FLAMEPROOFING SYNTHETIC FIBER

Abstract: Disclosed is a flameproofing synthetic fiber comprising a halogenated cycloalkane and at least one member select­ ed from phosphorus compounds represented by the follow­ ing general formulae (I) through (IV): According to the present invention, the flameproofing synthetic fiber which is excellent in flameproofing property and feeling and significantly improved in spinning property and corrosion protective property can be provided. Further­ more, the foaming during operation and the passing pro­ cessability through a stuffing crimper are also extremely improved.

Description: BACKGROUND OF THE INVENTION (1) Field of the Invention The present invention relates to a flameproofed synthetic fiber, comprising a synthetic fiber, a halogenated cycloalkane (A) and a phosphorus compound (B). (2) Description of the Prior Art Various methods for providing flameproofed synthetic fibers by applying flameproofing agents to the synthetic fibers have conventionally been proposed. Particularly, U.S. Pat. No. 4,116,702 discloses that a flameproofed synthetic fiber treated with a flameproofing agent which contains a brominated cycloalkane having 7 to 12 ring-constituent carbon atoms and 4 to 6 bromine atoms attached to the ring-constituent carbon atoms, a dispersant such as a lignin sulfonate, a protective colloid and water has an excellent flameproofing property. Further, Japanese Patent Application Laid-open No. 36032/1984 describes a flameproofing agent prepared by dispersing a polybrominated organic compound such as a brominated cycloalkane in water without use of any dispersant, for the purposes of further enhancement of a flameproofing effect, and prevention of lowering of color fastness, discoloration on high temperature treatments, corrosion of metals and the like. However, the above-mentioned halogenated cycloalkane compounds (hereinafter referred to as HCA for brevity) have a serious disadvantage that they corrode metals of HCA applying apparatus employed in the procedure of synthetic fiber manufacturing and apparatus for after-treatment of the synthetic fibers applied with HCA, such as heat-treatment apparatus, cutters, packaging apparatus, spinning machines and so on. Further, aqueous dispersions of HCA have a disadvantage that they extremely deteriorate the passing processability through crimping apparatus such as stuffing crimpers, when they are applied prior to the crimping treatment in the procedure of synthetic fiber manufacturing, because they have a function for increasing the frictional coefficient. Thus, the function for increasing the frictional coefficient causes various troubles such as the inferior passing processability of the fibers through cards, clogging induced by the fibers in coiler tubes and the like, also in the spinning process in which the synthetic fibers are converted to the spun yarns. Furthermore, there are problems in that remarkable forming in the aqueous dispersion causes deterioration of the workability and a large amount of white powder is produced in the spinning process. On the other hand, Japanese Patent Publication No. 22958/1974 discloses a flameproofing polyester containing a phosphate represented by the following general formula: wherein each of R₁, R₂ and R₃, which may be the same or different, is a substituted or unsubstituted aryl, alkyl or cycloalkyl group. DE-B-2 001 125 discloses a flameproofed synthetic fiber containing halogenated cycloalkane compound, preferably a brominated aliphatic or cycloaliphatic compound for example hexabromodicyclopentadiene, or tetrabromodicyclopentadiene and phosphorus compounds, i.e. triphenylphosphate. The US-A-3 974 310 relates to a process for the preparation of flame-retardant agents for synthetic materials containing halogenated aromatic compounds preferably brominated biphenyl, tetraphenyl, benzoic derivatives, polybrominated aromatic mono- and polyacids, anhydrides or esters of benzene. The particles of the brominated aromatic compounds are reduced to the optimum size dispersed in water and after the addition of strong surface active agents to effect a uniform and thorough wetting of the flame-retardant particles, the resulting dispersion is stabilized by adding small quantities of a protective colloid, for example carboxymethylcellulose or methoxycellulose, to achieve an optimum viscosity. The US-A-4 116 702 deals with flame-proofing agents containing brominated cycloalkenes with 7 to 12 ring carbon atoms and 4 to 6 bromine atoms bonded to these ring carbon atoms, a dispersant for preventing a rapid sedimentation of the cycloalkane compound and optionally protective colloids. From the DE-C-2 646 218 flame-retardants are known comprising phosphonic acid derivatives having hydrocarbon groups of 1 to 10 carbon atoms or/and halogen atoms as substituents. It is possible