JPH0651394B2 - Flame retardant heat resistant sheet - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a sheet material which is excellent in flame retardancy and heat resistance, and is also excellent in antifouling and weather resistance.

[0002]

2. Description of the Related Art Conventionally, polyester fibers (having a melting point of 255 to
260 ° C.), polyamide fiber (melting point 215 to 260 ° C.)
A thermoplastic resin such as polyvinyl chloride (PVC) (heat-resistant temperature 66 to 79 ° C.), polyurethane (heat-resistant temperature 90 to 120 ° C.), acrylic resin (heat-resistant temperature 60 to 88 ° C.) , Polyethylene (heat-resistant temperature 8
0-120 ° C), polypropylene (heat-resistant temperature 120-1)
60 ° C.), polyamide (heat-resistant temperature 80-150 ° C.) or polyester (heat-resistant temperature about 120 ° C.) is used as a sheet material. In this case, the melting point of the fibrous base cloth is relatively low, and even as a coating material to be coated on the fibrous base cloth, from the viewpoint that the fibrous base cloth must withstand the heat during the coating process, Low resins such as those mentioned above have been used. However, in recent years, these sheet materials are often used, for example, in firefighter clothes, heat-resistant clothing, building materials, etc., and in order to maintain safety from fires, burns and other thermal disasters, The demand for flame-retardant materials is increasing, and flame-retardant heat-resistant sheet materials are being developed. However, even in such a case, conventionally, even when a fibrous base cloth is made of a heat-resistant material, a conventional PVC, polyurethane, ethylene-vinyl acetate copolymer is used as a coating material for covering the fibrous base cloth. In most cases, (EVA) or the like is used, and sufficient heat resistance and flame retardancy have not yet been achieved.

Therefore, recently, P. T. F. E.
A flame-retardant tent film material coated with (polytetrafluoroethylene) has been developed and used. However, this is P. T. F. E. 60 as a dispersion
%, Viscosity 20 centipoise, soak in high temperature (about 4
It is manufactured by baking coating at 00 ° C. or 350 ° C. to 500 ° C.). Since such immersion and high-temperature baking are performed, the processing speed is as slow as about 30 cm / min, and when 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 also a downside in performance, such as occurrence of, and this operation is repeated twice or more several times, which is a problem in processing. Further, since a high temperature is applied during the processing as described above, the flame-retardant sheet material has a negative effect on the strong side, and the adhesive force also causes an unfavorable result.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied how to solve these drawbacks and formed a fluororesin film in advance, and made it a flame-retardant heat-resistant material through an adhesive substance layer. If you attach it to the base fabric, you can eliminate these drawbacks,
It was found to be extremely effective. As a result of further study,
In order to maintain the adhesive strength (peel strength) and strength, the melting point of the fluororesin film is 280 ° C or lower, preferably 250 ° C or lower, in order to reduce the deterioration of the base cloth due to high temperature processing heat and maintain the strength. The processing temperature is at least 3
50 ° C, preferably 300 ° C or less, more preferably 2
It has been found that if the melt-adhesion is performed at 70 ° C or lower, the strength of the flame-retardant heat-resistant base cloth is not reduced, the film is not deteriorated, and sufficient adhesive strength is given without diminishing the effect of the adhesive substance. The present invention has been completed.

[0005]

According to the present invention, there is provided a flame-retardant heat-resistant sheet having excellent weather resistance and stain resistance, which sheet has a melting point or a thermal decomposition point of 300 ° C.
The flame-retardant and heat-resistant base fabric made of the flame-retardant and heat-resistant fiber cloth as described above, and the melting point of at least one surface thereof melt-bonded to 28
It comprises a fluorine-based resin film at 0 ° C. or lower, and an adhesive substance layer arranged between the base cloth and the fluorine-based resin film.

The present invention will be described in more detail. The flame-retardant heat-resistant base cloth used in the sheet material of the present invention is made of a flame-retardant heat-resistant fiber cloth, and such cloth has a melting point or a heat resistance. A knitted woven fabric or non-woven fabric made of organic fibers having a decomposition point of 300 ° C. or higher is used. Examples of polymers useful for such fibers include those shown in the table below.

