JPH11323015A - Flame-retardant resin composition and flame-retardant fiber structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition having excellent flame retardancy, resin film formability and resin film strength, scarcely bleeding a frame retardant on the surface and not generating a poisonous substance containing a halogen on combustion by compounding a flame retardant encapsulated in microcapsules and a thermoplastic resin. SOLUTION: This flame-retardant resin composition comprises (A) a flame retardant preferably a flame retardant not containing a halogen, more preferably a phosphorous compound, especially a flame-retardant compound of the formula [R1 to R4 are each phenyl, cresyl or xylenyl; (n) is 1-20]} encapsulated in microcapsules and (B) a thermoplastic resin (a polyolefinic resin, a polyester- based resin, a polyurethane-based resin, etc.,). The microcapsules are added in a temperature B/temperature A ratio of preferably 100 pts.wt./(10-200 pts.wt.), more preferably 100 pts.wt./(20-80 pts.wt.).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition which is excellent in both flame retardancy, resin film formability and resin film strength, and which does not contain a halogen element and has excellent workability, and the resin composition. And a flame-retardant fiber structure treated with

[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 and the like has been studied in various fields, but in fields where flame retardancy and physical properties are regarded as important, for example, for tents and temporary sheets for building works, At present, satisfactory products have not been proposed yet. This application requires a high degree of flame retardancy, and when using a conventional hydrated metal hydroxide such as magnesium hydroxide or aluminum hydroxide as a flame retardant, 100 parts by weight or more is required to achieve the flame retardant standard. Is required, and a drastic decrease in resin properties cannot be avoided. In addition, when a phosphorus compound such as a phosphoric ester compound is used as a flame retardant, most of the phosphorus compounds are liquid at room temperature and have a poor affinity with a thermoplastic resin and cannot be uniformly mixed. Is significantly reduced, the physical properties of the resin are reduced, and the surface bleeding of the flame retardant is caused, thereby remarkably degrading the quality of a film-formed product. Some phosphorus-based compounds also exist as solids at normal temperature, but most of them have similar melting points because they have a melting point of about 100 ° C. and become liquid during resin molding.

[0004]

At present, there is no proposal of a halogen-free resin composition having a film-forming property, film physical properties, quality and the like, and a fiber structure treated with the resin.

The present invention is excellent in flame retardancy, resin film formability and resin film strength, and furthermore, the flame retardant does not easily bleed to the surface and has excellent flame retardancy which does not generate toxic substances containing halogen elements during combustion. It is an object to provide a resin composition and a flame-retardant fiber structure.

[0006]

The present invention employs the following means to solve the above-mentioned problems. That is, the flame-retardant resin composition of the present invention is characterized in that it is composed of a flame retardant and a thermoplastic resin encapsulated in microcapsules, and the flame-retardant fiber of the present invention. The structure is characterized in that at least one surface of the fiber cloth is covered with the flame-retardant resin composition.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention has been made to solve the above-mentioned problems, that is, it is excellent in both flame retardancy, resin film formability and resin film strength, and furthermore, the flame retardant hardly bleeds on the surface, and toxic substances containing a halogen element during combustion. The present inventors have conducted intensive studies on an excellent flame-retardant resin composition that does not generate any substance, and have tried to enclose the flame retardant in microcapsules. Further, according to the present invention, it has been further investigated that a uniform film can be formed on a fiber cloth by using such a resin composition, and a flame-retardant fiber structure having excellent quality in which a flame retardant hardly bleeds to the resin surface can be provided. Things.

The flame retardant used in the present invention is not particularly limited, and generally used compounds can be used, but those containing no halogen element are preferable from the environmental point of view, and the flame retardant performance is not so high. Therefore, a phosphorus compound is preferred. Among the phosphorus compounds, the following flame-retardant compounds are particularly preferably used, and at least one of them can be used.

