JPH0612923Y2 - Flame retardant heat resistant sheet - Google Patents

Description

[Detailed description of the device]

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant heat-resistant sheet. More specifically, the present invention relates to a sheet material having excellent flame resistance and heat resistance, as well as stain resistance, weather resistance, sewability and refraction resistance.

[0002]

2. Description of the Related Art In recent years, sheet materials containing various synthetic resins have been used as members for building materials, interior materials, vehicles, ships and aircraft. These synthetic resins have the drawback of generating a large amount of harmful or toxic gas and smoke when burned by a fire or the like. For example, a large amount of sheets containing a polyvinyl chloride resin is used as the above sheet material, and various proposals have been made for making such sheet material nonflammable or flame retardant.

For example, in Japanese Examined Patent Publication No. 55-4582, a borate, a zinc compound, or an iron compound, aluminum hydroxide, or barium sulfate is added to a polyvinyl chloride resin to be applied to a sheet material base cloth. However, the result is not yet satisfactory.

Japanese Patent Publication No. 53-13505, Japanese Patent Publication No. 51-
In 37397 and JP-A-54-68470, it is proposed to use a silicone resin as a non-combustible resin. In these cases, the effect of incombustibility or flame retardancy is considerably high, but the sheet material coated with such a silicone resin is remarkably used during its use when used outdoors, for example, as a tent sheet. Since this silicone resin coating layer is easily soiled and its surface is soft and fragile, it has a drawback that various solid dust powders are attached, penetrated and buried, or the coating layer is peeled off.

Therefore, recently, P. T. F.
E. Non-combustible tent curtain material coated with (polytetrafluoroethylene) has been developed and used. However,
P. T. F. E. Can not be formed into a film, for example, a base cloth is impregnated with a dispersion having a concentration of 60% and a viscosity of 20 centipoise, and the high temperature (about 400 ° C or even 350 ° C-
It is coated by baking at 500 ° C. Since such impregnation and high temperature firing are performed, the processing speed is slow at about 30 cm / min, and if a sufficient coating thickness is formed at one time, sagging, mud-like cracks, foaming, etc. occur on the coated surface and the coating cracks. There is a downside in performance, such as cracking, and the coating operation is repeated twice or more several times, which is a problem in processing. In addition, since high temperature is applied during processing, the strength of the non-combustible sheet material becomes negative, and the adhesive strength becomes insufficient. Therefore, it has been strongly desired in the art to eliminate the above-mentioned drawbacks of the non-combustible or flame-retardant coating layer.

Therefore, the present inventors have already developed a non-combustible or flame-retardant fluorine-containing resin on at least one side of a non-combustible base fabric (glass fiber, asbestos fiber, metal fiber and / or other inorganic non-combustible fiber). The non-combustible sheet obtained by adhering the above film was proposed (JP-A-61-61849 and JP-B-63-19337). This non-combustible sheet showed sufficient non-combustibility and excellent antifouling and weather resistance, but the problem of insufficient refraction resistance in harsh applications such as vibration, scatter and bending. There was a point.

[0007]

[Problems to be Solved by the Invention] A drawback of the conventional flame-retardant heat-resistant sheet using a base fabric made of non-combustible inorganic fibers, that is, low refraction resistance, difficult to sew, and easy to cut from perforations. It is an object of the present invention to eliminate such drawbacks.

[0008]

The flame-retardant heat-resistant sheet of the present invention comprises a fabric comprising flame-retardant heat-resistant inorganic fibers and heat-resistant organic synthetic fibers having a melting point of 300 ° C. or higher or a thermal decomposition point. A cloth and at least one side of this base cloth,
And a fluorine-containing resin film layer having a melting point of 280 ° C. or less, wherein the content of the heat-resistant organic synthetic fiber in the base cloth is in the range of 10 to 90% based on the weight of the base cloth. It is what

[0009]

The flame-retardant heat-resistant sheet according to the present invention comprises a base cloth 1 and fluorine-containing resin film layers 2a and 2b attached to both surfaces of the base cloth 1 as shown in FIG. It is formed. The fluorine-containing resin film layer may be attached to only one surface of the base fabric 1.

The base cloth is made of flame-retardant heat-resistant inorganic fibers and 300 ° C.
It is made of a fabric containing the heat-resistant organic synthetic fiber having the above melting point or thermal decomposition point.

The flame-retardant heat-resistant inorganic fiber used in the present invention can be selected from asbestos fiber, ceramic fiber, silica fiber, glass fiber, carbon fiber, and metal fiber.

The heat-resistant organic synthetic fiber used in the present invention has a melting point of 300 ° C. or higher or a thermal decomposition point, and the content of the heat-resistant organic synthetic fiber in the base cloth is equal to the weight of the base cloth. On the other hand, it is in the range of 10 to 90%.

