polyethylene elastomer, polyamide resin, and synthetic rubbers. Particularly preferred examples of resins include polyurethane resins, polyester resins, and chlorosulfonated polyethylene elastomers because they maintain flexibility and have good weather resistance. Conventionally used methods can be employed to process these resins by impregnating or coating the above-mentioned fiber base material. That is, a woven fabric or a nonwoven fabric sheet made of wholly aromatic polyamide fibers according to the present invention is impregnated with a solution obtained by dissolving or diluting the above-mentioned resin in a solvent, or a bar, a doctor knife, or a roll is used. Alternatively, it is also possible to directly apply a hot-melt resin as a melt, or to layer films made in advance and then heat-press them and impregnate them. The adhesion ratio of the resin to the fiber weight in the fiber base layer can be selected arbitrarily, but it is usually
It is adjusted within the range of 0.2 times to 3 times, preferably 0.3 to 1.5 times. Further, in order to make the performance of the laminated structure according to the present invention more effective or diversified, flame retardants, light stabilizers, antioxidants, pigments and other additives can be used in combination. The purpose of using the film layer, which is another component of the laminated structure related to the present invention, is to maintain weather resistance and exhibit gas barrier properties. Therefore, depending on the target level, material selection and Thickness design is performed. As the film for the purpose of imparting weather resistance, a fluorine-based polymer is used, and a polyfluorinated vinyl film is particularly preferred. As the gas barrier film, films of polyester, polyamide, aromatic polyamide, polyvinyl fluoride, ethylene/vinyl alcohol copolymer, polyvinylidene chloride, and the like are preferably used. As the lamination adhesive between the film and the film or fiber base material layer in the film layer formed by one or a combination of two or more of these, various thermosetting or thermoplastic adhesives can be used. Specific examples of such lamination adhesives include epoxy resins, polyester resins, polyamide resins, chlorosulfonated polyethylene, and ethylene.
Many materials such as vinyl alcohol copolymers, polyurethane resins, synthetic rubbers, etc. can be used. That is, when using two or more types of film layers, these films can be bonded together to form a so-called laminate film and then laminated with the aforementioned fiber base material layer. It is also possible to overlap the coated film(s) with a fiber base material layer and integrate them into a membrane by heat and pressure. Although it is possible to apply an adhesive in advance to bond the film layer and the fiber base material layer together, it is also possible to apply an adhesive in advance, but it is also possible to bond the film layer and the fiber base material layer together using the adhesive ability of the resin impregnated or coated on the fiber base material layer. It is also possible to dispense with adhesive coating. The thus obtained laminated structure is a laminated material that is not only lightweight and highly strong, but also has extremely good weather resistance and can withstand outdoor use. Also,
Due to the presence of the film layer constituting the laminated structure according to the present invention, gas permeability can be suppressed. Therefore, by using the laminated structure of the present invention, it is also possible to form a closed container that can contain gas (for example, helium, etc.). In order to explain the laminated structure according to the present invention in detail, an example of the configuration of the laminated structure is shown in the drawings. 1 to 3 are schematic cross-sectional views of a laminated structure according to an embodiment of the present invention. In Figures 1 to 3, 1: weather-resistant film 2: lamination adhesive 3: gas barrier film 4: wholly aromatic polyamide fiber 5: impregnated or coated resin 6: backing film. When the laminated structure according to the present invention is used as a membrane material outdoors, for example, the upper side in FIGS. 1 to 3 becomes the outer skin, and the lower side becomes the inside. That is, even in an outdoor exposure environment, the action of the weather-resistant film 1 prevents light transmission to the inside or corrosion by chemicals, and protects the components located inside, especially the fully aromatic polyamide fibers 4. It is possible to prevent strong deterioration of Further, the gas barrier film 3 suppresses gas permeation at the upper and lower interfaces of the laminated structure in FIGS. 1 to 3, and may be located in an intermediate layer of the structure. 1 or 3), or the innermost layer (Fig. 2). The laminated structure according to the present invention has excellent properties such as high strength, light weight, weather resistance, and gas barrier properties, so it can be used for large tents, air structure buildings, etc.
