JPH11269772A - Flame retardant resin fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an excellent flame-retardant fiber fabric not only excellent in flame resistance, antifouling properties and waterproof but also hardly causing a harmful gas containing a halogen element when burning the fabric. SOLUTION: This flame retardant resin-finished fabric has at least one face coated with a flame-retardant resin composition comprising a copolymerized polyester-based resin having <=0 deg.C glass transition temperature, and ammonium polyphosphate-based compound, and is characterized by satisfying the following flame resistance specification: (1) having flame-resistance classified as rating 2 of flammability test based on JIS A1322; (2) having flame resistance satisfying the specification of JIS L1092.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a sheet for truck hood, which is excellent in both flame retardancy, antifouling property and water resistance.
The present invention relates to a flame-retardant resin-processed cloth used for tents such as a warehouse tent and a tent for eaves, and a sheet for construction work such as a tarpaulin or a mesh sheet for construction.

[0002]

2. Description of the Related Art Conventionally, a soft vinyl chloride resin is coated on a fiber cloth by various methods such as a calendering method, an extrusion laminating method and a coating method, and is used for various events or for warehouses, eaves tents, truck hoods, and construction work. Widely used for various purposes such as curing sheets, various sheets such as open sheets, backlits for signboards, and flexible containers. Vinyl chloride resin has various advantages such as low cost and good handling properties, but has the serious disadvantage that toxic gas containing halogen elements, smoke and residues are generated during incineration, and it has a global environmental scale. Therefore, development of a product using a resin containing no halogen element for the purpose of environmental protection has been eagerly desired.

[0003] From this viewpoint, commercialization of olefin resin, acrylic resin, urethane resin, and the like has been studied in various fields, but in fields where flame retardancy and physical properties are regarded as important,
For example, in the field of temporary sheets for tents and construction work, satisfactory products have not yet been proposed.

[0004] Fabrics used for the various applications include:
When a high level of flame retardancy is required and conventional hydrated metal hydroxides such as magnesium hydroxide and aluminum hydroxide are used as flame retardants, filling of 100 parts by weight or more is required to achieve the flame retardant standard. This is necessary, and a significant decrease in resin properties is inevitable. Also, when using a phosphorus compound such as a phosphate compound as a flame retardant,
Most phosphorus compounds are liquid at room temperature, have a poor affinity for thermoplastic resins, and easily bleed to the surface, and therefore have the disadvantage that the surface is tacky and dirt easily adheres.

[0005]

SUMMARY OF THE INVENTION In view of the background of the prior art, the present invention is excellent in both flame retardancy, antifouling property and water resistance, and does not generate toxic substances containing halogen elements during combustion. To provide a flame-retardant fiber fabric.

[0006]

The present invention employs the following means in order to solve the above-mentioned problems. That is, the flame-retardant resin-processed cloth of the present invention is coated on at least one side of the fiber cloth with a flame-retardant resin composition comprising a copolymerized polyester resin having a glass transition point of 0 ° C. or lower and an ammonium polyphosphate compound. Characterized by satisfying at least the following flame retardancy standards.

[0007] (1) Flame proofing, when measured according to JIS A1322, meets the flame proof second class.

[0008] (2) The flame resistance is acceptable when measured according to JIS L1092.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention
In view of the fact that it was extremely difficult to obtain a fibrous structure that has antifouling properties and does not contain toxic halogen elements during combustion, we conducted intensive studies and found that it was an inorganic flame retardant that was powdery and did not cause bleeding. By coating at least one surface of the fiber base fabric with a specific copolymerized polyester resin having a glass transition point of 0 ° C. or less containing a certain ammonium polyphosphate compound, excellent flame retardancy, antifouling property, and resin physical properties are obtained. It was determined that the maintenance of the maintenance could be achieved.

In the present invention, as the copolymerized polyester resin used for the flame-retardant resin composition, a thermoplastic polyester resin containing no plasticizer which does not cause stain due to migration of the plasticizer onto the surface is preferable. As such a copolymerized polyester resin, an aqueous system and a solvent system can be used, but an aqueous system is preferable in view of recent environmental problems and processability.
The polyester resin is usually composed of a combination of a polyhydric alcohol and a polycarboxylic acid. The water-soluble polyester is a third or fourth polyester resin mainly composed of a saturated homopolyester resin containing ethylene glycol and terephthalic acid as main components. By introducing isophthalic acid, adipic acid, aliphatic dicarboxylic acid, and the like as components, the molecular skeleton is asymmetric, low crystallization and low melting point are achieved, and sodium sulfoisophthalate is copolymerized to reduce Those which have achieved crystallization, low melting point and water solubility are generally used.