according to the prior technical teaching to polymerize these phosphorus compounds into linear polyester without escaping remarkable amounts of these phosphorus components from the polymerization system. Furtheron said flame-retardant agents used in molding articles prevent secondary conversions, i.e. gelling reactions caused by the thermal decomposition of the phosphorus compounds during the polycondensation reaction, and prevent lowering of color fastness of the polyester articles. The DE-B-2 454 189 covers a method for producing flame-retardant linear polyester by using cyclic anhydrides or phosphorus compounds after prior solubilizing the anhydrides in diols. Further, Japanese Patent Application Laid-open No. 56488/1975 and Japanese Patent Application Laid-open No. 82392/1976 disclose a flameretardant polyester including a phosphorus compound represented by the following general formula: wherein R₄ is a saturated, open-chain or cyclic alkylene, arylene or aralkylene group, and R₅ is an alkyl, aryl or aralkyl group having 6 or less carbon atoms. Japanese Patent Application No. 47891/1977 also describes a flameresistant polyester containing a phosphorus compound represented by the following general formula: wherein R₆ is a monovalent, ester-forming functional group, each of R₇ and R₈, which may be the same or different, is a hydrocarbon group having 1 to 10 carbon atoms or R₆, A is a divalent or trivalent organic group, n₁ is an integer of 1 or 2, and each of n₂ and n₃ is an integer of 0 to 4. When the phosphorus compounds described above are contained in the polyesters, improvement of the flameproofing property is found, but its extent is insufficient. Therefore, further improvement of the flameproofing property has been requested. The primary object of the present invention is to provide a flameproofed synthetic fiber excellent in feeling and flameproofing property, overcoming the disadvantages described above, namely, improving the workability, processability and spinning property in the procedure of synthetic fiber manufacturing and further reducing corrosion of the apparatus. The object of the present invention is a flameproofed synthetic fiber comprising a synthetic fiber, a halogenated cycloalkane compound (A) and a phosphorus compound (B) which is characterized in that said phosphorus compound (B) is a phosphorus compound represented by the following general formula (I) wherein R is an alkyl group having 6 to 30 carbon atoms on an average, each of M and M', which may be the same or different, is an alkali metal, and n is an integer of 0 to 30; wherein said halogenated cycloalkane compound (A) and said phosphorus compound (B) of the general formula (I) are applied to said synthetic fiber in a total amount of 0.5 to 7% by weight based on the weight of said synthetic fiber, and the ratio of said halogenated cycloalkane compound (A) to said phosphorus compound (B) of the general formula (I) is in the range of 70:30 to 98:2. DESCRIPTION OF THE PREFERRED EMBODIMENTS As the synthetic fiber used in the present invention, there can be mentioned known synthetic fibers such as polyester fibers, polyamide fibers, polyacrylonitrile fibers, polyolefin fibers and polyvinyl chloride fibers. Particularly, in the case of the polyester fibers, the preferred results can be obtained in durable flameproofing property and feeling. The fibers may be in staple form or in continuous filament form. In particular, the fibers in staple form provide excellent effects. The fiber cross section may take any shapes such as circular hollow, noncircular solid and noncircular hollow shapes, without being limited to circular solid shape. As examples of HCA (A) applied to the synthetic fiber of the present invention, there can be mentioned 1,2,3,4,5,6-hexabromocycloheptane, 1,2,3,4-tetrabromocyclooctane, 1,2,4,6-tetrabromocyclooctane, and 1,2,5,6,9,10-hexabromocyclododecane. Particularly, in the case of the polyester fiber, 1,2,5,6,9,10-hexabromocyclododecane is preferably used, because the excellent adhesive fastness of the flameproofing agent to the fiber, the excellent flameproofing property and feeling can be obtained. Since HCA is a solid insoluble in water, it is dissolved in a solvent such as perchloroethylene or toluene, or dispersed in water for use. When an aqueous dispersion of HCA is prepared, HCA is ground in such a manner that the particles have an average diameter of less than 1µm, and then stirred for mixing with water and a protective colloid in a ball mill and the like for several hours. Thus, the aqueous dispersion excellent in dispersion stability can be obtained. The particles of HCA are preferable to be less than 1µm in average diameter, in terms of the dispersion stability of the aqueous dispersion, the adhesive efficiency and adhesive fastness of the flameproofing agent to the fiber. The protective