Classifications

• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
  • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
  • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F1/00—General methods for the manufacture of artificial filaments or the like
  • D01F1/02—Addition of substances to the spinning solution or to the melt
  • D01F1/07—Addition of substances to the spinning solution or to the melt for making fire- or flame-proof filaments
• • D—TEXTILES; PAPER
  • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
  • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
  • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
  • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
  • D01F8/12—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyamide as constituent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
  • Y10T428/2913—Rod, strand, filament or fiber
  • Y10T428/2933—Coated or with bond, impregnation or core

Definitions

• the present invention relates to a filament comprising a specific polyamide resin composition having excellent flame retardancy and strength, and more particularly to a multi-filament comprising a plurality of monofilaments, especially to crimped textured yarn, i.e., BCF (bulked continuous filament). Further, the present invention relates to carpets exhibiting a high safety and an excellent flame retardancy irrespective of no inclusion of halogen compounds by using the BCF. In addition, the present invention relates to application of the monofilament to guard nets for wire harness as well as mesh sheets, and a specific multi-layer filament suitably applicable to mesh sheets, etc.
• Flame retardant polyamide filaments have been used in the form of monofilament or multi-filament in various applications.
• the monofilament has been applied mainly to guard nets for wire harness of domestic electric appliances, vehicles, air planes, etc., as well as raw yarn for multi-filament, etc.
• BCF bulked continuous filament
• mat-shaped carpets comprising a ground fabric tufted with a twist yarn composed of 2 to 3 multi-filaments called BCF which are obtained by subjecting a non-flame retardant polypropylene or nylon to spinning-coupled stretching/crimping process, and a rubber sheet adhered to a rear surface of the tufted ground fabric.
• An object of the present invention is to provide a flame retardant polyamide filament having a excellent flame retardancy without using any halogen-based compound as well as a high safety to environments and an excellent strength, especially a multi-filament, a polyamide BCF obtained by crimping the multi-filament, and carpets using the polyamide BCF.
• a flame retardant polyamide filament comprising a polyamide resin composition which has a tensile strength of not less than 2.0 cN/dtex as measured according to JIS L1013 and comprises 98 to 80 parts by weight of a polyamide resin having a relative viscosity of 2.0 to 4.0 and 2 to 20 parts by weight of a triazine-based flame retardant which is dispersed in the polyamide filament and has an average particle size of less than 5 ⁇ m.
• the flame retardant polyamide filament as defined above which is in the form of a multi-filament comprising a plurality of monofilaments.
• a flame retardant polyamide BCF (bulked continuous filament) produced by subjecting the above multi-filament to a crimping process.
• the flame retardant polyamide filament as defined above which is in the form of a monofilament having a fineness of 300 to 56,500 dtex, and a guard net for wire harness produced by knitting the monofilament into a net around an electric cable.
• the flame retardant polyamide filament as defined above which is in the form of a monofilament having a fineness of 400 to 11,000 dtex, and a mesh sheet produced by knitting the monofilaments into a net which has a porosity representing a mesh size of 20 to 30%, and a basis weight of 100 to 600 g/m 2 .
• a flame retardant multi-layer filament which has said multi-layer filament comprises an inner layer constituted of a flame retardant polyamide resin layer A comprising a polyamide resin composition comprising 98 to 80 parts by weight of a polyamide resin having a relative viscosity of 2.0 to 4.0 and 2 to 20 parts by weight of a triazine-based flame retardant which has an average particle size of less than 5 ⁇ m and is dispersed in the filament; and a surface layer formed on the inner layer and constituted of any one of the flame retardant polyamide resin layer A, a polyamide resin layer B having a composition other than that of the flame retardant polyamide resin layer A and a polyolefin resin layer C.
• the flame retardant multi-layer filament as defined above, wherein a melting point of the polyamide resin contained in the polyamide resin layer A constituting the inner layer is higher by 5°C or more, than a melting point of the resin used in the surface layer, and a mesh sheet produced by interlacing the multi-layer filaments as defined in the above into a net, and heat-fusing crossing portions of the warp and weft filaments at the surface layer thereof.
• the polyamide resin there may be used various polyamides produced by polycondensation of 3 or more-membered lactams, polymerizable ⁇ -amino acids, dibasic acids, diamines and the like.
• the polyamides may include polymers of ⁇ -caprolactam, aminocaproic acid, enanthlactam, 7-amino-heptanoic acid, 11-amino-undecanoic acid, 9-amino-nonanoic acid, ⁇ -pyrrolidone, ⁇ -piperidone or the like; aliphatic polyamides or copolymers thereof such as polyamides 4, 6, 7, 8, 11, 12, 66, 69, 610, 611, 612, 6/66 and 6/12 as well as aromatic polyamides or copolymers thereof such as polyamides 6T, 6/6T, 6T/6I and MXD6 which are polymers or copolymers obtained by polycondensing a diamine such
• polyamide 6 copolyamide 6/66 and polyamide 66 from the standpoints of flame retardancy, mechanical strength and moldability.