The copolymerized polyester resin used in the flame-retardant resin composition according to the present invention is preferably flexible with low crystallinity from the viewpoint of preventing a decrease in film strength due to filler filling. Those having lower crystallinity using a diol are preferred.
If this standard is expressed by replacing it with a glass transition point, those having a glass transition point temperature of 0 ° C. or less are preferable, and more preferably −20 ° C.
C. or less can be preferably used. .

The ammonium polyphosphate compound used in the present invention is represented by the following formula as a general formula. A compound having a molecular weight of 4000 or more is preferably used from the viewpoint of durability. In addition, many of these compounds generally exhibit hygroscopicity, and may be a copolymer such as melamine from the viewpoint of improving water resistance, and may be a surface treatment from the viewpoint of improving compatibility with a resin. Is also preferably used.

(NH ₄ PO ₃ ) _{n In the} formula, n is a positive integer.

The combination with other phosphorus-based or inorganic-based flame retardants or auxiliaries can also be used as long as the physical properties are not impaired.

Regarding the amount of addition, the resin solid content 1
Flame retardancy can be achieved with an addition amount of 80 parts with respect to 00 parts by weight.
Part weight is preferred.

As the flame-retardant resin composition of the present invention, a composition containing at least one selected from a colorant, a weatherproofing agent and a light stabilizer in the copolymerized polyester resin can be used. . As such colorants, generally used pigment-based colorants are preferable in terms of compatibility and weather resistance. Further, as such an ultraviolet absorber, a benzotriazole-based, benzophenone-based or triazine-based one can be used as a mixture of one or more kinds, and preferably 0.1 to 3 parts by weight is added to 100 parts by weight of the resin. As the light stabilizer of the present invention, hindered amine compounds and hindered phenol compounds can be used.
0.1 to 3 parts by weight is preferably added to 0 parts by weight.
Further, an antioxidant, an antibacterial agent, and a fungicide may be added as necessary.

In the resin-coated fabric of the present invention, a resin for imparting antifouling property and water resistance can be laminated on the surface of the resin-coated fabric as required. As the resin having antifouling properties, known resins can be used, but polyester resins are preferred from the viewpoint of the interfacial adhesion with the flame retardant resin composition.

The polyester resin imparting antifouling property of the present invention is a resin which is laminated on the surface of the resin-treated cloth in order to impart antifouling property, water resistance and durability. Is required. If this standard is expressed in terms of the above glass transition point, those having a glass transition temperature of 10 ° C. or higher are preferable, and those having a glass transition temperature of 20 ° C. or higher can be preferably used.

The flame-retardant resin-treated fabric of the present invention is obtained by coating the surface of a base fabric such as a woven fabric, a knitted fabric or a nonwoven fabric with a resin, and the fiber material used for the base fabric is polyester, polyamide, or the like. It is a knitted or woven fabric composed of synthetic fibers such as vinylon or natural fibers such as cotton and hemp alone or as a mixture, and the fibers may be long fibers or short fibers. The fiber fabric of the present invention may contain a flame retardant compound. The flame retardant treatment of the fiber cloth may be a flame retardant compound which may be blended or copolymerized with the fiber or may be attached to the fiber surface, and is not particularly limited. In the present invention, long fibers of polyester fibers can be preferably used in view of the strength and dimensional stability of the fibers. The polyester fiber referred to in the present invention is a fiber made of polyethylene terephthalate, polybutylene terephthalate or a polyester obtained by copolymerizing or blending these with a third component such as isophthalic acid, isophthalic acid sulfonate, adipic acid, or polyethylene glycol. Yes, it may be a fiber which has been made flame retardant in advance. The polymer of the polyester fiber preferably has an intrinsic viscosity of 0.65
As described above, more preferably those having 0.8 to 1.0 are used. Further, the density of the fiber itself is 1.38 g / cm.
High-strength fibers having a tensile strength of ³ or more, preferably 6 g / d or more, and more preferably 7 to 9 g / d are preferably used.

