JP4787183B2 - Flame-retardant polyester fiber, flame-retardant material using the same, and method for producing flame-retardant polyester fiber - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a flame retardant polyester fiber containing ammonium polyphosphate as a flame retardant, a flame retardant using the same, and a method for producing the flame retardant polyester fiber.

  Polyethylene terephthalate is a useful material that has excellent mechanical properties and is widely used as fibers, films, and other plastic moldings. However, it has the drawback of being easily combustible, and in recent years, with the increasing awareness of fires, there is a strong demand for flame retardancy.

  Various attempts have been made to make such polyester flame-retardant. Conventionally, a method of kneading and mixing a flame retardant at the time of molding a fiber, a film, a method of post-treating the flame retardant to a molded product, A method of adding and blending by a legal method is known.

For example, Patent Document 1 discloses a polyester obtained by copolymerizing an organic phosphorus compound so that a phosphorus content in a polymer is 1.0% by mass, and hydrolyzing a product after completion of the reaction, A highly flame-retardant polyester fiber is disclosed in which an oligomer having a terminal acid value of less than 10 is added and blended so that the phosphorus content of the entire fiber is 0.4 to 2.0 mass%. In addition, for example, in Patent Document 2, a flame-retardant fiber product in which an ammonium polyphosphate-containing material coated with a thermoplastic resin is contained in a processing step in a fiber product after spinning, and in Patent Document 3, melamine coating is performed. A flame retardant fiber in which ammonium polyphosphate is contained in a post-spun fiber product is disclosed. Further, Patent Document 4 discloses a flame retardant fiber product obtained by fixing a polyphosphate flame retardant composed of composite particles of a polyphosphate compound and a silicone resin to fibers.
JP-A-8-127918 JP 2001-262466 A JP-A-9-310272 JP 2006-63465 A

  However, in the copolymerization method as in Patent Document 1, since a phosphorus compound that can be copolymerized is used during polyester synthesis, it is necessary to use an expensive compound as a flame retardant, which is uneconomical and the polyester resin itself. It is necessary to add a flame retardant at the stage of synthesizing, and it is difficult to produce a flame retardant thermoplastic polyester resin by reusing the thermoplastic polyester resin product after use.

  In addition, as in Patent Documents 2 to 4, the method of flame-retarding treatment after spinning polyester fibers is complicated or non-uniform in treatment, or the texture of the fibers is roughened, or is washed. There may be various drawbacks such as reduced flame retardancy. If the flame retardant treatment is not uniform, sufficient flame retardant effects cannot be obtained, and safety during use is also impaired.

  Further, in the case of obtaining a flame retardant polyester fiber, in the method of producing a compound by adding a flame retardant to the thermoplastic polyester resin itself, if the amount of the flame retardant is large in order to improve the flame retardant effect, the flame retardant during spinning May sublimate or significantly reduce the mechanical properties of the fiber.

  Accordingly, there is a need for a method capable of easily flame retarding a polyester having excellent mechanical properties, particularly a flame retardant polyester resin composition necessary for thermoplastic polyester fibers.

  On the other hand, such flame retardant polyester fiber is used for high-rise buildings such as curtains and display plywood, carpets, wall coverings, passenger aircraft carpets, curtains, seats, cushions and other interior materials, automobile interior materials, and railway vehicle interiors. It can be used in a wide range of materials, marine supplies, bedding, flameproof hoods, clothing, etc.

  In addition to organic phosphorus compounds, halogen compounds such as bromine and chlorine are used as flame retardants, but there are problems during combustion. That is, when a flame retardant using a halogen compound is burned or incinerated, dioxins that are generally noted as environmental pollutants are generated.

  In addition, the flame retardant material is required to have durability. This is because as a result of excellent durability, the amount of waste itself can be reduced, and the generation of carbon dioxide by incineration can be effectively suppressed. At the same time, if the conventional resources can be reused, it is possible to recycle the material to be incinerated, which contributes to environmental conservation and is economically advantageous. In particular, if the resources collected by the recent Containers and Packaging Recycling Law cannot be used effectively, there is no meaning for collection. Therefore, from the viewpoint of environmental conservation, a method for easily obtaining flame retardant fibers using existing resources is desired.