colloid is exemplified by polyvinyl alcohol, polyvinyl pyrrolidine, methyl cellulose, carboxymethyl cellulose, hydroxyethyl or hydroxypropyl cellulose, gelatins, acid casein, starch paste or polymers of monomers of the acrylic acid series, for example polyacrylic acid, ethyl acrylate or methylmethacrylate copolymers. Good results are obtained above all with polyvinyl alcohol, hydroxyethyl cellulose and, especially, with carboxymethyl cellulose. Considering the flameproofing property, feeling and spinning property of the fibers, an amount of the protective colloid used in the aqueous dispersion is desirable to be minimized. The protective colloid is preferable to be used in an amount of not more than 1% by weight, based on the weight of HCA. In the present invention, a phosphorus compound (B) represented by the formula (I) is used together with the foregoing HCA (A), and preferably the foregoing phosphorus compound (B) is applied to the synthetic fiber, and/or blended in the polymer constituting the synthetic fiber or copolymerized therewith. Particularly, it is preferable that the phosphorus compound (B) represented by the formula (I) is applied to the synthetic fiber by dipping the synthetic fiber in the liquor containing HCA (A) and the phosphorus compound (B) represented by the formula (I) as will be hereinafter described. In the foregoing general formula (I) representing the phosphorus compound (B), R is an alkyl group having 6 to 30 carbon atoms on an average, each of M and M' which may be the same or different, is an alkali metal, and n is an integer of 0 to 30. If the average carbon number of R is less than 6, the heat resistance of the fiber is deteriorated and the frictional resistance between fibers after the heat-set treatment is too increased. Therefore, such a compound is unsuitable. On the other hand, if the average carbon number of R exceeds 30, the foaming induced at the treating bath in drawing process can not be prevented to cause deterioration of the workability. Particularly, the average carbon number of R is preferable to be in the range of 8 to 20. Further, if the mole number n of added ethylene oxide exceeds 30, the heat resistance of the fiber is deteriorated and the frictional resistance between fibers after the heat-set treatment is too increased. Therefore, such a compound is unsuitable. Also when ethylene oxide is not added, namely, when n equals 0, the effects of the present invention can be achieved. However, it is preferable that ethylene oxide is added, because the dispersibility of the phosphorus compound represented by the formula (I) is maintained and the foaming induced in the treating bath during operation is reduced. The mole number of added ethylene oxide is particularly desirable to be in the range of 1 to 20. Such a phosphorus compound (B) can be obtained by reacting with phosphoric anhydride a higher alkyl alcohol wherein the average carbon number of the alkyl group is in the range of 6 to 30 or an alkyl ether prepared by adding thereto not more than 30 moles of ethylene oxide. In this case, a phosphoric ester or its salt having an acid value of 0 to 70, preferably, 0 to 50 is favorably used, which is prepared by neutralizing an acidic phosphoric ester having a degree of phosphoration (the gram-atom number of phosphorus atoms attached to 1 mole of an alcohol) of 0.2 to 2.0 with an inorganic alkali hydroxide. As the higher alkyl alcohol wherein the average carbon number of the alkyl group is in the range of 6 to 30, there can be mentioned, for example, octyl alcohol, decyl alcohol, dodecyl alcohol, tetradecyl alcohol, hexadecyl alcohol, octadecyl alcohol and docosa alcohol. These alcohols may be used alone, respectively, or as mixtures thereof. Further, the alcohol may be straight-chain or branched-chain, and saturated and/or unsaturated. Polyoxyethylene alkyl ether is exemplified by POE (2 moles) octyl ether, POE (7 moles) octyl ether, POE (2 moles) nonyl or isononyl ether, POE (7 moles) nonyl or isononyl ether, POE (10 moles) nonyl or isononyl ether, POE (7 moles) dodecyl ether, POE (12 moles) dodecyl ether, POE (5 moles) hexadecyl ether and POE (10 moles) hexadecyl ether and so on. If the acid value of the foregoing phosphorus compound (B) is too high, it is observed that the antistatic property and the heat resistance of the fiber tend to decrease. If the degree of phosphoration is too high, the inorganic phosphate increases to cause the high frictional resistance between fibers. On the other hand, if the degree of phosphoration is too low, a large amount of the unreacted alcohol or polyoxyethylene alkyl ether remains in the reaction mixture. The alkali hydroxide used in neutralization includes hydroxides of alkali metals such as lithium, sodium and potassium. In terms of the antistatic property, potassium hydroxide is particularly