JPS63125331A - Flame-retardant 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 Field of Application] The present invention relates to a sheet material that has excellent flame retardancy, stain resistance, and weather resistance.

[Conventional technology]

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

For example, Japanese Patent Publication No. 55-4852 proposes adding a borate, a zinc compound, or an iron compound, and aluminum hydroxide or barium sulfate to the polyvinyl chloride resin to be applied to the sheet material base fabric. However, the results are still not completely 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 nonflammable or flame retardant is quite high, but when sheet materials coated with such silicone resins are used outdoors, for example as sheets for tents, they can deteriorate significantly during use. Easy to get dirty,
Moreover, since the surface of this silicone resin coating layer is soft and brittle, there is a drawback that various solid dust powders and the like may deposit, penetrate and become buried, or the coating layer may be peeled off.

Recently, a non-combustible tent membrane material in which a glass fiber base fabric is coated with P, T, P, E, (polytetrafluoroethylene) has been developed and used. However, P, T, F
, E is difficult to form into a film, so for example, a dispersion with a concentration of 60% and a viscosity of 20 centipoise is immersed in a high temperature (approximately 400°C or even 350°C to 50°C).
It is manufactured by firing coating at 0°C). Since such immersion and high-temperature firing are performed, the processing speed is slow at about 30 μ/min, and if a sufficient coating thickness is formed at once, sagging, muddy cracks, and foaming may occur on the coated surface, resulting in cracks in the coating. There are also disadvantages in terms of performance, such as cracking, and there are problems in processing as this operation is repeated two or more times. In addition, since high temperatures are applied during processing, the strength of the non-combustible sheet material is also negative.
Furthermore, the adhesive strength also brought about unfavorable results.

[Problem that the invention seeks to solve]

The present inventors have studied how to solve these drawbacks, and have first formed a fluorine-based resin film, then melted it and adhered it to one side of the nonflammable base fabric, and also applied it to other surfaces of the base fabric. It has been found that forming a coating layer made of natural rubber, synthetic rubber, or non-fluorine-containing resin on one side of the material is effective in solving these drawbacks. As a result of further study, in order to maintain adhesive strength (peel strength) and strength, especially in order to reduce deterioration of the base fabric due to high temperature heating and maintain strength, the melting point of the fluororesin film should preferably be 310°C. below, more preferably 280°C or less, even more preferably 250°C
If the following is selected and the treatment temperature is at least 300°C or lower, preferably 270°C or lower, a non-flammable base fabric, e.g.
It has been discovered that there is no decrease in the strength of the glass base fabric (no deterioration of the film, and in particular, when it is attached through an adhesive substance, it provides sufficient and favorable adhesive strength without reducing the effect of the adhesive substance, In addition, the present invention was completed by forming a non-fluorine resin coating layer on the other surface of the base fabric to reinforce the strength of the sheet.

[Means for solving problems]

According to the present invention, a flame-retardant sheet is provided, which comprises a non-flammable base fabric made of non-flammable fiber fabric, a fluorine-based resin layer formed on one surface of the non-flammable base fabric, and a fluorine-based resin layer formed on one surface of the non-flammable base fabric. A covering polymer layer made of natural rubber, synthetic rubber, or a synthetic resin other than a fluorine-based resin is formed on the other side.

To further explain the present invention in detail, the noncombustible base fabric used in the sheet material of the present invention is made of noncombustible fiber fabric, and examples of such fabric include glass fiber, asbestos fiber, metal fiber, and/or noncombustible fiber fabric. Alternatively, knitted fabrics or nonwoven fabrics made of other inorganic flame-retardant fibers, such as carbon fibers, can be used.

As the glass fiber fabric for the base fabric, incineration Mff is used to improve adhesion with the coating layer, flexibility, water resistance, etc.
i is 1.5% or less, cross cover factor is 25-3
5 is preferable, and the tensile strength in longitudinal and latitudinal directions is 50 kg/25 mm or more, especially 200 kg/25 mm or more, and 100 g/% or more, especially 200 to 9
It is preferable to have a basis weight of 00 g/rrr. The type of glass fiber, the thickness of the single fiber, etc. are not particularly limited, but generally the thickness is about 2 to 10 μm, especially 3 μm.
The so-called beta yarn with a diameter of about m is used as a prize.

A fluorine-based resin may be attached to the fiber surface of such a base fabric. Moreover, such a base fabric may be one obtained by impregnating a nonflammable fiber fabric with a fluorine-based resin liquid, drying it, and then firing it.