In the flame-retardant heat-resistant sheet of the present invention, if necessary, in addition to the above-mentioned heat-resistant organic synthetic fibers, a small amount (70% or less based on the weight of the base cloth) of different kinds of different organic fibers is contained in the base cloth. You can leave. Such heterogeneous organic fibers include natural fibers such as cotton and hemp, regenerated fibers such as viscose rayon and cupra, semi-synthetic fibers such as di- and tri-acetate fibers, and synthetic fibers, For example, it can be selected from nylon 6, nylon 66, polyester (polyethylene terephthalate etc.) fiber, aromatic polyamide fiber, acrylic fiber, polyvinyl chloride fiber, polyolefin fiber and insolubilized or insolubilized polyvinyl alcohol fiber.

The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, split yarn, tape yarn, etc. The base fabric may be a woven fabric, a knitted fabric or a non-woven fabric or a composite fabric thereof. Either may be used. But,
Considering the strength and bending resistance of the sewn portion, the base fabric is preferably a woven fabric or a knitted fabric, and more preferably a woven fabric.

Further, the fiber is preferably in the form of long fibers (filaments) having a small elongation with respect to stress, and it is preferable to form a plain woven fabric. However, the knitting or weaving structure is not particularly limited, and for example, a special entangled fabric may be formed by arranging warp yarns and weft yarns arranged in parallel so as to intersect with each other and entwining them with entanglement yarns. The base fabric is useful for maintaining the mechanical strength of the obtained sheet at a high level, and the heat-resistant organic synthetic fiber and the heterogeneous organic fiber increase the mechanical strength of the base fabric, and It is useful for maintaining a high level of mechanical strength.

In the flame-retardant heat-resistant sheet of the present invention, the heat-resistant organic synthetic fiber contained in the base fabric has a melting point of 300 ° C. or higher, or a thermal decomposition point. Table 1 shows the polymers that form fibers.
There are the ones shown in FIGS.

[0017]

[Table 1]

[0018]

[Table 2]

[0019]

[Table 3]

[0020]

[Table 4]

[0021]

[Table 5]

[0022]

[Table 6]

Among the heat-resistant polymers shown in Tables 1 to 6, especially polymetaphenylene isophthalamide and polyparaphenylene terephthalamide are common,
As a para-aramid fiber other than the above, Teijin Ltd. "H
M-50 "and the like can also be used.

Aromatic polyamides useful in such fibers are:
In addition, at least 50 mol% of the following formulas (I) and (I
I): —Ar ₁ —CONH— (I) —Ar ₁ —CONH—Ar ₂ —NHCO— (II) [wherein, Ar ₁ and Ar ₂ represent a divalent aromatic group, and these are mutually substituted. They may be the same or different] as the main repeating unit.

In the above formulas (I) and (II), Ar ₁
And a divalent aromatic group represented by Ar ₂ has the following formula:

[Chemical 1] It is preferable to be selected from the aromatic residue group represented by. These aromatic residues may contain an inert substituent such as halogen, an alkyl group and a nitro group.

Generally, the aromatic polyamide has the following formula:

[Chemical 2] Those having a repeating unit represented by as a main component are more preferable.

As the heat-resistant organic synthetic fiber used in the present invention, in addition to the above, the melting point or the decomposition point is 300 ° C.
Fluorine-based fibers and other fibers can also be used as long as they are as described above. The content of the heat-resistant organic synthetic fiber in the base cloth is in the range of 10% to 90% with respect to the weight of the base cloth,
It is preferably in the range of 15% to 70%. Also,
In order to promote adhesiveness to the fluorine-containing resin film layer and other properties, it is possible to mix an organic fiber having a lower melting point or decomposition point and different from the heat-resistant organic synthetic fiber in the base cloth. In this case, the heterogeneous organic fibers to be mixed are not particularly limited and can be appropriately selected from the above-mentioned fibers. However, the mixing ratio of the different fibers having a low melting point or a low decomposition point to be mixed is preferably 70% or less, more preferably 50% or less, based on the weight of the base fabric.

In the base fabric used in the present invention, the inorganic fibers and the organic fibers may be mixed in any manner. That is, any of mixed spinning, mixed knitting, mixed twisting, drawing and the like may be used.

When glass fibers are used as the inorganic fibers, the type of glass fibers, the thickness of the single fibers, etc. are not particularly limited, but are generally called beta yarns having a thickness of about 2 to 10 μm, especially about 3 μm. Is prized.