In order to impart flame retardancy to such a polyester fiber, a flame retardant compound is copolymerized at the time of polymerization of polyester, or a flame-retardant raw yarn blended at the time of polymerization or spinning, or after forming a polyester fiber, Any method of post-processing the flame-retardant compound may be used, and known flame-retarded polyester fibers can be used.
Polyester fibers obtained by copolymerizing a flame-retardant compound during the polymerization of polyester are preferred from the viewpoint of stability of flame-retardant performance.

Compounds for producing polyester fibers flame-retarded by such copolymerization include phosphoric esters such as triphenyl phosphate and phosphonic acids such as ethylene dimethylphosphonic acid and benzenephosphonic acid derivatives. Such phosphorus compounds and brominated bisphenols, their hydroxyalkyl derivatives, halogenated compounds such as brominated aromatic dicarboxylic acids and the like can be used, and flame retarded polyester fibers suitable for the present invention include: At least 85 mol% of the repeating units of the polyester are polyesters such as polyethylene terephthalate and polyethylene 2,6 naphthalate, and the content of phosphorus atoms in the repeating units is in the range of 0.2 to 1.0% by weight. Copolymer with bifunctional phosphorus compound It is possible to use the Ranaru fiber.

The fiber cloth used in the present invention may be further subjected to a water repellent treatment, an adhesive treatment, an antistatic treatment, a weathering agent, an antibacterial agent, a fungicide, etc., according to the purpose.

[0023]

[Example] (Flame retardancy A) The carbonized area, residual flame time, and residual dust time were measured by the JIS L 1091 A-1 method.
The number of times of flame contact was measured, and those that passed were indicated by 、, and those that failed were indicated by x. In addition, the measurement of the flame retardancy was performed by
The test was immersed in hot water at 0 ° C. for 30 minutes and air-dried.

(Flame Retardancy B) The residual flame time, residual dust time, and carbonization length were measured by the methods specified in JIS A 1322. Flameproof grade 2 or higher was indicated by ○, and that of less than 2 grades was indicated by x.
The measurement of the flame retardancy was performed on a work cloth immersed in hot water at 50 ° C. for 30 minutes and subjected to a pretreatment of method B, which was dried.

(Stain resistance) A stain test was conducted for 180 days by the 45 degree outdoor exposure method specified in JIS A-1410, and the surface before and after the contamination was measured with a digital colorimeter (manufactured by Suga Test Instruments Co., Ltd.). ) Was measured, and the degree of contamination was determined by the following formula.

Contamination degree (%) = A / B × 100 where A is the L value after the contamination, and B is the L value before the contamination, and the smaller the numerical value of the contamination degree, the more severe the contamination.

(Resin Physical Properties) 1000 times of 1 kg of Scott rubbing test specified in JIS K-6328. When the resin was cracked or peeled, the result was indicated by x, and when the resin was not caused, the result was indicated by ○.

Examples 1-4, Comparative Examples 1-6 A 1,000 denier, 96-filament polyester yarn (manufactured by Toray Industries, Inc.) was used for warp and weft.
Table 1 shows the results of weaving an open mesh fabric having a weft density of 13 yarns / inch, treating it by the following method, and evaluating its performance.

Resin (Resin A): Copolymerized polyester resin emulsion (Tg = −20 ° C.) (Resin B): 〃 (Tg = −5 ° C.) (Resin C): 〃 (Tg = 10 ° C.) (Resin D) 〃 (Tg = 20 ° C.) Flame retardant (flame retardant a) ammonium polyphosphate having a molecular weight of about 5,000 (flame retardant b) aluminum hydroxide A thermoplastic resin A, B, C is mixed with a flame retardant, and a blue pigment is further added. The woven fabric was immersed in a mixture of 3% of a liquid (aqueous dispersion having a solid content of 70%), adjusted to have an attached solid content of 150 g / m ² , dried at 130 ° C, and heat-treated at 160 ° C. Then, it is immersed in a solution of a polyester resin, adjusted so that the attached solid content becomes 4%, dried at 120 ° C., and dried.
Heat treatment was performed at 50 ° C.

Further, the surface polyester layer was coated with a copolymerized polyester resin solution so as to give a resin coating amount of 5 g / m ² , dried at 130 ° C., and heat-treated at 170 ° C.