The fluorine-based resin used in the present invention has film-forming properties, sintered film-forming properties, and heat-melting film-forming properties, and any fluorine-containing resin can be used as long as it can be heat-melted and bonded. -For example, F,
E, P, (tetrafluoroethylene-hexafluoropropylene copolymer CF, (111,1), 27
5°C) P, F, A, (tetrafluoroethylene-perfluoroalkyl → CF, -CI', → -(
-CF2-CF h? 0Rt) (Ill, P, 310°C), etc. However, for the reasons described later, fluorine-based resin films with m, p, 250°C or less, such as P, C, T, F, H, (polychlorotri Fluoroethylene-+ CCIF-CF2→)
(m, p, 215°C), P, V, D, I'.

(Polyvinylidene fluoride→CPz C1l□→
-) (m, p, 165-180℃"), P, V, F
, (Polyvinyl fluoride→CHF -CIl□→
) (m, p, 210-210°C), E, C, T, F,
E, (chlorotrifluoroethylene-ethylene copolymer-+CHz CHz→ -(CCe F CFz
-χ) (m, p, 245°C), and P, T, F, E, etc. may also be selected depending on the method of adhesion. The fluorine-based resin film may be formed by directly melt-molding a resin, or may be formed by casting a resin liquid onto a support and then heating and solidifying it. At least one side of such a film is melted and attached to a glass base cloth.

In this case, the glass base fabric should not be heated (although it is possible to attach the film by sufficiently melting at least one surface of the film to be attached. However, it is preferable to melt and flow the molten resin between the fibers of the glass base fabric. In order to strengthen the adhesion, it is more preferable to heat the glass base cloth in advance, preferably to the melting temperature.

The temperature is preferably higher than the melting point of 50°C, but it is not preferable to make it too high than necessary. The fluorine-based resin layer may be formed by applying a resin solution or emulsion to one side of the base fabric and solidifying it.

Although the fluororesin film can be attached to the glass base fabric without intervening an adhesive substance, it is preferable to interpose an adhesive substance for the purpose of improving adhesion and durability. In this case, the purpose of using this substance is to improve adhesive strength, and there is no need to interpose it particularly thickly beyond the purpose of improving adhesive strength. Examples of adhesive substances include silane coupling agents used as surface treatment agents for glass fibers, such as T-methacryloxypropyltrimethyloxysilane, T-aminopropyltrimethoxysilane, polyfunctional aminosilane, and γ-mercapto. Propyltrimethoxysilane is used, but other known ones can also be selected. Furthermore, instead of aiming to form a film as an adhesive substance, a known substance can be used as an adhesive. For example, acrylates containing amino groups, imino residues, ethyleneimine residues, alkylene diamine residues, acrylates containing aziridinyl groups, amino ester-modified vinyl polymer-aromatic epoxy adhesives, amino nitrogen-containing meccrylate polymers, etc. An adhesive may also be used. Furthermore, a fluororesin may be used as the adhesive substance.

When such an adhesive substance is used, the processing temperature is 3.
At temperatures above 00-350℃ or 400℃, these substances lose their properties and lose their effectiveness as adhesives.
The glass base fabric base material has a temperature of 300°C or lower, and therefore a fluororesin film that can be melted at a temperature of 280°C or lower, further preferably around 250°C or lower, will give more preferable results.

In the present invention, the fluorine-based resin layer is formed on one side of the base fabric, but is required on the other side to compensate for the fragility, chipping, and low abrasion resistance of the glass base fabric. Natural rubber, neoprene rubber, chloroprene rubber, silicone rubber, Hypalon and other synthetic rubbers, PvC resin, ethylene-vinyl acetate copolymer (EV
A) Form a coating polymer layer made of synthetic resin such as M resin, acrylic resin, silicone resin, urethane resin, polyester resin, or other synthetic resin. In this case, it is more preferable that these resins have an N fuel ratio. If the coating polymer layer formed on the other side is made of silicone rubber or silicone resin, the sheet will have a flexible finish, making it suitable for use as heat-resistant cloth for heat-resistant ducts, heat-resistant covers, and the like.

It is preferable that the fluororesin film is attached in such a way that it forms a layer rather than the entire glass base fabric being impregnated with the resin. Regarding the relationship between the fluorine-based resin film and the base fabric, the molten resin of the fluorine-based resin film penetrates and adheres to the surface of the base fabric, but it does not penetrate into the entire base fabric. is preferable in terms of hardness, flexibility, and ease of handling. However, there is no problem even if the resin permeates the entire base fabric. Further, the thickness of the fluororesin film stuck on the nonflammable base fabric is preferably 5 to 2000 μm, particularly 10 to 1500 μm. The sheet of the present invention may be formed into a tape shape, or may be cut into tape shapes.