As a result of detailed examination of a combination of a thermoplastic polyester resin and a flame retardant, the present inventors have obtained an excellent flame retardant effect by adding a small amount of ammonium polyphosphate, and safety at the time of product disposal and combustion. Thus, the present invention was completed by finding that a flame retardant having excellent light resistance can be obtained. That is, the present invention provides the following (1) to ( 10 ).

(1) A fiber obtained by melt spinning the flame retardant polyester resin composition comprising an ammonium polyphosphate and a thermoplastic polyester resin, 0.1 to 10 mass respectively of ammonium polyphosphate based on the fiber維重amount %, A polyester resin is contained in 99.9 to 90% by mass , and the thickness of the fiber is 1.0 to 17.0 dtex .
(2) The flame-retardant fiber according to (1), wherein the ammonium polyphosphate is a powder having an average particle size of 30 μm or less .

( 3 ) The flame-retardant fiber according to (1) or (2) , wherein the decomposition temperature of ammonium polyphosphate is 270 ° C. or higher.

( 4 ) The flame retardancy according to any one of (1) to (3) , which is a fiber obtained by melt spinning at a take-up speed of 350 to 1000 m / min and a spinning temperature of 200 to 300 ° C. by a dry method. fiber.

( 5 ) The flame retardant polyester resin composition further contains a colorant, 0.1 to 10% by mass of ammonium polyphosphate, 0.02 to 5% by mass of colorant, and polyester resin based on the fiber weight. flame-retardant fiber according to any one of the above characterized in that it contains from 99.88 to 85 wt% (1) to (4).

( 6 ) The flame retardant fiber according to ( 5 ), wherein the colorant is carbon black.

( 7 ) A flame retardant containing 5 to 100% by mass of the flame retardant fiber according to (1) to ( 6 ) above.

( 8 ) The flame retardant material according to ( 7 ), which is used as an automobile interior material.

( 9 ) Any one of the above (1) to (6), wherein a masterbatch containing ammonium polyphosphate and a masterbatch base material and a thermoplastic polyester resin are melt-mixed and then melt-spun. method for producing a flame retardant of textiles according to One.
(10) A masterbatch containing ammonium polyphosphate and a masterbatch substrate, a masterbatch containing a colorant and a masterbatch substrate, and a thermoplastic polyester resin are melt-mixed and then melt-spun. The manufacturing method according to (9) above .

  According to the present invention, a flame retardant polyester fiber and a flame retardant having excellent flame resistance and light fastness can be obtained. In particular, by using ammonium polyphosphate, not only a resin composition excellent in flame retardancy can be obtained, but also the production process of flame retardant fibers and flame retardants, and even when incinerated, phosphine is generated. There is no safety.

  And it can color by mix | blending colorants, such as carbon black, with a resin composition, This can be used for a flame-retardant black curtain etc. as a fabric.

  In particular, when a flame retardant is blended with a polyester resin composition, fiberization often becomes difficult. However, in the present invention, by using a master batch of ammonium polyphosphate, the compatibility between polyester and ammonium polyphosphate is increased and stable. Can be obtained, and polyester fibers having excellent mechanical properties can be obtained.

  The present invention relates to a fiber obtained by melt spinning a flame retardant polyester resin composition containing ammonium polyphosphate and a thermoplastic polyester resin, wherein the polyester resin content is based on the fiber weight. 0.1 to 10% by mass and 99.9 to 90% by mass of a polyester resin.

  In the present invention, ammonium polyphosphate used as a flame retardant has the following general formula:

It is a compound represented by these. The decomposition temperature is defined as the temperature at which 5% weight loss occurs in DSC analysis. The flame retardant used in the present invention can exhibit high flame retardancy due to the synergistic effect of the phosphate ester group and the ammonium group. The decomposition temperature of the compound is 250 ° C. or higher, and particularly preferably 270 ° C. or higher. Although the upper limit of the decomposition temperature is not particularly limited, it is generally known that the decomposition temperature increases with the degree of polymerization n, and those having a high degree of polymerization are preferred. Accordingly, the highest polymerization degree that can be produced as the ammonium polyphosphate can be said to be the upper limit of the decomposition temperature. Further, when the degree of polymerization becomes high, it has cross-linking and branching. In the present invention, ammonium polyphosphate is usually used in the form of powder, and the average particle diameter of the powder is preferably 30 μm or less, and more preferably 10 μm or less. If the average particle size of the powder is 30 μm or less, ammonium polyphosphate can be mixed with the thermoplastic polyester resin as it is and dispersed uniformly. In this case, the smaller the particle size, the better the dispersibility. Therefore, the lower limit of the average powder particle size is not particularly limited. In the above powder, it is desirable that the particle size distribution is uniform below the average particle size, and the particle size distribution is narrow by using a sieve having a predetermined mesh size, for example, two mesh sizes, by sieving, etc. You may utilize what was adjusted to the thing with the same diameter. In addition, the reason why ammonium polyphosphate is used is that it is excellent in flame retardancy when added in a smaller amount than red phosphorus or phosphate ester.