preferred. The flameproofed synthetic fiber of the present invention has HCA (A) and the phosphorus compound (B) represented by the general formula (I) deposited thereon in an amount of 0.5 to 7.0% by weight, preferably, 1.5 to 4.0% by weight, based on the weight of the synthetic fiber. If the amount of HCA (A) and the phosphorus compound (B) is too small, the flameproofing property becomes insufficient. On the other hand, if the amount thereof is too large, it is observed that white powders are produced to tend to deteriorate the spinning property of the fiber. The ratio of HCA (A) to the phosphorus compound (B) represented by the general formula (I) is in the range of 70:30 to 98:2. Too little phosphorus compound tends to lower the corrosion preventive effect and to deteriorate the passing processability through a stuffing crimper and the spinning property. On the contrary, too much phosphorus compound is liable to cause remarkable foaming in the treating bath and detrioration of compatibility with the aqueous dispersion of HCA (A), because the phosphorus compound (B) does not act as a dispersant for HCA (A). The flameproofing synthetic fiber of the present invention is desirable to be crimped for the purpose of improvement of the spinning property. It is preferable that the number of crimps is 10 to 18 crimps per 25mm of the fiber, particularly 12 to 15 crimps per 25mm of the fiber, and the percentage crimp is 8 to 38%, particularly 10 to 20%. The crimps may be not only planar, but also three-dimensional in shape, as obtained by the conjugate spinning process, the unsymmetrical cooling spinning process or the like. For producing the flameproofing synthetic fiber of the present invention by the combination of HCA (A) and the phosphorus compound (B) represented by the foregoing general formula (I), the synthetic fiber may be treated with the aqueous dispersion containing HCA (A) and the phosphorus compound (B) above described, prior to the crimping in the procedure of synthetic fiber manufacturing. The aqueous dispersion may be applied to the synthetic fiber in the undrawn state immediately after the melt spinning or in the state after the drawing, so long as it is applied prior to the crimping. The aqueous dispersion is preferable to be applied to the synthetic fiber, while the synthetic fiber is still in the undrawn state, because HCA (A) sufficiently penetrates into the inside of the synthetic fiber so as to be favorably prevented from the elimination in the spinning, dying and weaving processes. The phosphorus compound (B) can be incorporated in the synthetic polymer in any step. For example, in the case that the phosphorus compound (B) is copolymerized with the polyester, the phosphorus compound (B) may be added on the ester interchange reaction, after the ester interchange reaction and before the condensation polymerization reaction, or in a relatively early stage of the condensation polymerization reaction. Further, in the case that the phosphorus compound (B) is blended in the synthetic polymer, the phosphorus compound (B) is added after the conclusion of the polymerization reaction and before the melt spinning. The melt spinning of the synthetic polymer containing the phosphorus compound (B) can be conducted in the usual way. The synthetic fiber thus obtained is treated with the aqueous dispersion containing HCA (A). This aqueous dispersion may be applied to the synthetic fiber in an arbitrary stage, but is preferable to be applied thereto, while the synthetic fiber is still in the undrawn state, as is the case with the foregoing aqueous dipspersion containing HCA (A) and the phosphorus compound (B) represented by the general formula (I). When the phosphorus compound (B) represented by the general formula (I) is used together with HCA (A) in the aqueous dispersion, the foaming induced in the treating bath is depressed, and the corrosion preventive property, the passing processability through a stuffing crimper and the spinning property are also highly improved. The aqueous dispersion containing HCA (A) may contain an ultraviolet absorbent such as a compound of the benzotriazole series so far as the object of the present invention is not failed to be achieved. Flameproofing agents other than HCA can also be used therewith to such an extent that the spinning property, feeling and the like of the synthetic fiber are not inhibited. When the treating bath is liable to foam, a slight amount of antifoaming agent can be used therewith so far as the flameproofing property is not impaired. Further, after the aqueous dispersion of HCA is applied on the synthetic fiber, dried, fixed by heating and then washed with water at need, another oiling agent for enhancing the spinning property can be applied to the synthetic fiber by the spray method, the padding method and the like, if necessary. The