For example, this tape-like material can be used to coat or wrap electric wires, cables, and other applications that require heat resistance and flame retardancy.

〔Example〕

Although the present invention is configured and implemented as described above, the present invention will be explained in more detail below with reference to Examples.

Reference example 1 Glass base fabric: basis weight 290 g / nr gray strong strength warp 180 kg / 3 cm weft 167 kg
/ 3 cm, and this base fabric was not treated with an adhesive substance (sample ■), γ-methacryloxypropyltrimethoxysilane
0.5% by weight (manufactured by P.P., trade name A-174) (sample ■), and one coated with Sony Chemical's acrylic adhesive 5C462 at 30 g/rd on one side (sample ■). and heated each of these samples to 330°C.
P, F, 8-(m, p, 310°C) films (thickness: 50 cm) were superimposed and bonded under heat and pressure to prepare a composite. The water pressure resistance of the composite thus obtained sufficiently exceeded a water column of 1000 mm, which was preferable, and it was sufficiently durable for use as a nonflammable membrane material.

The physical properties of these sheets were measured as follows.

As can be seen from the table above, the strength is slightly lower than that of gray fabric, but it is not enough to cause a problem, and there is almost no difference, and the difference in adhesive strength due to the adhesive substance was not significant enough to be recognized. .

Reference Example 2 Three samples (Samples I, ■, and ■) used in Reference Example 1 were coated with P, V, D, F, and films (m, p,
180°C), the samples were heated to 330°C and 260°C, respectively, and the composites were bonded together by stacking them and applying heat and pressure. The resulting product has a water pressure resistance of 1000mm.
The amount of water column or more was sufficient to withstand use as a noncombustible sheet membrane material, but just to be sure, the performance was measured and the results are shown in the table below.

As can be seen from the table above, the strength retention rate is better when treated at 260℃ than when treated at 330℃, and the adhesive strength durability is considerably better than when treated at 330℃. The effect of the adhesive substance was difficult to recognize.

However, it shows a clear effect at 260° C., and it can be seen that even more excellent durability is exhibited when higher performance is required (condition ①).

Example 1 A coating layer of PVC resin or silicone resin with a thickness of 0.5111 m was formed on the exposed surface of the glass base fabric of each of the composites obtained in Reference Examples 1 and 2. All of the obtained laminated sheets exhibited good strength and flexibility, sufficient resistance to breakage and abrasion deterioration, and good stain resistance and weather resistance.

Furthermore, since the glass resin was not exposed, there was no tingling sensation to the human body.

〔Effect of the invention〕

The present invention has the above configuration and can provide a flame-retardant sheet that fully takes advantage of the weather resistance, antifouling properties, and flame retardant properties of fluorine-based resins. In addition, when manufacturing these sheets, there is no pollution caused by decomposition gas or unproductiveness due to the processing speed, which is caused by conventional P, T, F, and E coating methods, and there is no sagging of processing agents. There are no troubles such as muddy cracks or foaming, and the obtained film is homogeneous, making it possible to easily obtain a more preferable flame-retardant sheet. Also,
By selecting the processing conditions and materials, it is possible to obtain a more preferable durable membrane material, and by further selecting the laminated structure, it is possible to obtain a nearly perfect flame-retardant or non-combustible membrane material, which increases the practical value of the sheet of the present invention. There is something very big about it.

Claims (1)

[Scope of Claims] 1. A nonflammable base fabric layer made of nonflammable fiber fabric, a fluorine-based resin layer formed on one surface thereof, and a natural rubber, synthetic rubber, or fluorine-based resin layer formed on the other surface. A flame-retardant sheet comprising a coating polymer layer made of a synthetic resin other than resin. 2. The sheet according to claim 1, wherein the nonflammable base fabric is made of glass fiber fabric. 3. The coating polymer layer on the other side is selected from natural rubber, neoprene rubber, chloroprene rubber, silicone rubber, Hypalon, PVC resin, ethylene-vinyl acetate copolymer resin, acrylic resin, silicone resin, urethane resin, and polyester resin. The sheet according to claim 1 or 2, comprising at least one type of. 4. The sheet according to any one of claims 1 to 3, wherein the fluororesin layer has a melting point of 310°C or less. 5. The sheet according to any one of claims 1 to 4, wherein the fluororesin layer has a melting point of 280°C or less. 6. The sheet according to any one of claims 1 to 5, wherein the fluororesin layer has a melting point of 250°C or less. 7. The sheet according to any one of claims 1 to 6, wherein the fluororesin layer is attached via an adhesive layer. 8. The sheet according to any one of claims 1 to 7, wherein the fluororesin layer has a thickness of 5 to 2000 μm.