  Next, the thermoplastic polyester resin used in the present invention will be described. There is no restriction | limiting in particular as a thermoplastic polyester resin used by this invention, Any polyester resin can be used regardless of the structural component, if it is thermoplastic. This is because the present invention has been found to be able to impart extremely excellent flame retardancy to polyester by blending ammonium polyphosphate. Therefore, the obtained flame-retardant polyester resin composition can be molded into a film, sheet, laminate, foam or the like, or molded into a desired shape by injection, blow inflation, or the like. However, it is particularly preferred that the resin composition can be spun into a fiber. This is because if it becomes a fiber, it can be subsequently formed into a fabric or felt, which is particularly easy to use as an interior material. For this reason, it is preferable that the polyester resin can be spun. Note that spinning is not limited to a wet type or a dry type. Moreover, the reason for limiting to the thermoplastic polyester resin is that the waste polyester can be reused if it is thermoplastic.

Examples of the dicarboxylic acid component constituting such a thermoplastic polyester resin include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, bis- ( 4-carboxyphenyl) sulfone Hong, bis (4-carboxyphenyl) ether, 1,2-bis (4-carboxyphenyl) ethane, 5-sodium sulfoisophthalic acid, diphenyl -p, p'-dicarboxylic acid, p- phenylenediamine Examples include diacetic acid, trans-hexahydroterephthalic acid, and alkyl esters, aryl esters, and ethylene glycol esters thereof. On the other hand, as glycol components, ethylene glycol, butylene glycol, 1,2-propylene glycol, 1,4-butanediol, trimethylene glycol, 1,6-hexanediol, 1,4-cyclohexanediol, neopentyl glycol 1,4-cyclohexanedimethanol, bisphenol A, bisphenol S and its ethylene glycol, polyethylene glycol adduct, diethylene glycol, polyethylene glycol and the like. In the present invention, the polyester resin composition can be used after being formed into a desired shape, but polyethylene glycol, polybutylene glycol, etc. are preferred particularly when spinning into fibers.

Moreover, in this invention, the discarded material after using as this thermoplastic polyester and the end material at the time of manufacturing an industrial product can also be utilized. In the present invention , the discarded polyester resin includes a wide range of polyester resins other than products, such as used polyester resins, pre-use but non-standard products, and not used as products. Examples of such waste polyester resin include synthetic resin manufacturers, film manufacturers, PET bottle manufacturing industries, polyester resins that are less than standard grades from polyester polymerization manufacturers, and polyester resins obtained by the General Waste Containers and Packaging Recycling Law. it can. This is because it is possible to material-recycle waste materials that should be discarded or subject to incineration.

  In the flame retardant polyester resin composition used in the present invention, all the flame retardant polyester resins may be such waste polyester resins. Rather, if all of the thermoplastic polyester resin has been used, the waste material can be used effectively as a raw material component, and it is not necessary to incinerate what is originally incinerated. It can contribute to conservation.

  In the flame-retardant polyester resin composition used in the present invention, ammonium polyphosphate is 0.1 to 10% by mass, more preferably 1 to 8% by mass, and plastic polyester resin 99.9 to 90% by mass, more preferably It is preferable that it is a flame-retardant polyester resin containing 99-92 mass%. This is because if the ammonium polyphosphate is less than 0.1% by mass, it is difficult to impart flame retardancy, while if it exceeds 10% by mass, it becomes difficult to perform spinning thereafter (in Table 1 described later). (See Comparative Example 4). That is, by blending ammonium polyphosphate in the above range into the resin composition, a fiber having excellent flame retardancy and excellent spinnability can be obtained.