[0009]

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[0010] ★

[0011]

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[0012] ★

[0013]

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★

[0015]

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[0016] ★

[0017]

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★ The present invention is to microencapsulate a flame retardant. Known methods can be used for producing microcapsules, and for example, the methods described in “New Edition Microcapsules, Their Manufacturing Methods, Properties, and Applications (Sankyo Shuppan Co., Ltd.)” can be used. Rather, it can be appropriately selected according to the type of the flame retardant and the type of the thermoplastic resin, and the microencapsulated flame retardant can be selected from aqueous dispersion and solvent depending on the method of forming the thermoplastic resin resin. It can be used in dispersion or powder form.

In the production of the microcapsules of the present invention, not only one kind of flame retardant is microencapsulated but also a mixture of two or more kinds of flame retardants can be used.

The content of the flame retardant in the microcapsule of the present invention is not particularly limited, but it is preferable that the amount of the flame retardant is large because the amount of the flame retardant can be reduced in the thermoplastic resin. However, the weight ratio to the total weight of the outer wall resin is preferably 5% or more, and more preferably 10% or more, since the resin is damaged and the flame retardant bleeds.

The particle size of the microcapsules of the present invention is preferably as small as possible, preferably 10 μm or less, more preferably 5 μm or less, particularly preferably 3 μm or less.

In the present invention, two or more kinds of microcapsules having different types of flame retardants may be mixed and used.

As the thermoplastic resin of the present invention, those generally used can be used and are not particularly limited, but those containing no halogen element are preferable from the viewpoint of environmental protection. At least one selected from polyolefin-based resins, polyester-based resins and polyurethane-based resins is preferably used in view of film-forming properties and flame retardancy.

Examples of the polyolefin resin include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / alkylene alkylene ester, ethylene / alkylene methacrylate, and ethylene / propylene alkylene ester.
Vinyl acetate copolymer nad can be used. Further, as the polyester resin, two or more aromatic dicarboxylic acids and / or aliphatic dicarboxylic acids,
A copolymer composed of two or more alkylene glycols is preferably used. Further, as the polyurethane resin, for example, a polyurethane obtained by reacting an organic diisocyanate with a long-chain diol and a chain extender is typical. As the organic diisocyanate, alicyclic organic diisocyanate, aliphatic organic diisocyanate, aromatic Group organic diisocyanates can be used, and as long-chain diols, polyester diols, polyether diols, polyamide ester diols, polycarbonate diols, and the like can be used. Compounds containing two active hydrogens, such as glycols, low molecular weight diamines, and low molecular weight amino alcohols can be used. These polyurethanes are
Two or more kinds may be used in combination. Among them, polycarbonate-based polyurethane is preferably used in terms of weather resistance, hydrolysis resistance and the like.

The thermoplastic resin of the present invention can be used in a form dissolved or dispersed in pellets, a solvent or water.

The mixing ratio between the microcapsules of the present invention and the thermoplastic resin is determined by the type of the flame retardant, the type of the thermoplastic resin, the desired resin coating amount, and the like. Generally, the flame retardant is preferably 10 to 200 parts by weight, based on 100 parts by weight of the thermoplastic resin,
More preferably, the microcapsules are mixed to become 20 to 80 parts by weight.

The resin composition of the present invention can be used as a solid mixture or a liquid mixture. As the liquid, a water-dispersed liquid that does not use a solvent is preferable from the viewpoint of the working environment.

The resin composition of the present invention contains a coloring agent. As such a coloring agent, a commonly used pigment-based coloring agent is preferably used in terms of compatibility and weather resistance.

The resin composition of the present invention can also contain an ultraviolet absorber and a light stabilizer, and generally used compounds can be used. Is a benzotriazole type,
One or more benzophenone-based or triazine-based ones can be used as a mixture, and the UV absorber is preferably added in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the thermoplastic resin. Such light stabilizers include:
Hindered amine-based and hindered phenol-based compounds can be used, and the light stabilizer is preferably added in an amount of 0.1 to 3 parts by weight based on 100 parts by weight of the thermoplastic resin. Further, an antioxidant, an antibacterial agent, and a fungicide may be added as necessary.