It is extremely useful as a material that can be applied not only to conventional systems such as oil fences and balloons, but also to new systems such as semi-permanent membrane buildings, sea walls, breakwaters, and flying objects. The present invention will be explained in more detail with reference to Examples below. In the examples, "parts" simply represent parts by weight. Furthermore, the present invention is not limited to the following examples. Reference example 3.10.72 parts of 4'-diaminophenyl ether and 5.79 parts of paraphenylene diamine were dissolved in 500 parts of N-methylpyrrolidone under a stream of dry nitrogen, and after cooling to 0°C, with vigorous stirring, terephthalic acid was dissolved. 21.74 parts of chloride powder was quickly added to carry out polymerization, and about 5 hours later, calcium oxide was added to neutralize by-product hydrochloric acid. Intrinsic viscosity of the thus obtained polymer (polymer concentration 0.5 g/dl in concentrated sulfuric acid,
(measured at a temperature of 30℃) is 3.02, and the solution viscosity is
It was approximately 500 poise at 100°C. The yarn physical properties of the multifilament (300de/100fil) obtained by excessively defoaming this neutralized solution, spinning it by a half-dry and half-wet method, washing it with water, drying it, and then hot-drawing it through a hot plate heated to 500℃ are as follows. It was as follows. {Strength 26.2g/Young's modulus 630g/Elongation 3.9
%} Example 1 (1) Preparation of fiber base layer The multifilament of fully aromatic polyamide fiber obtained in the reference example was plain-woven (35 fibers/2.5 cm x 35 fibers/
2.5cm) fabric. The basis weight of this fabric is 96g/
m ² and thickness was 160 microns. This fabric was impregnated with Bostik 4050, a polyurethane adhesive resin manufactured by Bostik Japan (a 25% solids solution dissolved in an ester solvent), and passed between two bars with a clearance of 250 microns. The amount of adhesion was controlled. The fabric weight of the aromatic polyamide fiber fabric impregnated with the polyurethane resin thus obtained was 160 g/m ² (adhesion rate 67.7% by weight). (2) Lamination with film layer Using a doctor knife (0.1 mm) on a 25 micron thick polyethylene terephthalate film,
After coating the above-mentioned "Bostik 4050" (solution), the solvent was evaporated to obtain a polyethylene terephthalate film provided with an adhesive coating. A polyfluorinated vinyl film ("Tedlar Film"#100BG30WH manufactured by DuPont) was superimposed on this polyethylene terephthalate film, and then the resin-impregnated wholly aromatic polyamide fiber base material and backing film were layered to form the structure shown in Figure 1. After laminating 9 micron polyethylene terephthalate films as films, they were heated and pressed using a press heated to 140°C to form a laminated structure. In Example 1, the laminated structure shown in FIG. 1 specifically has the following configuration. 1: Weather-resistant film (polyfluorinated vinyl film, 100BG30WH, 25μ) 2: Lamination adhesive (Bostik 4050) 3: Gas barrier film (polyethylene terephthalate film, 25μ) 4: Fully aromatic polyamide fiber (fabric) 5: Impregnation Resin (Bostik 4050) 6: Backing film (polyethylene terephthalate film, 9μ) (3) Characteristics of the laminated structure The total basis weight of the laminated structure obtained in the previous section is:
The weight was 257g/m ² and the thickness was 234μ. The uniaxial tensile strength of the structure was 224 Kg/2.5 cm, and the elongation at break was 13%, confirming that it exhibited extremely excellent strength. In addition, the laminated structure is used as a sunshine weather meter (Toyo Rika Kogyo “Standard Weather Meter”).
We-SuN-DC type) was subjected to a weather resistance accelerated test, and the strength retention rate after 500 hours of acceleration was 85 ~
It was 90%. In addition, as a blank, use the aforementioned polyfluorinated vinyl film (Tedlar).