• the polyamide resin used in the present invention may be terminal-sealed with carboxylic acids or amines, preferably with carboxylic acids or amines having 6 to 22 carbon atoms.
• carboxylic acids used for the terminal-sealing may include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and behenic acid, or the like.
• amines used for the terminal-sealing may include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine and behenylamine, or the like.
• the amount of the carboxylic acid or amine used for the terminal-sealing is about 30 ⁇ eq/g.
• the polyamide resin used in the present invention has such a degree of polymerization that its relative viscosity as measured with respect to a 1% solution of polyamide in 98% sulfuric acid at 25°C according to JIS K6810, is in the range of 2.0 to 4.0.
• the relative viscosity is less than 2.0, the polyamide resin may show a too low melt viscosity, resulting in not only difficulty in spinning, but also poor mechanical strength and, therefore, rupture upon BCF processing stage.
• the relative viscosity is more than 4.0, the polyamide resin not only may fail to show a good melt fluidity, but also may not be stably spun due to heat deterioration upon shearing.
• Triazine-based flame retardant Triazine-based flame retardant
• Examples of the triazine-based flame retardant used in the present invention may include compounds represented by the following general formula (1) or (2): wherein R 1 to R 6 are independently hydrogen or alkyl; melamines; and reaction products obtained by reacting cyanuric acid with the melamines at a molar ratio of 1:1.
• Specific examples of the compounds represented by the above general formula (1) may include cyanuric acid, trimethyl cyanurate, triethyl cyanurate, tri(n-propyl) cyanurate, methyl cyanurate, diethyl cyanurate or the like.
• Specific examples of the compounds represented by the above general formula (2) may include isocyanuric acid, trimethyl isocyanurate, triethyl isocyanurate, tri(n-propyl) isocyanurate, diethyl isocyanurate, methyl isocyanurate or the like.
• melamines there may be used melamine, melamine derivatives, compounds having a similar structure to that of melamine, condensates of melamine or the like.
• Specific examples of the melamines may include melamine, ammelide, ammeline, formoguanamine, guanyl melamine, cyanomelamine, aryl guanamine, melam, melem, melon or like.
• reaction products obtained by reacting cyanuric acid with melamines at a molar ratio of 1:1 are preferred, because these compounds show a good thermal stability, i.e., are free from defects such as blooming of decomposition products onto the surface of molded products upon molding process, and more preferred is melamine cyanurate.
• melamine cyanurate some of amino groups or hydroxyl groups of the melamine cyanurate may be substituted with other groups.
• the melamine cyanurate may be produced, for example, by mixing an aqueous cyanuric acid solution and an aqueous melamine solution with each other, reacting these compounds at a temperature of 90 to 100°C under stirring, and then filtering the resultant reaction solution to separate precipitates produced therefrom.
• the melamine cyanurate is commercially available in the form of a white solid, and the commercially available melamine cyanurate may be used immediately or may be preferably pulverized into a fine powder before use.
• the triazine-based flame retardant is usually present in the form of agglomerates composed of fine particles each having a particle size of submicron order.
• the average particle size of the triazine-based flame retardant is expressed by an average particle size of dispersed particles in the form of the agglomerates composed of fine particles each having a particle size of submicron order.
• the average particle size means a number-average particle diameter.
• the average particle size of the triazine-based flame retardant represents an average value of measured particle sizes of the dispersed particles contained in the stretched filament.
• the average particle size of the triazine-based flame retardant dispersed in the filament can be determined, for example, by cutting the filament, removing the triazine-based flame retardant from the cut section of the filament, and observing traces formed on the section after removal of the triazine-based flame retardant by SEM to measure the sizes thereof.
• the average particle size of the triazine-based flame retardant dispersed in the filament is less than 5 ⁇ m.
• the monofilament may be ruptured during the filament molding process, i.e., at any stage of monofilament-spinning, stretching and crimping processes.
• the agglomerates thereof may be broken upon blending or spinning step.
• the agglomerates of the triazine-based flame retardant are preferably previously pulverized into a suitable size before use.
• the average particle size of the triazine-based flame retardant before blending in the polyamide resin may be measured by existing particle size measuring devices, for example, a precipitation granulometer, a laser diffraction-type granulometer, ordinary optical microscopes or the like.
• the amount of the triazine-based flame retardant blended is usually 2 to 20 parts by weight, preferably 3 to 20 parts by weight based on 98 to 80 parts by weight of the polyamide resin.
• the amount of the triazine-based flame retardant blended is less than 2 parts by weight, the obtained composition tends to be deteriorated in flame retardancy.
• the amount of the triazine-based flame retardant blended is more than 20 parts by weight, the monofilament tends to be ruptured upon the production of BCF.
• the blending of the triazine-based flame retardant in the polyamide resin may be conducted by various known methods at any optional stages up to the time immediately before the spinning step upon the production of BCF.
• the simplest one is such a method of melt-mixing given amounts of the triazine-based flame retardant and the polyamide resin, and then melt-extruding the resultant mixture to form pellets thereof.
