JPS61177240A - Flame-retardant heat-resistant sheet - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Industrial applications The present invention relates to a flame-retardant and heat-resistant sheet.

More specifically, the present invention relates to a sheet material that is excellent in flame retardancy and heat resistance, and also has excellent stain resistance, weather resistance, sewing properties, and refraction resistance.

BACKGROUND OF THE INVENTION In recent years, sheet materials containing various synthetic resins have been used as building materials, interior materials, and members for vehicles, ships, aircraft, and the like. These synthetic resins have the disadvantage of generating a large amount of harmful or toxic gas or smoke when burned in a fire or the like. For example, if a large amount of sheet material containing polyvinyl chloride resin is used as the above-mentioned sheet material,
Various proposals have been made to make such sheet materials nonflammable or flame retardant.

For example, Japanese Patent Publication No. 55-4582 discloses that a borate, a sulfur compound, or an iron compound, and aluminum hydroxide or barium sulfate are added to a polyvinyl chloride resin to be applied to a sheet material base fabric. However, the results are not yet fully satisfactory.

Japanese Patent Publications No. 53-13505, Japanese Patent Publication No. 51-37397, and Japanese Unexamined Patent Publication No. 54-68470 propose the use of silicone resin as the nonflammable resin. In these cases, the effect of making it non-combustible or flammable is quite high, but when sheet materials coated with such silicone resins are used outdoors, for example as tent sheets, they can cause significant damage during use. Easy to get dirty,
In addition, since the surface of this silicone resin coating layer is soft and brittle, there is a drawback that various solid powders may stick, penetrate and become embedded, or the coating layer may peel off. .

So recently, P, T, F, and E were added to the glass fiber base fabric. A noncombustible tent curtain material coated with (polytetrafluoroethylene) has been developed and is now in use. However, P, T, F
,E. For example, since it cannot be formed into a film, the density is 60.
q6, impregnated into a dispersion base fabric with a viscosity of 20 centipoise, and heated to high temperatures (approximately 400°C and even 350°C to 500°C).
) is coated by firing. In addition, since such impregnation and high-temperature firing cannot be carried out, the processing speed is slow at approximately 30 cm/rnin, and if a sufficient coating thickness is formed at one time, sagging, muddy cracks, and foaming may occur on the coating surface, causing the coating to deteriorate. There are also disadvantages in terms of performance, such as cracking, and there are problems in processing as the coating operation is repeated two or more times. Unfortunately, high temperatures were applied during processing, which was detrimental to the strength of the non-combustible sheet material, and also resulted in insufficient adhesive strength.

Therefore, there has been a strong desire in the industry to solve the above-mentioned drawbacks of non-flammable or flame-retardant coating layers.

Therefore, the present inventors have already pasted a film of a nonflammable or flame-retardant fluorine-containing resin on at least one side of a nonflammable base fabric (glass fiber, asbestos fiber, metal fiber, and/or other inorganic noncombustible fiber). (Japanese Patent Application No. 59-183789). This noncombustible sheet showed sufficient noncombustibility and was excellent in stain resistance and weather resistance, but it had the problem of insufficient refraction resistance in applications that are subject to severe vibrations, flaps, and bending. There was a point.

Problems to be Solved by the Invention The drawbacks of conventional flame-retardant and heat-resistant sheets using base fabrics made of non-flammable inorganic fibers are that they have low refraction resistance, are difficult to sew, and cannot be cut from perforations. It is an object of the present invention to eliminate the drawbacks such as easy tearing.

Means and Function for Solving the Problems The flame-retardant and heat-resistant sheet of the present invention comprises a base fabric made of a fabric containing flame-retardant and heat-resistant inorganic fibers and organic fibers, and at least one surface of the base fabric. The invention is characterized in that it has a fluororesin-containing resin film attached to the fluororesin-containing resin film.

The flame-retardant and heat-resistant inorganic fibers used in the present invention include asbestos fibers,
You can choose from ceramic fibers, silica fibers, glass fibers, carbon fibers, and metal fibers.