The flame-retardant resin composition of the present invention can be used as a flame-retardant fibrous structure obtained by coating it on at least one surface of a fiber cloth. The method of coating the resin of the present invention can be a known method, and a film is formed by a calendering method or an extrusion method and pressed against a fiber cloth, or a solution-type resin is applied by a coating method, a dipping method, or the like. May be dried and fixed.

The fiber fabric referred to here is a knitted or woven fabric composed of synthetic fibers such as polyester, polyamide and vinylon, and natural fibers such as cotton and hemp alone or mixed.
Non-woven fabric or the like can be used. The fibers constituting such a fabric may be long fibers or short fibers.

In the present invention, long fibers of polyester fibers are preferred from the viewpoint of fiber strength and dimensional stability. 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. There may be.

The polyester fiber preferably has a polymer intrinsic viscosity of preferably 0.65 or more, more preferably 0.8 to 1.0. Further, the fiber is preferably a high-strength fiber having a density of 1.38 g / cm ³ or more and a tensile strength of preferably 6 g / d or more, more preferably 7 to 9 g / d.

The fiber fabric may further contain a flame retardant compound. The flame retardant treatment of the fiber fabric may be a flame retardant compound blended or copolymerized with the fiber, or may be attached to the fiber surface, and is not particularly limited.

For example, in order to impart flame retardancy to a polyester fiber, a flame-retardant compound is copolymerized at the time of polymerization of polyester, or a flame-retardant raw yarn or polyester fiber blended at the time of polymerization or at the time of spinning is formed. later,
Any method of post-processing the flame-retardant compound may be used, and a known flame-retarded polyester fiber can be used. However, a polyester fiber obtained by copolymerizing the flame-retardant compound at the time of polymerization of the polyester has a flame-retardant performance. It is preferable from the viewpoint of stability.

Compounds for producing polyester fibers flame-retarded by such copolymerization include phosphoric esters such as triphenyl phosphate and phosphonic acids such as ethylenedimethylphosphonic acid and benzenephosphonic acid derivatives. Phosphorus compounds and brominated bisphenols, hydroxyalkyl derivatives thereof, halogenated compounds such as brominated aromatic dicarboxylic acids and the like can be used, particularly preferred flame retarded polyester fibers of 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. Copolymers containing certain bifunctional phosphorus compounds It may be used fibers made of.

The fiber cloth according to the present invention may further be subjected to a water repellent treatment, an adhesive treatment, an antistatic treatment, etc.
Those treated with a weathering agent, an antibacterial agent, a fungicide or the like can also be used.

[0038]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

The performance values shown in Examples and Comparative Examples were measured by the following methods. (Flame Retardancy A) The carbonization area, residual flame time, and residual dust time were measured by the A-1 method of JIS L 1091, and the number of flame contact times was measured by the D method. In addition, the measurement of the flame retardancy was performed by immersing the work cloth in hot water of 50 ° C. for 30 minutes.
Naturally dried ones were also performed. (Flame retardancy B) The residual flame time, residual dust time, and carbonization length were measured according to the method specified in JIS A 1322. (Resin surface tack) The surface tack due to the flame retardant was determined by tactile sensation and displayed as a grade.

1: Extremely sticky 2: Slightly sticky 3: Not sticky (waterproof) Water resistance was measured according to JIS-L-1096. (Anti-fouling property) A 180-day contamination test is performed by a 45-degree outdoor exposure method specified in JIS-A-1410, and the surface before and after the contamination is measured with a digital colorimeter (manufactured by Suga Test Instruments Co., Ltd.). Measure the L value and calculate the degree of contamination using the following formula.
I did.

Degree of contamination (%) = A / B × 100 where A is the L value after contamination, and B is the L value before contamination, and the smaller the numerical value of the degree of contamination, the more severe the contamination. Examples 1 to 9 and Comparative Examples 1 to 6 Using a 1000 denier, 96 filament polyester yarn (manufactured by Toray Industries, Inc.) as a warp and a 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. (Flame retardant capsule) A microcapsule aqueous dispersion of the following flame retardant was prepared using a urea resin for the wall material. The weight ratio of the flame retardant / wall material is 90/10, the solid content concentration in the aqueous dispersion is 50%, and the average particle system is 3 μm.