  The resin composition used in the present invention may further contain 0.02 to 5 parts by weight of a colorant such as carbon black, and more preferably 0.5 to 3 parts by weight with respect to 100 parts by weight of the resin composition. Good. For example, light fastness can be imparted to the spun fiber by blending carbon black as a colorant. In particular, when used in automobile interior materials as a flame retardant, light resistance is an extremely important factor because it is always subject to deterioration by light. In the present invention, it has been found that blending carbon black can prevent the flame-retardant fiber from fading and at the same time impart light fastness to the fiber itself. Further, by coloring with carbon black, for example, it can be used as a dark curtain for light shielding. In addition, a colorant can be used instead of or in combination with carbon black depending on the specification application. By using a colorant, the fibers can be colored. The reason why the preferable amount of the colorant such as carbon black is 0.02 part by weight or more is that if it is less than this, the coloring becomes insufficient. On the other hand, the reason why it is 5 parts by weight or less is that even if it exceeds this, the target coloring level does not change, but rather, subsequent spinning becomes difficult. Examples of colorants other than carbon black include azo, anthraquinone, quinacridone, cyanine green, titanium yellow, phthalocyanine, α-type phthalocyanine, β-type phthalocyanine, perinone, berylene, polyazo, ultramarine, synthetic metal compounds, iron oxide , Petal, titanium oxide, anatase titanium oxide, rutile titanium oxide, a mixture of these colorants, dioxazine, and the like, and the flame-retardant fiber can be colored as desired depending on the type of the colorant.

  In the flame-retardant polyester resin composition used in the present invention, the ratio of ammonium polyphosphate and the thermoplastic polyester resin should satisfy the above-mentioned ratio with respect to the total amount of 100% by mass. Colorants, or other additives in addition to these may also be included. Such additives include retarders such as calcium carbonate and talc, other flame retardants such as aluminum hydroxide, magnesium hydroxide, antimony oxide, sodium carbonate and mixtures thereof, phthalates, phosphates, fats There are plasticizers such as aromatic carboxylic acids, stabilizers such as inorganic salts and metal soaps, antioxidants such as alkylphenols and alkylenebisphenols, ultraviolet absorbers such as salicylic acid esters, benzotriazoles, and hydroxybenzophenones.

  In the flame-retardant polyester resin composition used in the present invention, it is preferable to use antimony oxide or aluminum hydroxide in combination because flame retardancy can be increased. These compounding amounts are 0.1 to 5 parts by weight of aluminum hydroxide or antimony oxide, more preferably 0.1 to 4 parts by weight, and particularly 0.1 to 3 parts by weight to 100 parts by weight of the resin composition of the present invention. You may contain a weight part. When the amount is less than 0.1 parts by weight, the combined effect is not exhibited. On the other hand, when the amount exceeds 5 parts by weight, the flame retardancy does not change, and on the other hand, spinning becomes difficult.

  In order to prepare the resin composition used in the present invention, it is preferable to use a master batch of ammonium polyphosphate as a flame retardant. For example, a masterbatch containing ammonium polyphosphate is prepared in advance on a masterbatch substrate, and a thermoplastic polyester resin is mixed and melted therein. In addition, when a colorant such as carbon black is included in the resin composition, a masterbatch containing ammonium polyphosphate in advance and a masterbatch containing a colorant such as thermoplastic polyester resin and carbon black are prepared. And mix both. It is not necessary to adopt a special method for melt mixing the masterbatch and the polyester resin. For example, each chip before melting may be melted after mixing, or both may be melted separately and then statically mixed using a static mixer or the like immediately before spinning.

  In addition, when using a masterbatch, it is preferable to contain ammonium polyphosphate 5-40 mass% in this masterbatch, More preferably, it is 10-30 mass%. If the amount is less than 5% by mass, the amount of ammonium polyphosphate is small and the significance of using the masterbatch is lessened. On the other hand, if the amount exceeds 40% by mass, the preparation of the masterbatch itself becomes difficult. The resin used in the masterbatch can be used without particular limitation as long as it is a thermoplastic resin and does not lose the properties of the resin composition after being blended in the polyester resin composition, and most preferably It is a plastic polyester resin, and includes a polyethylene terephthalate-based polyester and a polybutylene terephthalate-based polyester as main components. In addition, such a master batch can use a commercial item.