100BG30WH) strength retention rate is 25
It decreased to ~30%. In other words, it was confirmed that the laminated structure according to the present invention has extremely high strength and also exhibits extremely excellent weather resistance in the accelerated weather resistance test. Furthermore, the folding strength of the laminated structure measured by an MIT type folding durability tester was 16,500 times (the number of swings before breaking). Comparative Example 1 In place of the fully aromatic polyamide fiber in Example 1, a yarn (400 de/267 fil) of "Kevlar 29" manufactured by Dupont was used, and trial weaving was carried out to have the same gray fabric weight as the fabric of Example 1. did. The gray fabric weight of the comparative fabric (plain weave) obtained was 97 g/m ² . Impregnated with resin in exactly the same manner as in Example 1,
Next, when we tried laminating polyfluorinated vinyl film and polyethylene terephthalate film, the laminated structure had a basis weight of 262 g/m ² and a uniaxial tensile strength of 208 Kg/2.5 cm, but an MIT bending strength of 8200. It was extremely bad. Example 2 Trial weaving of the fully aromatic polyamide fiber multifilament obtained in the reference example (25 pieces/2.5 cm x 25 pieces/
The fabric weight of the plain weave fabric obtained by 2.5 cm) was 69 g/m ² . Using the wholly aromatic polyamide fiber fabric, in the same manner as in Example 1, 1: Polyfluorinated vinyl film (100BG30WH) 2: Lamination adhesive (Bostik 4050) 3: Polyethylene terephthalate film
(25 microns) 4, 5: Fully aromatic polyamide fiber fabric impregnated with Bostik 4050 6: Polyethylene terephthalate film
(9 microns) Laminated structure (fabric weight 248 g/m ² , thickness 204 mm)
Micron) was prepared. The uniaxial tensile strength of the laminated structure is 165Kg/2.5
cm, MIT bending strength was extremely good at 36,000 times. Example 3 The procedure was the same as in Example 2, except that chlorosulfonated polyethylene elastomer ("Hypalon 20" manufactured by DuPont) was used instead of Bostik 4050, which was used as the lamination adhesive and impregnating resin in Example 2. A laminated structure was prepared. The properties of the laminated structure were extremely good as shown in Table 1. Example 4 Bostik 4050, which was used as the lamination adhesive and impregnation resin in Example 2, was added with 5% by weight of Tinuvin 326 as an ultraviolet stabilizer, and a polyfluorinated vinyl film ( A laminated structure was prepared in the same manner as in Example 2, except that 100BG30UT) was used. The properties of the laminated structure are shown in Table 1. Example 5 Same as Example 4 except that instead of Bostic 4050 with Tinuvin 326 (5% by weight) added in Example 4, Bostic 4050 with 5% of carbon black added and thoroughly kneaded in a ball mill was used. A laminated structure was prepared. The properties of the laminated structure are shown in Table 1.

【table】 [Brief explanation of drawings]

1 to 3 are schematic cross-sectional views of a laminated structure according to one embodiment of the present invention. 4...Fully aromatic polyamide fiber.

Claims (1)

[Scope of Claims] 1 (a) A fiber obtained from a wholly aromatic polyamide having structural units substantially represented by the following general formula (A) and general formula (B) or/and (C). A laminated structure consisting of a fiber base layer impregnated or coated with a resin and (b) a film layer. [However, in the above general formulas (A), (B), and (C), Ar ₁ , Ar ₂ , and Ar ₃ are the same or different, and are biaxial with bond chains extending along coaxes and/or parallel axes. Represents aromatic hydrocarbon ring residues, aromatic heterocyclic residues bonded by the ring atoms representing the maximum spacing, and combinations thereof, where X is the same or different halogen group, alkyl group, aralkyl group , aryl group, and alkoxy group, n represents an integer of 1 to 3, and Y represents -O-, CH ₂ -, -SO ₂ -, -CO −，−
Represents a divalent residue selected from the group consisting of S-, [Formula] -NH-, [Formula] (R is an alkyl group having 5 or less carbon atoms). ] 2. The laminated structure according to claim 1, wherein Y is -O-. 3 Claim 1 in which X is a halogen atom
The laminated structure according to item 1 or 2. 4. The laminated structure according to claim 1, 2 or 3, wherein the resin is a thermosetting resin. 5. The laminated structure according to claim 1, 2 or 3, wherein the resin is a thermoplastic resin.