Flame retardant A: The following compounds were used.

[0043]

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★ Flame retardant B: The following compounds were used.

[0045]

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★ Flame retardant C: The following compounds were used.

[0047]

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★ Flame retardant D: The following compounds were used.

[0049]

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★ Flame retardant E: The following compounds were used.

[0051]

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★ (Thermoplastic resin) Resin a: Aqueous dispersion of ethylene / vinyl acetate copolymer (solid content 30%) Resin b: Aqueous dispersion of polycarbonate urethane (solid content 37%) (Resin processing) Resin A or b is mixed with a flame retardant microcapsule, and the resin is mixed so that the amount of the flame retardant is 40% based on the solid content of the resin.
(Aqueous dispersion) was mixed at 4% to obtain a treatment liquid. The mesh fabric was immersed in the liquid, adjusted to have an attached solid content of 150 g / m ² , dried at 130 ° C, and heat-treated at 160 ° C.

For comparison, the flame retardants A, B, C, D and E were 4
An emulsion having a concentration of 0% was processed in the same manner. The results are shown in Table 1.

As is evident from Table 1, those using the microencapsulated flame retardant of the present invention have no surface tack and are hardly contaminated, and are suitable as a curing mesh for building works. I understand. On the other hand, an emulsion of the flame retardant used for comparison has poor compatibility with the resin, and the resin surface has sticky contamination.

Example 10 and Comparative Example 7 As a flame retardant, one obtained by microencapsulating the compound of the formula 16 (Example 10) and one emulsified (Comparative Example 7) were used. The results were evaluated in the same manner as in Example 1 except that the blending amount was changed to 100%.

Flame retardant F: The following compounds were used.

[0057]

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As is clear from Table 1, the composition of Example 10 satisfied the flame retardancy after the hot water treatment.
In the case of Comparative Example 7, the flame retardancy after hot water treatment was rejected because the water resistance of the flame retardant was poor. That is, it can be seen that in the case of Example 10, the water resistance of the flame retardant is also improved.

[0059]

[Table 1]

Example 11, Comparative Examples 8 to 9 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. (Microcapsule of Flame Retardant) Compound 12 was formed into a water-dispersed microcapsule having a urea-based resin as a wall material and a weight ratio of flame retardant / wall material of 85/15. The concentration of the microcapsules is 60% and the average particle system is 4 μm. (Resin) Emulsion of polycarbonate urethane (solid content 38%) (Preparation of treatment liquid) The flame retardant solid content to resin solid content is 5%
The resulting mixture was further mixed with 3 parts of a yellow pigment (a 70% solid dispersion in water).

The woven fabric is immersed in the treatment liquid and adhered so that the solid content of the treatment liquid is 300 g / m ^2.
And heat-treated at 160 ° C.

For comparison, the same treatment as in the example was carried out except that the flame retardant was a 35% emulsion.

[0063]

[Table 2]

As is clear from Table 2, the product of Example 11 has less surface tack and is less susceptible to contamination than those of Comparative Examples 8 and 9, and is suitable as a waterproof sheet for tents and the like. It turns out that it is something.

Example 12, Comparative Examples 10 to 11 Using a 20th-count polyester spun yarn (manufactured by Toray Industries, Inc.) for warp and weft, the warp / weft density was 54/4.
Table 3 shows the results obtained by weaving a plain woven fabric of 8 pieces / inch, treating it by the following method, and evaluating the performance. (Microcapsule of Flame Retardant) Compound 12 was used as a water-dispersible microcapsule having a urea-based resin as a wall material and a flame retardant / wall material weight ratio of 85/15. A 30 micron powder microcapsule was obtained. (Resin) Polycarbonate urethane solvent-soluble resin (solid content 25%) (Preparation of treatment liquid) Flame retardant solid content to resin solid content is 5%
The resulting mixture was further mixed with 20 parts of a green pigment (solid content: 30%).