  The master batch of a colorant such as carbon black contains 5 to 60% by mass, more preferably 10 to 35% by mass, particularly 20 to 30% by mass of a colorant such as carbon black in the master batch. It is. If the amount is less than 5% by mass, the amount of the colorant such as carbon black is small and a desired color cannot be obtained. On the other hand, if the amount exceeds 60% by mass, the colorant such as carbon black may be mixed uniformly. Because it becomes difficult.

  In this case, polyethylene terephthalate-based polyester is preferable as the resin for blending the colorant such as carbon black in the master batch. This polyester is particularly preferably one in which 5 to 20 mol% of isophthalic acid is copolymerized based on the total acid components constituting the polyester. When the copolymerization ratio of isophthalic acid is less than 5 mol%, it is not preferable because the physical properties of the resulting fiber may be deteriorated and troubles such as yarn breakage during yarn production may be increased. On the other hand, when the copolymerization ratio of isophthalic acid exceeds 20 mol%, the physical properties of the resulting yarn are deteriorated and colored spots are likely to occur, which is not preferable. The polyethylene terephthalate copolymer polyester may be further copolymerized with a copolymer component other than the isophthalic acid component in a range of 5 mol% or less based on the total acid component. As examples, adipic acid, sebacic acid, naphthalene dicarboxylic acid, phthalic acid, and glycol components include propylene glycol, butylene glycol, diethylene glycol, and the like. When such a masterbatch is used, the colorant such as carbon black is pre-dispersed in the isophthalic acid copolymer polyethylene terephthalate, so the periphery of the colorant such as carbon black is mainly surrounded by the isophthalic acid copolymer polyethylene terephthalate. Structure. As a result, polyethylene terephthalate does not have much thickening effect due to colorants such as carbon black, while isophthalic acid copolyester has a thickening effect due to the thinning effect of isophthalic acid component. As a whole, the drip effect is improved and the flameproof performance is improved. However, in this invention, when using a masterbatch, it is not restricted to such resin, Any can be used if it does not impair the characteristic of the target resin composition. In addition, when mix | blending another additive, it can mix in this resin composition by a well-known method.

  The present invention is a fiber obtained by melt spinning the flame retardant polyester resin composition described above, wherein the polyester resin content is 0.1 to 10% by mass of ammonium polyphosphate, carbon based on the fiber weight. It is a flame-retardant fiber characterized by containing 0.02 to 5% by mass of a colorant such as black and 99.88 to 85% by mass of a polyester resin.

  The flame-retardant fiber can be obtained by fiberizing the resin composition by a known melt spinning method. The cross-sectional shape in that case is arbitrary and any of a round cross-section fiber, an irregular cross-section fiber, and a hollow fiber may be sufficient.

  In addition, in the flame retardant fiber, the ammonium polyphosphate is 0.1% by mass or more, less than this, when the flame retardant is prepared by blending ammonium polyphosphate and the like, less flame retardant effect, On the other hand, the reason why the amount is set to 10% by mass or less is that if the amount exceeds this, the amount of ammonium polyphosphate is too large, resulting in increased yarn breakage and lack of fiber properties. Similarly, the reason why the colorant such as carbon black is 0.02 part by weight or more is that if it is less than this, the coloring becomes insufficient. On the other hand, the reason why the colorant such as carbon black is 5% by mass or less is that the thread breakage increases even if the content exceeds 5% by mass, and there is no difference in imparting light fastness. That is, the flame-retardant fiber of the present invention reduces the addition amount of the flame retardant and imparts light fastness by blending a colorant such as carbon black, and at the same time, fiberized without impairing the mechanical properties of the polyester fiber. It is a flame retardant fiber.

The flame retardant fiber of the present invention thus obtained is used as a fiber cotton such as a short fiber or a filament, or the fiber cotton is simply compressed and used as a felt, or used as a flame retardant filler as it is. Can do. Under the present circumstances, it is preferable that the thickness of the flame-retardant fiber of this invention is 1.0-660 dtex, More preferably, it is 3.3-330 dtex, Most preferably, it is 5.0-17.0 dtex. . If the thickness is less than 1.0 dtex, yarn breakage may occur. On the other hand, if the thickness exceeds 660 dtex, it is difficult to process due to rigidity. Such short fibers or filaments may be used alone or in combination with other fibers to be woven or knitted by a conventionally known method to form a fabric. For example, a satin weave using a flame retardant fiber yarn as a weft and a normal white polyester drawn yarn as a warp, or a double weave with a flame retardant fiber yarn arranged on one side may be used as a fabric. Good.