aqueous dispersion containing HCA can be applied to the synthetic fiber by any conventional method, for example, by dipping, padding, spraying or oiling roller coating. The synthetic fiber treated with the aqueous dispersion containing HCA (A) is heat treated at a temperature of at least 130°C, preferably at least 155°C, for at least 30 seconds, preferably at least 10 minutes, thereby HCA (A) being allowed to penetrate into the inside of the synthetic fiber. This heat treatment may also be used for the heat treatment to set the crimps. The present invention will now be described in detail with reference to the following examples. In the following examples, the add-on of the treating agent on the synthetic fiber, the flameproofing property, the adhesive fastness of HCA to the synthetic fiber, the spinning property, the feeling, the stability of the treating liquor, the foaming during operation, the passing processability through a stuffing crimper, the corrosion protective property and the crimp properties were evaluated by the following methods: (1) The add-on of the treating agent on the synthetic fiber The add-on of the treating agent on the synthetic fiber = (Weight of treating agent/weight of fiber) x 100% by weight (2) The flameproofing property The washing by water in the flameproofing test method of the Japanese fire protection law was repeated 5 times, wherein the water hardness was adjusted by 75ppm with calcium chloride, and then the number of flame contact was determined as a mean value of 5 samples according to Japanese Industial Standard (JIS) L-1091 D method. The number of flame contact is more, the flameproofing property is better. The number of flame contact permissible in practical use is at least 2, preferably at least 3. (3) The adhesive fastness of HCA to the synthetic fiber The adhesive fastness of HCA on dry cleaning With respect to the above value, at least 50% was defined as "good" (marked by O), and less than 50% was defined as "inferior" (marked by X). (4) The spinning property The spinning property was evaluated by the occurrence of clogging induced by the fibers in coiler tubes when 10Kg of fibers was carded. No occurrence of clogging was defined as "good" (marked by O), the case that the coiling became impossible by clogging was defined as "inferior" (marked by X), and the case that the spinning was somehow possible, lying between both, was defined as "approximately good" (marked by Δ). (5) The feeling "Good" (marked by O) and "inferior" (marked by X) were judged by the touch. (6) The foaming during operation In the circulation tank, the dipping treating bath and the like, the case that the foaming was remarkable was defined as "inferior" (marked by X), the case that no problem occurred was defined as "good" (marked by O), and the case that the extent of foaming lay between both was defined as "ordinary" (marked by Δ). (7) The passing processability through a stuffing crimper The case that the stuffing crimper could not be normally operated, accompanied with rattling, was defined as "inferior" (marked by X), the case that the crimper could be operated almost without problem was defined as "good" (marked by O),and the operating condition of the crimper lay between both was defined "ordinary" (marked by Δ). (8) The corrosion protective property An appropriate amount of the treating liquor was placed in a test tube, and an iron nail was immersed therein. When allowed to stand for a whole day and night, the case that rust was generated on the surface of the nail was defined as "inferior" (marked by X), the case that no rust was generated was defined as "good" (marked by O), and the intermediate state between both was defined as "ordinary" (marked by Δ). (9) The crimp properties The crimp number and the percentage crimp of the flameproofed synthetic fiber was measured in accordance with Japanese Industrial Standard (JIS) L-10l5. Examples 1 to 8 45 parts of 1,2,5,6,9,10-hexabromocyclododecane (hereinafter referred to as HBCD for brevity) having an average particle size of 0.5µm, 0.5 part of carboxymethyl cellulose having an average molecular weight of 400,000 as the protective colloid and 54.5 parts of water were ground and mixed in a ball mill for 5 hours to produce an aqueous dispersion of HBCD wherein effective ingredient of 45% by weight was contained and which viscosity is 4,500 mPa.s (centipoises) when measured by a rotary B type viscometer. 