[0031]

[Table 1] As is clear from Table 1, those of Examples 1 to 4 have excellent flame retardancy, and those that have been surface-treated with a polyester resin have no surface tack and also have antifouling properties. . The thing according to the present invention could be suitably used as a curing mesh for building work.

Examples 5 to 8, Comparative Examples 7 to 8 Twenty-numbered polyester spun yarn (manufactured by Toray Industries, Inc.) was used for warp and weft, and the warp / weft density was 54/4.
Table 2 shows the results obtained by weaving a plain woven fabric of 8 pieces / inch, treating it by the following method, and evaluating the performance.

Resin (Resin A): Copolymerized polyester resin emulsion (Tg = −20 ° C.) (Resin B): 〃 (Tg = −5 ° C.) (Resin C): 〃 (Tg = 10 ° C.) (Resin D) 〃 (Tg = 20 ° C.) Flame retardant (flame retardant a) Ammonium polyphosphate having a molecular weight of about 5,000 (flame retardant b) aluminum hydroxide A thermoplastic resin A, B, C is mixed with a flame retardant, and a blue pigment is further added. A 3% mixture of a liquid (aqueous dispersion having a solid content of 70%) was subjected to knife coating on the woven fabric, and the adhered solid content was 150 g /
m ² , dried at 130 ° C., 160 ° C.
Was heat-treated. Next, it was immersed in a solution of a polyester-based resin, adjusted to have a solid content of 4%, dried at 120 ° C, and heat-treated at 150 ° C.

Further, the surface layer was coated with a copolymerized polyester resin solution so as to give a resin coating amount of 5 g / m ² , dried at 130 ° C. and heat-treated at 170 ° C.

[0035]

[Table 2] As is clear from Table 2, those of Examples 5 to 8 have both flame retardancy and antifouling properties, and can be suitably used as a membrane material used outdoors, a canvas for a tent warehouse, and a sheet for construction work. there were.

[0036]

According to the present invention, it is possible to supply a resin-processed base fabric having excellent flame retardancy, antifouling properties and resin properties. Further, the resin-treated base fabric of the present invention does not generate a toxic gas containing a halogen element during combustion, and is very friendly to the environment.

The present invention can be suitably used as a resin processed base fabric for industrial materials, such as truck tops, warehouse tents, eaves tents, and other tents such as tarpaulins and construction mesh sheets. It was something that could be done.

Claims (10)

[Claims] At least one surface of a fiber cloth is coated with a flame-retardant resin composition comprising a copolymerized polyester resin having a glass transition point of 0 ° C. or lower and an ammonium polyphosphate compound, and at least the following flame retardant: A flame-retardant resin-processed fabric characterized by satisfying standards. (1) When the flame resistance is measured based on JIS A1322, the flame resistance is 2nd. (2) When the flame resistance is measured based on JIS L1092, it passes. 2. The ammonium polyphosphate has a molecular weight of 40.
The flame-retardant resin-processed fabric according to claim 1, which is not less than 00. 3. The method according to claim 1, wherein the copolymerized polyester resin comprises a colorant,
The flame-retardant resin-treated fabric according to claim 1, comprising at least one selected from a weathering agent and a light stabilizer. 4. The flame-retardant resin processed fabric according to claim 1, wherein the copolymerized polyester resin is an aqueous dispersion. 5. The flame-retardant material according to claim 1, wherein the surface of the resin-treated fabric is laminated with a resin having at least one function of stain resistance and water resistance. Resin processed fabric. 6. The flame-retardant resin processed fabric according to claim 5, wherein the resin having at least one of the functions of stain resistance and water resistance has a glass transition temperature of 10 ° C. or higher. 7. The flame-retardant resin-processed fabric according to claim 5, wherein the resin having at least one function of antifouling property and water resistance is a copolymerized polyester resin. 8. The flame-retardant resin-processed fabric according to claim 1, wherein the fiber fabric is made of a polyester fiber. 9. The flame-retardant resin-treated cloth according to claim 1, wherein the fiber cloth contains a flame-retardant compound. 10. The flame-retardant fibrous structure, wherein the film material for a building is
The flame-retardant resin-processed fabric according to any one of claims 1 to 9, which is used for any of a tent warehouse canvas, a construction work sheet, and a construction work net.