The organic fibers used in the present invention include natural fibers such as cotton and linen, recycled fibers such as viscose rayon,
cupro, semi-synthetic fibers such as g- and tri-acetate fibers, and synthetic fibers such as nylon 6, nylon 66, polyester (polyethylene terephthalate, etc.) fibers, aromatic polyamide fibers, acrylic fibers, polyvinyl chloride fibers, polyolefins Fibers and insolubilized or poorly soluble polyvinyl alcohol fibers, etc.
You can choose from. The fibers in the base fabric may be of any shape such as short fiber spun yarn, long fiber yarn, striped yarn, or teno yarn, and the base fabric may be woven, knitted, nonwoven, or a composite fabric of these. There may be. However, in consideration of the strength and bending resistance of the sewn portion, a woven or knitted fabric is preferable as the base fabric, and a woven fabric is more preferable.

In addition, as for the form of the fibers, long fibers (filament) that have little elongation under stress are preferable.
In addition, it is preferable to form a plain woven fabric. However, there are no particular limitations on the weaving structure or its form. The organic fiber base fabric is useful for maintaining the mechanical strength of the resulting flame-retardant sheet at a high level.

In the flame-retardant sheet of the present invention, it is preferable that the organic fibers constituting the base fabric have a melting point or thermal decomposition point of 300° C. or higher. Polymers that form such high melting point or high decomposition point fibers include those shown in Table 1.

Among the heat-resistant polymers shown in Table 1, polymetaphenylene isophthalamide and No. Rihara phenylene terephthalamide is commonly used, and other para-aramid fibers such as r)k-50J manufactured by Mitsuryu Co., Ltd. can also be used.

Aromatic polyamides useful in such fibers also have at least 50 moles of the following formulas (I) and (H), + A, r
1-C0NH+ (1)(-Ar
-CONH-Ar -NHCO+ (II)
[In the above formula, Ar and Ar 2 represent a divalent aromatic group, and these may be the same or different.] At least one type of unit selected from the following: It is preferable that it has as a main repeating unit. In the above formulas (I) and (II), the divalent aromatic groups represented by Ar1 and Ar2 are represented by the following formula, [wherein A is 10-, -8-, -8O-, - 8o2-
.

-CO-, -CH2- or -C(CH3)2-] is preferably selected from aromatic residue moieties represented by -CO-, -CH2- or -C(CH3)2-.

The aromatic residues of cholera may contain inert substituents such as halogens, alkyl groups, and nitro groups.

Generally, as aromatic polyamides, those having repeating units represented by the following formula as a main component are more preferred.

In addition to the above-mentioned heat-resistant organic fibers, fluorine-based fibers and other fibers can also be used as long as they have a melting point or decomposition point of 300° C. or higher.

The content rate of heat-resistant organic fiber in the base fabric is 1% based on the weight of the base fabric.
It is preferably within the range of 0% to 90%', 15%
More preferably, it is within the range of 70%. In addition, this fluorine-containing resin film layer has adhesive properties and other properties.
To assist, fibers with lower melting or decomposition points can also be mixed into the base fabric. In this case, there are no particular limitations on the fibers to be mixed. However, the proportion of low melting point or low decomposition point fibers to be mixed is preferably 70% or less, more preferably 50% or less.

The fibers in the base fabric may be in any form such as short fiber spun yarn, long fiber yarn, split yarn, or tape yarn, and the base fabric may be woven, knitted, nonwoven, or a composite thereof. It can be made of any cloth. Generally, the fibers used for the base fabric may be of any shape, but long fibers (filaments) are light and heavy. The structure of the fabric constituting the base fabric is not particularly limited either, but it is preferably a plain woven fabric. Moreover, it is particularly preferable that the fabric for the base fabric is a fabric constructed by stacking warp yarns and weft yarns arranged in parallel so as to cross each other, and pressing these together with leno yarns. The base fabric is useful for maintaining the mechanical strength of the resulting sheet at a high level.

In the base fabric used in the present invention, inorganic fibers and organic fibers may be mixed in any manner.

That is, it may be a blended fabric, a blended knitted fabric, a blended twist, a pulled arrangement, or the like.

When glass fiber is used as the inorganic fiber, there are no particular limitations on the type of glass fiber or the thickness of the single fibers, but in general, beta yarns with a thickness of about 2 to 10 μm% and about 3 μm are preferred. May be.