  The second of the present invention is a flame retardant containing 5 to 100% by mass of the flame retardant fiber. As a flame retardant, it can be prepared using the above flame retardant fiber, felt, cloth, fiber cotton, or the like. At this time, it is preferable that the flame retardant material contains 5 to 100% by mass, more preferably 10 to 50% by mass, particularly 15 to 30% by mass of the flame retardant fiber. Since the flame-retardant fiber of the present invention has a large flame-retardant effect, it can be effectively used as a flame-retardant material when it contains at least 5% by mass. Therefore, it can be blended with the conventional member to impart flame retardancy, and since the blending amount is small, the product price can be reduced, and the flame retardant effect can be achieved without impairing the texture of the conventional member. Can be granted.

  Flame retardant materials containing such flame retardant fibers include, for example, sheets used for automobile interiors, linings such as pyraganish and rear parcels, floor linings such as mats and carpets, sun visors, package trays, assist grips In addition, it can be used as a heat insulating material, various sound insulating materials, and a vibration insulating material.

  In the third aspect of the present invention, (1) a masterbatch containing ammonium polyphosphate having a decomposition temperature of 270 ° C. or higher, a thermoplastic polyester resin, and a masterbatch containing a colorant such as carbon black are melt-mixed, A method for producing a flame-retardant polyester fiber characterized by melt spinning, and (2) a masterbatch containing a colorant such as carbon black, ammonium polyphosphate having a decomposition temperature of 270 ° C. or higher, and a thermoplastic polyester resin And flame spinning, and then melt spinning.

  Originally, it is difficult to add an inorganic compound to a polyester resin and spin it into a fiber. Particularly, since the compatibility between the polyester resin and the inorganic compound is insufficient, yarn breakage or the like is likely to occur. However, in the present invention, by using a master batch, the additive can be uniformly melted simply by melt mixing, and as a result, spinning can be performed without breaking the yarn. The melt mixing using this master batch is the same method as described above in the preparation of the resin composition of the present invention. For melt spinning itself, a conventionally known spinning method can be employed. Rather, it is characterized in that the conventional melt spinning method can be employed as it is while compounding ammonium polyphosphate.

  Hereinafter, examples of the present invention will be described in detail.

(Examples 1-5 and Comparative Examples 3-4)
A master containing ammonium polyphosphate 1 (Pekoflam TC 204 powder (average particle size 8 μm) manufactured by Clariant Japan KK, P content 31.5%, N content 14.5%, polymerization degree 1000, decomposition temperature 270 ° C. or higher) The batch and a polyethylene terephthalate resin (trade name “NOVAPEX” manufactured by Mitsubishi Chemical Corporation) are melt-mixed with an extruder, and the flame-retardant polyester resin composition (resins 1 to 5 and comparative resin) in the ratio shown in Table 1 3-4) were obtained respectively. Next, these were melt-spun by a dry method at a take-up speed of 520 m / min and a temperature of 240 to 270 ° C., and 6.6 decitex flame-retardant staple (combustible fiber 1 to 5 and comparative flame-retardant fiber ratio 3) Got. As for Comparative Resin 4, as shown in Comparative Example 4 in Table 1, melt spinning was performed at a take-up speed of 520 m / min and a temperature of 240 to 270 ° C. by a dry method similar to the above, but spinning could not be performed. It was not possible to obtain flammable staples. Moreover, as for the master batch containing the said ammonium polyphosphate 1, what mixed 30 mass% of ammonium polyphosphate 1 was used for any Example and comparative example. Further, a polyethylene terephthalate resin (manufactured by Mitsubishi Chemical Corporation, trade name “NOVAPEX”) was used as the resin of this master batch.

  With respect to the flame retardant fibers 1 to 5 of Examples 1 to 5 thus obtained and the comparative flame retardant fiber ratio 3 of Comparative Example 3, flame retardancy, light resistance and mechanical properties (strength and elongation) were examined. . The results are shown in Table 1. The measurement of flame retardancy, light resistance and mechanical properties (strength and elongation) were as follows.

  (1) Flame retardancy was measured according to the method described in JP-A-2001-279073. A flame retardant fiber or a flame retardant obtained in advance was used in a constant temperature dryer at 170 ± 2 ° C. for 10 minutes.