The treatment liquid was applied to the woven fabric using a comma coater so that the solid content of the treatment liquid was 150 g / m ^2.
It was dried at 20 ° C and heat-treated at 160 ° C.

A comparative example was treated in the same manner as in the example except that the flame retardant was not encapsulated.

[0068]

[Table 3]

As is evident from Table 3, Example 12 has less surface tack than Comparative Examples 10 and 11, and is less likely to be contaminated, and may be suitable as a waterproof cloth such as a tent. Recognize.

Example 13, Comparative Examples 12 to 13 Water was evaporated from the aqueous dispersion of microcapsules of the flame retardant C of Example 1 by a spray-drying method to obtain powdery capsules having an average particle size of about 30 μm. The mixture was put into a roll kneader at 180 ° C. together with the polymer pellets and mixed to form a sheet having a thickness of 300 μm.

The ethylene / vinyl acetate copolymer pellets were prepared by mixing the ethylene / vinyl acetate copolymer with an ultraviolet absorber / light stabilizer / tinuvine 326 / antioxidant.
Chimasorb 944 / Irganox 1010 (all manufactured by Ciba Geigy) were added in an amount of 0.5 part by weight / 0.5 part by weight / 0.05 part by weight with respect to 100 parts by weight of the copolymer.
A pigment containing 3 parts by weight of titanium oxide (particle diameter 0.2 μm) was used.

The sheet thus prepared was pressed on both sides of the same fabric as in Example 1 with a flat plate press at 170 ° C.

As a comparison, the flame retardant C was similarly introduced into the kneader and mixed as it was, but the flame retardant melted on the roll surface and the resin slipped, so that a sheet could not be obtained. Table 4 shows the results.

[0074]

[Table 4]

As is clear from Table 4, Example 13
It can be seen that a sheet suitable as a building material having excellent film forming properties, flame retardancy, antifouling properties, and the like can be obtained as compared with Comparative Examples 12 and 13.

[0076]

According to the present invention, it is possible to stably supply a flame-retardant resin composition and a flame-retardant fibrous structure excellent in processability, flame retardancy and stain resistance. Since the resin composition and the fibrous structure of the present invention do not generate harmful substances including a halogen element even when burned, they are preferable from the viewpoint of environmental protection.

The flame-retardant fiber structure of the present invention can be suitably used as various curing sheets for construction work, canvases for tent warehouses and truck hoods, membrane materials for construction, backlits, container base fabrics. .

Claims (13)

[Claims] 1. A flame-retardant resin composition comprising a flame retardant encapsulated in microcapsules and a thermoplastic resin. 2. The flame-retardant resin composition according to claim 1, wherein the flame retardant is a compound containing no halogen element. 3. The flame-retardant resin composition according to claim 2, wherein the compound containing no halogen element is a phosphorus compound. 4. The flame-retardant resin composition according to claim 3, wherein the phosphorus compound is at least one selected from compounds represented by the following formula. Embedded image ★ [Formula 2] ★ [Formula 3] ★ [Formula 4] ★ [Formula 5] ★ 5. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is a resin containing no halogen element. 6. The resin containing no halogen element is at least one selected from a polyolefin resin, a polyester resin, a polyamide resin and a polyurethane resin.
The flame-retardant resin composition according to claim 5, which is a seed. 7. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin contains a coloring agent. 8. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin contains at least one selected from an ultraviolet absorber and a light stabilizer. . 9. The flame-retardant resin composition according to claim 1, wherein the resin composition is an aqueous dispersion. 10. A flame-retardant fiber structure, wherein at least one surface of a fiber cloth is covered with the flame-retardant resin composition according to claim 1. 11. The flame-retardant fiber structure according to claim 10, wherein the fiber cloth is a polyester-based fibrous cloth. 12. The flame-retardant fiber structure according to claim 10, wherein the fiber cloth contains a flame-retardant compound. 13. The flame-retardant fibrous structure is used as a building membrane material,
The flame-retardant fiber structure according to any one of claims 10 to 12, which is used for a canvas for a tent warehouse, a sheet for construction work, or a net for construction work.