[0007]

[Table 1]

[0008]

[Table 2]

[0009]

[Table 3]

[0010]

[Table 4]

[0011]

[Table 5]

Of these, polymetaphenylene isophthalamide and polyparaphenylene terephthalamide are particularly common, and as the para-aramid fibers other than the above, "HM-50" manufactured by Teijin Limited can be used. Aromatic polyamides useful in such fibers also include at least 50 mol% of the following formulas (I) and (II):

[0013]

[Chemical 1]

At least one selected from the units represented by the formula: wherein Ar ₁ and Ar ₂ represent a divalent aromatic group, and these may be the same or different from each other. It is preferable to have one as a main repeating unit. In the above formulas (I) and (II), Ar ₁ and A
The divalent aromatic group represented by r ₂ has the following formula:

[0015]

[Chemical 2]

[In the above formula, A is -O-, -S-, -SO
_{-, - SO 2 -, -} CO -, - CH 2 - or -C (CH
₃ ) Representing _2- ]] is preferable. These aromatic residues may contain an inert substituent such as a halogen, an alkyl group or a nitro group. Generally, as the aromatic polyamide, the following formula,

[0017]

[Chemical 3]

Those having a repeating unit represented by as a main component are more preferable. As the heat resistant fiber, in addition to the above, fluorine-based fibers and other fibers can be used as long as they have a melting point or a thermal decomposition point of 300 ° C. or higher.
In addition, fibers having a lower melting point or thermal decomposition point may be mixed in the base fabric in order to promote adhesion with the fluororesin film to be coated.

The fluorine resin film useful in the present invention preferably has a heat resistant temperature of 180 to 260 ° C. and a melting point of 160.
It is a fluorine-containing resin having flame retardant heat resistance of 280 ° C. and film forming property. Specifically, F.I. E. P. (Tetrafluoroethylene-hexafluoropropylene copolymer

[0020]

[Chemical 4]

Etc. can be used, but for the reasons described later,
Fluorine-based resin having an mp of 250 ° C. or less, such as P. C. T.
F. E. (Polychlorotrifluoroethylene

[0022]

[Chemical 5]

It is preferable to use the following. Although the weather resistance of these resins is extremely good, an ultraviolet absorber may be incorporated into 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, a fluorine-based resin is formed into a film in advance, and at least one surface of the film is melted and attached to a 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 preferable to heat the base cloth in advance and, if possible, to heat it to the melting temperature of the fluorine-based resin film or higher. More preferable. The temperature is preferably 50 ° C. or higher, which is the melting point of the fluororesin, but it is not preferable that the temperature is set higher than necessary.

The fluororesin film is attached to the base cloth by interposing an adhesive substance in the middle for the purpose of improving adhesion and durability. The purpose of using this substance is to improve the adhesive force, and it is not necessary to intervene particularly thickly in order to improve the adhesive force. The adhesive substance is not used for forming a film, and therefore 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 performing the adhesion with such an adhesive substance interposed, the processing temperature is 350 ° C to 4 ° C.
When the temperature is higher than 00 ° C, the properties of these substances are lost, and not only the effectiveness as an adhesive is lost but also the strength of the base fabric may be lowered. Particularly preferable results are obtained by selecting a fluorine-based resin film that can be melted at a temperature of about 250 ° C. or lower.

The fluororesin film of the present invention may be applied on one side, but it may be applied on both sides in order to compensate for the low weather resistance of the base fabric, etc. Adhesion becomes an essential condition. It is preferable that the fluororesin film is adhered in a state in which a layer is formed instead of including the resin in the entire base cloth. Regarding the relationship between the fluorine-based resin film and the base cloth, the molten resin of the fluorine-based resin film is ingested and adhered to the surface of the base cloth, but it does not seem to penetrate into the entire base cloth. Are preferable in terms of hardness, flexibility, and ease of handling. However, it does not matter if the resin penetrates the entire base cloth. Further, the thickness of the fluororesin film adhered on the flame-retardant heat resistant base fabric is preferably 5 to 2000 μm, particularly preferably 10 to 1500 μm.

[0027]

As described above, according to the present invention, since the surface of the base cloth is uniformly and uniformly covered with the defect-free fluororesin film, unlike the conventional covering by the impregnation sintering process. It is possible to obtain a flame-retardant heat-resistant sheet which does not cause defects on the surface of the base cloth, effectively protects the base cloth from ultraviolet rays, and has extremely preferable antifouling properties and weather resistance.