  As a test piece, 10 g of flame-retardant cotton loosened in a 150 mm × 100 mm × 20 mm stainless steel basket so that the entire surface is uniform and the fiber direction is constant in the vertical direction was placed. When packed, the surface was lightly applied and flattened with a drier so that fiber cotton did not come out of the outer shape, and used as a test piece. This test piece was fixed horizontally at a position of 252 mm from the installation base so that the lid side of the test piece was down. The mesh is made of 0.2 to 0.4 mmφ aluminum wire knitted into 18 mesh, and the upper lid is made by opening two 65 mm × 80 mm windows side by side.

  The fire source was Chukkaman (Vesta Chukkaman Tokai Co., Ltd.) with sufficient fuel, the flame length was 50 mm, and the distance from the ignition port to the test piece was 20 mm.

  The test piece was ignited at almost the center, and after ignition, the air around the fire source was kept calm and left until combustion was completed. A flame was applied to the test piece for 10 seconds to observe how it burned. The average time (seconds) from ignition to ignition (seconds), the average time (seconds: afterflame average time) and maximum time after ignition (seconds: maximum afterflame time), and the maximum char length (Mm) was measured and evaluated. Five test pieces were used for one sample, and each test piece was evaluated at two points. Therefore, the average is an average of 10 measurements, and the maximum is a maximum value of 10 measurements.

(2) light resistance is room temperature, then it was allowed to stand for 24 hours with a mercury lamp 15cm, a Delta] E ^* ab value was measured with CM-3600d (manufactured by Konica Minolta). Further, the light fastness was shown by JIS L0842 (-1996) “ultraviolet carbon arc lamp (third exposure method)” after 40 hours of irradiation. The number of tests was 3.

  (3) Mechanical properties (strength and elongation) were measured with a desktop material testing machine STA-1150 (manufactured by Orientec Co., Ltd.). Ten measurements were made on one sample.

(Examples 6 to 8)
Ammonium polyphosphate 1 (Pekoflam TC 204 powder (average particle size 8 μm) manufactured by Clariant Japan KK, P content 31.5 ± 0.5%, N content 14.5 ± 0.5%, polymerization degree 1000, decomposition A masterbatch containing 270 ° C. or more), a masterbatch in which 35% by mass of carbon black is blended in polyester, and a polyethylene terephthalate resin (trade name “NOVAPEX” manufactured by Mitsubishi Chemical Corporation) are melt-mixed with an extruder. Thus, flame retardant polyester resin compositions (resins 6 to 8) having the ratios shown in Table 1 were obtained. Subsequently, these are melt-spun by a dry method at a take-up speed of 520 m / min and a temperature of 240 to 270 ° C. to obtain a flame-retardant staple (flame-retardant fibers 6 to 8) having a single yarn of 6.6 dtex and an L value of 10 to 20 It was. In addition, as for the masterbatch containing the said ammonium polyphosphate 1, what mixed 30 mass% of ammonium polyphosphate 1 was used for all the Examples. Further, a polyethylene terephthalate resin (manufactured by Mitsubishi Chemical Corporation, trade name “NOVAPEX”) was used as the resin of this master batch. Polyethylene terephthalate resin (trade name “NOVAPEX” manufactured by Mitsubishi Chemical Corporation) was used for the master batch polyester containing 35% by mass of carbon black.

  The flame retardant fibers 6 to 8 of Examples 6 to 8 thus obtained were evaluated for flame retardancy, light resistance, and mechanical properties in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
Instead of ammonium polyphosphate 1, the same procedure as in Example 3 was used except that ammonium polyphosphate 2 (fire cut P-760; (average particle size 8 μm)) manufactured by Suzuhiro Chemical Co., Ltd. having a decomposition temperature of 250 ° C. was used. A flame retardant staple (comparative flame retardant fiber ratio 1) was obtained.

  The comparative flame retardant fiber ratio 1 of Comparative Example 1 thus obtained was evaluated in the same manner as in Example 1 for flame retardancy, light resistance and mechanical properties. The results are shown in Table 1.

(Comparative Example 2)
Only polyethylene terephthalate resin (trade name “NOVAPEX” manufactured by Mitsubishi Chemical Corporation) is melt-spun at a take-off speed of 520 m / min and a temperature of 240 to 270 ° C. by a dry process, and a single-fiber 6.6 dtex flame-retardant staple (comparison) A flame retardant fiber ratio 2) was obtained.