The fluorine-containing resin used in the present invention may be any one as long as it has a film-forming property and can be heat-melt attached. As an example, the F.I. E. P. (Tetrafluoroethylene-hexafluoropropylene copolymer, mp.275
℃)

[Chemical 3] Etc. can be used, but m. p. 25
Fluorine-containing resin having a temperature of 0 ° C. or lower, such as P.I. C. T. F. E.
(Polychlorotrifluoroethylene,-(CClF-C
F ₂₎ -, m. p. 215 ° C.), P. V. D. F. (Polyvinylidene _{fluoride, - (CF 2 -CH 2)} -,
m. p. 165 to 180 ° C.), P. V. F. (Polyvinyl _{fluoride, - (CHF-CH 2)} -, m.p.2
00-210 ° C), E. C. T. F. E. (Chlorotrifluoroethylene - ethylene copolymer, - (CH ₂ -C
_{H 2) - (CClF-CF} 2) -, m. p. 245 ° C)
Etc. can also be used.

Although the weather resistance of these fluorine-containing resins is extremely good, an ultraviolet absorber may be added to these resins for the purpose of protecting the base cloth. Further, it goes without saying that a colorant or other performance-imparting agent may be added. The coating film made of these resins may be microporous, or may have open or discontinuous cells.

In the present invention, it is preferable that a fluorine-containing resin is previously formed into a film, and at least one surface of the film is melted to be stuck on the base cloth. In this case, even if the base cloth is not heated, it can be stuck if at least one sticking surface of the film is sufficiently melted. However, in order to preferably melt and flow the molten resin between the fibers of the base cloth to strengthen the adhesion, it is more preferable to heat the base cloth in advance, preferably to the melting temperature if possible. The temperature is preferably 50 ° C. or higher, which is the melting point, but it is not preferable to set the temperature higher than necessary.

Adhesion of the fluorine-containing resin film to the base cloth is
Although it can be achieved without an intervening adhesive substance, an adhesive substance may be interposed for the purpose of improving adhesion and durability. In this case, the purpose of using the intervening substance is to improve the adhesive force, and it is not necessary to intervene in a particularly thick amount than the amount effective for improving the adhesive force.

As the adhesive substance, a substance known as an adhesive can be used. For example, amino group, imino group, ethyleneimine residue, acrylate containing alkylenediamine residue, acrylate containing aziridinyl group, aminoester-modified vinyl polymer, aromatic epoxy adhesive, amino nitrogen-containing methacrylate polymer, other You may use an adhesive together. Further, it is also possible to arbitrarily select a resin having the same quality as the resin constituting the fiber base cloth such as polyamide-imide or polyimide, or an RFL-modified substance.

When interposing such an adhesive substance,
When the processing temperature is 350 ° C to 400 ° C or higher, the properties of these substances are lost, and not only the effectiveness as an adhesive is lost, but also the strength of the base cloth may be reduced.
Preferred results can be obtained by selecting a fluorine-containing resin film that can be melted at a temperature of 280 ° C. or lower, preferably around 250 ° C. or lower.

The fluorine-containing resin film may be adhered to one side of the base cloth, but may be adhered to both sides in order to compensate for the low weather resistance of the base cloth, etc. It may be necessary to attach both sides. When the fluorine-containing resin film is attached to only one side of the base cloth, natural rubber, neoprene rubber, chloroprene rubber, silicone rubber, hypalon or other synthetic rubber, or other one side, depending on the performance required for the sheet, on the other side, or It is also possible to use PVC resin, ethylene-vinyl acetate copolymer (EVA) resin, acrylic resin, silicone resin, urethane resin, polyester resin and other synthetic resins. In this case, it is more preferable that these resins are flame-retarded.

It is preferable that the fluorine-containing resin film is adhered in a state in which the surface layer is formed instead of impregnating the entire base cloth with the resin. Regarding the relationship between the fluorine-containing resin film and the base cloth, the molten resin of the fluorine-containing resin film is ingested and adhered to the surface of the base cloth, but it is said that it does not penetrate into the entire inside of the base cloth. , Hardness, flexibility, etc. are suitable, and it is preferable from the viewpoint of easy handling. However, it does not matter if the resin penetrates the entire base cloth.

The thickness of the fluorine-containing resin film adhered on the flame-retardant heat-resistant base fabric is preferably 5 to 2000 μm, particularly 10 to 1500 μm.

[0039]

【Example】

 The flame-retardant heat-resistant sheet of the present invention will be further described with reference to examples.

Example 1 and Comparative Example 1 In Comparative Example 1, the following glass fiber woven fabric was used as a base fabric. Fabric A: basis weight 290 g / m ² having the following structure
Fiberglass cloth (Turkish satin weave)

[Equation 1]

In Example 1, in the same structure as the above-mentioned cloth A, the length and length of one glass fiber yarn per one aromatic polyamide long fiber yarn, 195d / 130f (trademark-
Kevlar, manufactured by DuPont) was punched in at a ratio of 2 and the obtained fabric B was used as a base fabric. The content of Kevlar fibers in the base cloth was about 60% based on the weight of the base cloth.