[0028]

EXAMPLES The present invention is constructed and implemented as described above, and the present invention will be described in more detail with reference to the following examples. Example 1 Aromatic Polyamide (Kevlar, DuPont) Fiber Fabric:

[0029]

[Equation 1]

Thickness 0.12 mm Weight 60 g / m ² Tensile strength (warp × latitude, kg / 3 cm) 130 × 168 Tensile elongation (warp × latitude,%) 3.2 × 3.7 After scouring and drying, 20 at 350 ℃
Heat set for 2 seconds, as it is (Sample I), or an acrylic adhesive (SC-462, Sony Chemical Co., Ltd.) applied to one side of Sample I at an amount of 30 g / m ² (Sample)
II) was prepared and each of the samples was heated to 280 ° C. V. D. F. (Mp180 ° C.) One side of a film (thickness: 50 μm) was heated to 250 ° C. to melt, overlap, and pressure-bonded to prepare samples Ia and II-b, respectively. In addition, in Sample II, P. V. D. F. A film was prepared by simply adhering one surface of the film without melting it, and designated this as sample II-c.

The water pressure resistance of the thus obtained composite was well over 1000 mm of water column, which was preferable, and it was sufficiently durable as a flame-retardant heat-resistant membrane material. The physical properties of these sheets were measured as follows.

[0032]

[Table 6]

As can be seen from the above table, the strength is not much lower than that of the raw machine, and tends to increase due to the binding force of the adhesive. In the peeling strength, the effect of the adhesive substance layer was clear because it was a filament woven fabric, and it was extremely high for the melt-bonding sample II-b. Further, this composite sheet was flame-resistant and heat-resistant, had a smooth surface, and had very good weather resistance and antifouling property, and was extremely preferable as a film material for tents.

Example 2 Aromatic Polyamide (Conex, Teijin) Fiber Base Fabric:

[0035]

[Equation 2]

Thickness 0.23 mm Weight 90 g / m ² Tensile strength (warp × weft, kg / 3 cm) 70 × 62 Tensile elongation (warp × weft,%) 24 × 25, the same operation as in Example 1 Repeat P. V.
D. F. Using the film, it was stuck on both the front and back surfaces of the base fabric. As a result, similar to that of Example 1, it has sufficient waterproofness. The physical properties of these sheets were as follows.

[0037]

[Table 7]

As can be seen from the above table, the strength is almost the same as that of the raw machine, and the peeling strength is extremely high for the sample for melt sticking, especially for the sample II'-b stuck with an adhesive. It was In addition, since the sample II'-b used the spun yarn woven fabric as the base fabric, it was extremely preferable as a material for work clothes having excellent drape, heat resistance and flame retardancy.

The sheet of the present invention may be formed in a tape shape, or may be a sheet cut into a tape shape. For example, this tape can be used by being coated or wound for applications requiring heat resistance and flame retardancy such as electric wires and cables.

Claims (5)

[Claims] 1. A flame-retardant heat-resistant base fabric made of an organic fiber cloth having a melting point or a thermal decomposition point of 300 ° C. or higher, and a fluorine-based resin film having a melting point of 280 ° C. or lower adhered to at least one surface thereof. A flame-retardant heat-resistant sheet, comprising: an adhesive material layer disposed between the base cloth and a fluorine-based resin film. 2. The sheet according to claim 1, wherein the fluororesin film is attached to both sides of the flame-retardant heat-resistant base fabric. 3. The adhesive substance layer has an acrylate containing an amino group, an imino group, an ethyleneimine residue or an alkyleneimine residue, an acrylate containing an aziridinyl group, an aminoester-modified vinyl polymer, an aromatic epoxy adhesive, and amino. The sheet according to claim 1 or 2, comprising at least one selected from a nitrogen-containing methacrylate polymer, a polyamide-imide resin, a polyimide resin and an RFL-modified substance. 4. The sheet according to claim 1, wherein the melting point of the fluorine-based resin film is 250 ° C. or lower. 5. The thickness of the fluorine-based resin film layer is 5 to 20.
The sheet according to claim 1, which has a thickness of 00 μm.