  With respect to the comparative flame retardant fiber ratio 2 of Comparative Example 2 thus obtained, the flame retardancy, light resistance and mechanical properties were evaluated in the same manner as in Example 1. The results are shown in Table 1.

Example 9
Flame retardant cotton obtained by blending the flame retardant fibers 1, 4 and 6 obtained in Examples 1, 4 and 6 with flame retardant processed untreated fibers (indicated in the table as untreated fibers) in the proportions shown in Table 2. Were prepared as flame retardants 1-4. These flame retardancy was investigated. In addition, a flame-retardant processed untreated fiber is an untreated fiber which spun the polyester resin composition prepared like Example 4 except not containing ammonium polyphosphate as a polyester resin composition. For the flame retardancy of flame retardant materials 1 to 4 (flame retardant cotton), the same method as in Example 1 was adopted. The results are shown in Table 2.

  Moreover, in Table 2, using the comparative flame retardant fiber 1, the comparative flame retardant fiber 2 and the comparative flame retardant fiber 3, which are commercially available flame retardant fibers, flame retardant cotton is applied according to the above flame retardant material 1. It prepares and is set as the comparative flame retardant 1-3, and the result of having investigated these flame retardances is shown collectively. The flame retardant used in these comparative flame retardant fibers 1 to 3 is a comparative flame retardant fiber 1: 8% by mass of a bromo flame retardant (trade name “Frame Cut 110R”, component decabromodiphenyl ether, manufactured by Tosoh Corporation). The flame retardant bromide (made by Tosoh Corporation, trade name “Frame Cut 610R”, component antimony trioxide) 3% by mass and polyethylene terephthalate 89% by mass. Comparative flame retardant fiber 2 is manufactured by Teijin Limited. The trade name “Trevira” and the comparative flame retardant fiber 3 are the product name “Heim” manufactured by Toyobo Co., Ltd.

  In addition, the flame retardant fibers obtained in Comparative Flame Retardant Fibers 1 to 3 and Comparative Examples 1 to 3 (Comparative Flame Retardant Fiber Ratios 1 to 3), the ratio of the flame retardant processed untreated fibers shown in Table 2 The flame retardant cotton was prepared according to the flame retardant 1 described above, and these flame retardant properties were examined as comparative flame retardants 4 to 9, and the results are shown in Table 2. For the flame retardancy, the same method as in Example 1 was adopted.

Claims (10)

The flame-retardant polyester resin composition containing ammonium polyphosphate and a thermoplastic polyester resin, a fiber obtained by melt spinning, from 0.1 to 10 wt%, respectively ammonium polyphosphate, based on the fiber維重amount, Containing 99.9 to 90% by mass of a polyester resin ,
The flame retardant fiber, wherein the fiber has a thickness of 1.0 to 17.0 dtex . The flame-retardant fiber according to claim 1, wherein the ammonium polyphosphate is a powder having an average particle size of 30 μm or less . The flame-retardant fiber according to claim 1 or 2 , wherein the decomposition temperature of ammonium polyphosphate is 270 ° C or higher. The flame-retardant fiber according to any one of claims 1 to 3 , which is a fiber obtained by melt spinning at a take-up speed of 350 to 1000 m / min and a spinning temperature of 200 to 300 ° C by a dry method. The flame retardant polyester resin composition further contains a colorant, 0.1 to 10% by mass of ammonium polyphosphate, 0.02 to 5% by mass of colorant , and 99% of polyester resin based on the fiber weight. The flame retardant fiber according to any one of claims 1 to 4 , wherein the flame retardant fiber is contained in an amount of .88 to 85% by mass. The flame retardant fiber according to claim 5 , wherein the colorant is carbon black. It claims 1 to flame retardants containing 5 to 100 wt% of the flame-retardant fiber according to 6. The flame-retardant material according to claim 7 , which is used as an automobile interior material. The flame retardant according to any one of claims 1 to 6, wherein a masterbatch containing ammonium polyphosphate and a masterbatch base material and a thermoplastic polyester resin are melt-mixed and then melt-spun. For producing a conductive fiber . A masterbatch containing ammonium polyphosphate and a masterbatch substrate, a masterbatch containing a colorant and a masterbatch substrate, and a thermoplastic polyester resin are melt-mixed and then melt-spun. Item 10. The manufacturing method according to Item 9 .