The fluorine-containing resin used in the present invention may be any resin as long as it has film-forming properties and can be hot-melted and bonded. -For example, F'', E, P, (f
Dorafluoroethylene-perfluoropropylene copolymer P, F, A, (tetrafluoroethylene-perfluoroalkyl+CF2-.CF2+(-CF2-C,F-
) o-Rf) Crn, p, , 310°C), etc. can be used, but m, p may be used for reasons described later. Fluorine-containing resins below 250°C, such as P, C, T, F, E, (polychlorotrifluoroethylene+cctF-cF2-)-) (m, p, 215
℃), P, V, D.

F, (polyvinylidene fluoride + CF2-CH2+
) (m, p. 165-180°C), P, V, F, (polyvinyl fluoride + CHF-CH2-)-) (m
, p, 2o o ~ 210°C), E, C8T, F, E,
(chlorotrifluoroethylene-ethylene copolymer + CH2-CH2++ CCtF-CF2+) (m, p,
245℃) etc.

Although these fluorine-containing resins have extremely good weather resistance, ultraviolet absorbers may be added to these resins in order to maintain the stiffness of the base fabric. ~Also, it goes without saying that colorants and other performance-improving agents may be added.

Moreover, P, T, F, and E can also be used as the fluorine-containing resin. The coating made of these resins may be microporous and may have one continuous or discontinuous cell.

In the present invention, it is preferable that the fluorine-containing resin be formed into a film in advance, and that at least one side of this film be in a molten state and then adhered onto the base fabric. In this case, adhesion is possible without heating the base fabric as long as at least one adhesion surface of the film is sufficiently melted. However, in order to preferably melt and flow the molten resin between the fibers of the base fabric and to strengthen the adhesion, it is more preferable to warm the base fabric in advance, preferably to the melting temperature. The temperature is 50° below the melting point.
Although the temperature is preferably higher than 0.degree. C., it is not preferable to make it too high than necessary.

Although the fluorine-containing resin film can be attached to the base fabric without intervening an adhesive substance, an adhesive substance may be interposed therebetween for the purpose of improving adhesion and durability. In this case, the purpose of using this intervening substance is to improve adhesive strength, and there is no need to interpose it particularly thickly beyond the amount effective for improving adhesive strength. As the adhesive substance, a substance known as an adhesive can be used. For example, amino group, imino group,
Acrylates containing ethyleneimine residues and alkylene diamine residues, acrylates containing aziridinyl groups,
An amino ester-modified vinyl polymer-aromatic epoxy adhesive, an amino nitrogen-containing methacrylate polymer, and other adhesives may all be used in combination. Resin of the same quality as the resin constituting the fiber base fabric such as Amada polyamideimide and polyimide, or RFL
Modifying substances and the like can also be arbitrarily selected. When such adhesive substances are used, if the processing temperature exceeds 350°C or 400°C, the properties of these substances will be lost, not only will they lose their effectiveness as adhesives, but also the strength of the base fabric will decrease. Therefore, it is preferable to select a fluorine-containing resin film that can be melted at a temperature of 280°C or lower, more preferably around 250°C or lower.

The fluorine-containing resin film may be attached to one side of the base fabric, but it may also be attached to both sides to compensate for the low weather resistance of the base fabric, and depending on the usage situation, it may be attached to both sides. becomes a necessary condition. When a fluorine-containing resin film is attached to only one side of the base fabric, the other side may be made of natural rubber, neograin rubber, chloroglene rubber, silicone rubber, Hypalon or other synthetic rubber, or PVC resin, depending on the required performance. Ethylene-vinyl acetate copolymer (EvA) 4tJ resin, acrylic resin, silicone resin, urethane resin, polyester resin, and other synthetic resins can also be used.

In this case, if these resins are made flame retardant, they will be even lighter and heavier.

The state in which the fluorine-containing resin film is attached is preferably such that a surface layer is formed, rather than the entire base fabric being impregnated with the resin. Regarding this relationship between the fluorine-containing resin film and the base fabric, the molten resin of the fluorine-containing resin film penetrates and adheres to the surface of the base fabric, but it does not penetrate into the entire interior of the base fabric. It is preferable because it has appropriate hardness, flexibility, etc., and is easy to handle. However, there is no problem even if the resin permeates the entire base fabric.