44 parts of the resultant aqueous dispersion was brought up to 100 parts as a whole by adding aqueous solutions of various phosphate compounds shown in Table 1 to prepare various treating baths, respectively. On the other hand, polyethylene terephthalate tows of 50000 tex (450,000 deniers) were drawn to 3.5 times in a hot water bath of 90°C to produce drawn tows having a monofilament fineness of 2.2 dtex (2 deniers). The drawn tows was dipped in and passed through the foregoing various treating baths, and thereafter crimped by a stuffing crimper in such a manner that the crimp number of 12 crimps/25mm and the percentage crimp of 12% could be obtained. As well as crimping, the treating liquor contained in the tows was squeezed in such a manner that the add-on of the treating agents shown in Table 1 could be obtained. The tows were subsequently heat treated under relaxation by a continuous dryer at 170°C for 15 minutes, and then cut in length of 51mm to prepare the staple fibers. The staple fibers thus obtained were spun to spun yarns of 30/2, and the yarn dyeing was carried out by a package dyeing machine under the following two conditions: Two kinds of dyed yarns thus obtained were woven to a jacquard fabric having the weight of 400g/m² by a jacquard weaving machine. The fabrics were scoured in a bath containing 0.5g/l of the nonionic surfactant (Scourol 400# (TM)) in a bath ratio of 1:20 at a temperature of 80°C for a period of 10 minutes. Then, the flameproofing property, the adhesive fastness of HBCD, the spinning property and the feeling of the resultant fabrics were determined. The stability of the various treating liquors, the corrosion protective property, the foaming during operation and the passing processability through a stuffing crimper were also evaluated. The results obtained were as shown in Table 2. Comparative Example 1 The treatment was conducted in the same manner as in Example 1 with the exception that the phosphate compound (B) was not used. Comparative Examples 2 to 4 The treatments were conducted in the same manner as in Example 1 with the exception that HBCD as a flameproofing agent was substituted for Antiblaze 19 (TM) (supplied by Mobile Chemical Co., cyclic phosphate, effective ingredient of 100%) as Comparative Example 2, for an emulsion of tris(2,3-dichloropropyl)phosphate (effective ingredient of 45%) as Comparative Example 3 and for an emulsion of tetrabromobisphenol A (effective ingredient of 45%) as Comparative Example 4. The results obtained were also shown in Table 2. As apparent from Table 2, the synthetic fibers of the present invention comprising HCA (A) and the phosphorus compound (B) (Examples 1 to 8) were excellent in flameproofing property, adhesive fastness of HBCD, spinning property, feeling and corrosion protective property and passing processability through a stuffing crimper, and further the treating liquors used in the present invention were stable and the foaming thereof was little. On the contrary, when the phosphorus compound (B) was not contained (Comparative Example 1), the spinning property, the corrosion protective property and the passing processability were deteriorated. When the other conventional flameproofing agents were used instead of HBCD (Comparative Examples 2 to 4), the fibers were lowered in not only flameproofing property, but also in adhesive fastness of the flameproofing agent, spinning property and feeling. Examples 9 and 10 The treatments were conducted in the same manner as in Example 4 with the exception that HBCD was substituted for 1,2,3,4-tetrabromocyclooctane (Example 9) and for 1,2,3,4,5,6-hexabromocycloheptane (Example 10). The results were as shown in Table 3. The fibers obtained in each Example showed good properties. Examples 11 to 21 The synthetic fibers deposited with various amounts of HCA (A) and the phosphorus compound (B) and various ratios of HCA (A) to the phosphorus compound (B) as shown in Table 4 were prepared by varying a mixing ratio of HCA (A) and the phosphorus compound (B) in the treating bath in Example 7. The results were as shown in Tables 4 and 5. As apparent from Tables 4 and 5, it is preferable that a total amount of HCA (A) and the phosphorus compound (B) deposited on the synthetic fibers is in the range of 0.5 to 7.0% by weight, preferably, 1.5 to 4.0% by weight, in terms of the flameproofing property and the spinning property. A ratio of HCA (A) to the phosphorus compound (B) is preferable to be in the range of 70:30 to 98:2, in terms of the spinning property, the corrosion protective property, the passing processability through a stuffing crimper and the foaming of the treating bath during operation. Examples 22 to 28 In Example 7, the fibers varied in crimp properties were prepared and the spinning property thereof was evaluated. The results were as shown in Table 6, and it was observer that the fibers having a crimp number of 10 to 18 crimps/25mm and a percentage crimp of 8 to 38% showed the good spinning property. Example 29 to 31 The mixture of 97 parts of dimethyl terephthalate, 69 parts of ethylene glycol, 0.09 part of calcium acetate and 0.03 part of antimony trioxide was heated at 165°C to 220°C until the distillation of methanol was completed. Then, 0.7 part of trimethyl phosphate