An acrylic adhesive SC-462 manufactured by Sony Chemicals Co., Ltd. was applied to both sides of each base cloth at a coating amount of 30 g / m ² .

Each of the adhesive-coated base fabrics was heated to 330 ° C., and F. E. P. (Mp 275 ° C.) films (thickness: 50 μm) were superposed, and heated and pressed to stick. Each of the obtained sheets showed a water pressure resistance of 2000 mm or more, and also showed good flame retardant heat resistance, antifouling property, and weather resistance.

Each sheet is compliant with JIS P8115 (197).
It was subjected to a bending resistance test according to 6). The sheet of Comparative Example 1 was folded and folded at 3,000 times. However, the sheet of Example 1 did not break even after 10,000 times of bending, and practically exhibited almost infinite bending resistance.

Each sheet is made of Singer 112W-
No. 115, an industrial sewing machine (two-needle, lock stitch thread feed, for tent) was sewn using Nomex multifilament thread (500d) as a sewing thread. Although refused, Example 1
The sheet could be sewn well without tearing at the perforations.

Example 2 and Comparative Example 2 The same operations as in Example 1 and Comparative Example 1 were performed. However, carbon fiber threads were used instead of the glass fiber threads in the base fabric. The bending resistance of the heat-resistant sheets obtained in Example 2 and Comparative Example 2 was as shown in Example 1 and Comparative Example 1, respectively.
The sheet of Example 2 exhibited a bending resistance of 10,000 times or more, and good flame retardant heat resistance, antifouling property, and weather resistance. Also in terms of sewability, the sheet of Comparative Example 2 was torn at the perforations during sewing,
The sheet of Example 2 could be smoothly subjected to sewing machine sewing.

Example 3 The same operation as in Example 1 was performed. However, together with the Kevlar fiber yarn, polyethylene terephthalate multifilament yarn (250d / 48f) was used at a ratio of 1 to 1 glass fiber yarn. In addition, P. F. Instead of A film, P. V. D. Melt adhesion temperature of 2 using F film
It was set to 60 ° C. The obtained sheet showed good flame resistance, heat resistance, stain resistance and weather resistance, as well as bending resistance of 10,000 times or more. When the sewing machine was sewn, it could be sewn smoothly.

[0048]

EFFECTS OF THE INVENTION In the flame-retardant heat-resistant sheet of the present invention, the surface of the base cloth is uniformly and evenly covered with a defect-free fluorine-containing resin film. This fluorine-containing resin film layer does not cause defects on the sheet surface unlike the conventional coating layer formed by impregnation and sintering, effectively protects the base fabric from ultraviolet rays, and has extremely favorable stain resistance and weather resistance. It is possible to obtain a flame-retardant heat-resistant sheet which has excellent refraction resistance and sewability.

[Brief description of drawings]

FIG. 1 is a cross-sectional explanatory view of an embodiment of a flame-retardant heat-resistant sheet of the present invention.

[Explanation of symbols]

 1 ... Base cloth 2a, 2b ... Fluorine-containing resin film layer

Claims (8)

[Scope of utility model registration request] 1. A base fabric made of a fabric comprising a flame-retardant heat-resistant inorganic fiber and a heat-resistant organic synthetic fiber having a melting point of 300 ° C. or higher or a thermal decomposition point, and at least one surface of the base fabric. And a fluorine-containing resin film layer having a melting point of 280 ° C. or less, the content of the heat-resistant organic synthetic fiber in the base cloth is 10 to the weight of the base cloth.
Flame-retardant heat-resistant sheet in the range of 90%. 2. The sheet according to claim 1, wherein the inorganic fibers are selected from asbestos fibers, ceramic fibers, silica fibers, glass fibers, carbon fibers, and metal fibers. 3. The sheet according to claim 1, wherein the fluorine-containing resin film is attached to both sides of a base cloth. 4. The melting point of the fluorine-containing resin film is 25.
The sheet according to claim 1, which has a temperature of 0 ° C or lower. 5. The sheet according to claim 1, wherein the fluorine-containing resin film is attached via an adhesive substance layer. 6. The sheet according to claim 1, wherein the fluorine-containing resin film is melt-bonded. 7. The fluorine-containing resin film layer is 5 to 20.
The sheet according to claim 1, having a thickness of 00 μm. 8. The sheet according to claim 1, wherein the base fabric further contains an organic fiber different from the heat-resistant organic synthetic fiber.