In addition, the thickness of the fluorine-based resin film stuck on the flame retardant surface J thermal base fabric is 5 to 2000 μm1, especially 10 to 150 μm.
Preferably, it is 0 μm.

Example The flame retardant sheet of the present invention will be further explained with reference to Examples.

Example 1 and Comparative Example 1 In Comparative Example 1, the following glass fiber fabric was used as the base fabric.

Fabric A: Rust fiber weight 290 jJ/rn2 Example 1 In the structure of the above fabric A, aromatic polyamide long fiber yarn, 195d/130f (trademark - Kevlar (manufactured by DuPont), and the resulting fabric B was used as a base fabric. The content of Kepler fibers in the base fabric was about 60% based on the weight of the base fabric.

Acrylic adhesive 5C-462 manufactured by Sony Chemical Co., Ltd. was applied to both sides of each base fabric in a coating amount of 3'O/7/ln2.

Each adhesive-coated base fabric was heated to 330°C, and on both sides,
P, F, and A (rri, p, 310° C.) films (thickness: 50 μm) were stacked on top of each other and adhered by heating and pressure.

The obtained sheets all exhibited water pressure resistance of 200'Om1 or more, and also exhibited good flame retardant and heat resistance, stain resistance, weather resistance, and sewability.

Each sheet was subjected to a bending strength test according to JIs P811 (1976).

The sheet of Comparative Example 1 was bent 3000 times and then broken. However, the sheet of Example 1 did not break even after being folded 10,000 times, and showed practically infinite folding strength.

Example 2 and Comparative Example 2 The same operations as in Example 1 and Comparative Example 1 were performed. However, is it possible to use car instead of glass fiber thread in the base fabric? The fiber thread was used. The bending strength of the heat-resistant sheets obtained in Example 2 and Comparative Example 2 is almost the same as that obtained in Example 1 and Comparative Example 1, respectively.
0,000 It exhibited good bending strength upon recovery, and also showed good flame retardant and heat resistance, stain resistance, weather resistance, and sewability.

Example 3 The same operation as in Example 1 was performed. However, polyethylene terephthalate multifilament yarn (250d/48f) was used instead of Kevlar fiber yarn. Also, P, F, A
Instead of the film, VCP, V, D, F films were used and the melt bonding temperature was 260°C. The obtained sheet has good flame retardant heat resistance, stain resistance, weather resistance, and sewing properties, as well as i
o, o o o Indicates the strength of recovery.

Effects of the invention ゛In the present invention, the surface of the base fabric is evenly and uniformly covered with a fluorine-based resin film that has no defects. A heat-resistant sheet that effectively protects the base fabric from ultraviolet rays, has extremely favorable stain resistance and weather resistance, and has excellent refraction resistance and seamability without causing defects on the surface. is obtained.

Claims (1)

[Scope of Claims] 1. A base fabric made of a fabric containing flame-retardant, heat-resistant inorganic fibers and organic fibers, and a fluorine-containing resin film layer adhered to at least one surface of this base fabric. A flame-retardant and heat-resistant sheet having 2. The sheet according to claim 1, wherein the organic fiber is a heat-resistant organic synthetic fiber having a melting point of 300° C. or higher or a thermal decomposition point. 3. The sheet according to claim 1, wherein the content of the heat-resistant organic synthetic fiber in the base fabric is within a range of 10 to 90% based on the weight of the base fabric. 4. 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. 5. The sheet according to claim 1, wherein the fluorine-based resin film is adhered to both sides of the base fabric. 6. The sheet according to claim 1, wherein the fluororesin film has a melting point of 280°C or less. 7. The sheet according to claim 6, wherein the fluororesin film has a melting point of 250°C or less. 8. The sheet according to claim 1, wherein the fluororesin film is attached via an adhesive layer. 9. The sheet according to claim 1, wherein the fluorine-based resin film is melt-bonded. 10. The sheet according to claim 1, wherein the fluororesin film layer has a thickness of 5 to 2000 μm.