and 0.99 part of p-diphenylcarboxylic acid were added thereto, and the reaction was continued under an atmosphere of nitrogen at 275°C for 200 minutes, gradually reducing the pressure with the progress of the reaction, finally to 53,32 Pa (0.4mm Hg). The polyester thus obtained had an intrinsic viscosity of 0.64. This polyester was melt spun in the usual way to obtain a tow of 4,995 x 10⁻² 8g/m (450,000 deniers), and the tow was further drawn to 3.5 times in a hot water bath of 90°C to produce a drawn tow having a monofilament fineness of 2 diniers. On the other hand, 45 parts of HBCD having an average particle size of 0.5µm, 0.5 part of carboxymethyl cellulose having an average molecular weight of 400,000 as the protective colloid and 54.5 parts of water were ground and mixed in a ball mill for 5 hours to produce an aqueous dispersion of HBCD wherein effective ingredient of 45% by weight was contained and which viscosity is 4,500 mPa.s (4,500 centipoises) when measured by a rotary B type viscometer. 44 parts of the aqueous solution containing HBCD was brought up to 100 parts as a whole by adding aqueous solutions of various phosphate compounds shown in Table 7 and used as a treating bath. The foregoing drawn tow was dipped in and passed through this treating bath, and thereafter crimped by a stuffing crimper in such a manner that the crimp number of 12 crimps/25mm and the percentage crimp of 12% could be obtained. As well as crimping, the treating liquor contained in the tow was squeezed in such a manner that the treating agent were deposited on the tow in an amount of 1.0% by weight. The tow was subsequently heat treated under relaxation by a continuous dryer at 170°C for 15 minutes, and then cut in length of 51mm to prepare the staple fibers. Trimethyl phosphate was contained in the staple fibers in an amount of 0.7% by weight. The staple fibers thus obtained were spun to spun yarns of 30/2, and the yarn dyeing was carried out by a package dyeing machine under the following two conditions: Two kinds of dyed yarns thus obtained were woven to a jacquard fabric having the weight of 400g/m² by a jacquare weaving machine. The fabric was scoured in a bath containing 0.5g/l of the nonionic surfactant (Scourol 400#) a registered trademark) in a bath ratio of 1:20 at a temperature of 80°C for a period of 10 minutes. The results were as shown in Table 7. The addition of the phosphate compound represented by the foregoing general formula (I) caused the foaming of the treating bath to be depressed, and the corrosion protective property, the passing processability through a stuffing crimper and the spinning property to be remarkably improved. As hereinbefore described, according to the present invention, by allowing the synthetic fiber to comprise the specific phosphorus compound in addition to HCA, the flameproofing synthetic fiber which is excellent in flamproofing property and feeling and significantly improved in spinning property and corrosion protective property can be provided. Furthermore, the stability of the treating liquor, the foaming during operation and the passing processability through a stuffing crimper in the procedure of synthetic fiber manufacturing are also extremely improved. The flameproofing synthetic fiber of the present invention is extremely useful for textile, filling, interior, nonwoven fabric, artificial leather and artificial fur uses.

Claims: A flameproofed synthetic fiber comprising a synthetic fiber, a halogenated cycloalkane compound (A) and a phosphorus compound (B) characterized in that said phosphorus compound (B) is a phosphorus compound represented by the following general formula (I): wherein R is an alkyl group having 6 to 30 carbon atoms on an average, each of M and M', which may be the same or different, is an alkali metal, and n is an integer of 0 to 30; wherein said halogenated cycloalkane compound (A) and said phosphorus compound (B) of the general formula (I) are applied to said synthetic fiber in a total amount of 0.5 to 7% by weight based on the weight of said synthetic fiber, and the ratio of said halogenated cycloalkane compound (A) to said phosphorus compound (B) of the general formula (I) is the range of 70:30 to 98:2. A flameproofed synthetic fiber according to claim 1, wherein the halogenated cycloalkane compound (A) is hexabromocyclododecane. A flameproofed synthetic fiber according to claims 1 or 2, wherein the synthetic fiber is composed of polyester. A flameproofed synthetic fiber according to claims 1, 2 or 3, wherein the synthetic fiber is crimped, having a crimp number of 10 to 18 crimps/25mm and a percentage crimp of 8 to 38%.

Inventors: MITAMURA, TAMIO, ORII, KAZUNORI, SAKASHITA, NOBUO, TASHIRO, MIKIO, TATSUOKA, YASUNORI
Applicants: TEIJIN LIMITED
Application year: 1986
Main classification: D06M13
IPC codes: D06M101, D06M13, D06M15