• the polyamide resin composition having a predetermined blending ratio may be produced by previously forming master pellets by kneading an excessive amount of the triazine-based flame retardant in the polyamide resin according to the requirement, and then dry-blending the thus obtained master pellets with polyamide resin to dilute in the predetermined ratio. After the dry-blending, the obtained composition may be further melt-mixed and melt-extruded into pellets.
• the polyamide resin composition may contain, in addition to the triazine-based flame retardant, various known additives such as pigments, dyes, fillers, nucleating agents, mold release agents, stabilizers, antistatic agents or the like. Further, the polyamide resin composition of the present invention may be blended with thermoplastic resins other than polyamide resins unless the effects of the present invention are adversely affected by the addition thereof.
• the polyamide filament of the present invention may be in the form of either a monofilament constituted of a single yarn obtained by an ordinary melt spinning process, or a multi-filament obtained by bundling or twisting a plurality of such monofilaments. Further, the polyamide filaments may be split fibers obtained by tearing films, slit (flat) fibers or the like. Among these filaments or fibers, the present invention is excellently applicable to the monofilament obtained by melt-spinning process or the multi-filament produced from such monofilaments.
• the monofilament may be in the form of either short fibers or long fibers, and may have a cross-section of a round shape and an elliptical shape as well as other shapes.
• the monofilament may be used as raw yarn for producing a multi-filament by bundling or twisting a plurality of the monofilaments, or may be used to produce a multi-filament by combining the monofilament as core with fibers made of other resins, or on the contrary, by combining the fibers made of other resins as core with the monofilament.
• the monofilament may be sometimes directly used as fishing line, gut or the like.
• the monofilament may be processed, for example, knitted or woven to produce guard nets for wire harness, mesh sheets for building construction work, or the like.
• the multi-filament, split fibers and slit fibers may also be practically used either immediately or after processing in similar applications to those of the monofilament.
• the polyamide multi-filament of the present invention is produced by melting and spinning the polyamide resin composition obtained by blending a specific amount of the triazine-based flame retardant having a specific particle size in the polyamide resin, stretching the obtained filament, if required, and then subjecting the filament to bundling, twisting or the like processes.
• the thus spun monofilament may be formed into various sectional shapes, e.g., by varying the sectional shape of a spinning nozzle.
• the monofilament thereof may be a bulked continuous filament whose cross-section is formed into a Y-shape (Y-shaped section), a trilobal shape, etc., as well as hollow structures of these shapes and different shapes such as -shaped (lattice-shape) hollow structure.
• the thickness (fineness) of the spun monofilament may be appropriately selected according to the applications of the multi-filament and, therefore, is not particularly restricted.
• the monofilament When applied to BCF, the monofilament has a fineness of 4 to 90 dtex.
• the diameter of each monofilament When the section of the multi-filament is a round shape, the diameter of each monofilament may be in the range of 0.02 to 0.1 mm, and the total fineness of the multi-filament may be in the range of 1,111 to 3,333 dtex (1,000 to 3,000 denier).
• the multi-filament is usually produced by bundling or twisting a plurality of the monofilaments.
• BCF Band-CF
• about 10 to 100 monofilaments are bundled, and especially when ordinary BCF production apparatuses are used, 64 to 68 monofilaments are usually bundled.
• the flame retardant polyamide BCF (bulked continuous filament) of the present invention is made of a bulky continuous textured yarn having different cross-sections such as a trilobal cross-section, -shaped (lattice-shape) hollow cross-section, etc., which has been frequently used for the purpose of improving a covering property or antifouling property of carpets or the like, and can be produced by usually subjecting the polyamide resin composition containing the above flame retardant as raw material to three processes including spinning, stretching and crimping processes.
• KOKAI Japanese Patent Application Laid-Open
• the BCF production is performed at a line speed of 2,000 to 3,000 m/min.
• the above BCF also includes a twist yarn (occasionally referred to as BCF pile yarn) obtained by further twisting 2 to 4 BCF multi-filaments (each occasionally referred to as BCF ply yarn) each composed of 64 to 68 monofilaments.
• the polyamide monofilament of the present invention may be directly applied to fishing line, gut, etc.
• the polyamide monofilament may be processed into woven fabric or knitted fabric, and suitably applied to guard nets for wire harness as well as curing or protective sheets with a mesh structure, i.e., so-called mesh sheets used for building construction work, etc.
• the guard net for wire harness is a tubular protective net formed by densely knitting monofilaments, for the purpose of protecting the wire harness (such as electric cables and signal cables) used in domestic electric appliances, vehicles, air planes, etc., against impact and stress exerted thereon from outside.
• the polyamide monofilament used for this purpose is stretched, for example, at a stretch ratio of 3.5 to 5.0 times, preferably 3.5 to 4.5 times.
• Such a polyamide monofilament has a diameter of preferably 0.01 to 3 mm, more preferably 0.02 to 2.5 mm.
• the polyamide monofilament When applied to the guard nets for wire harness, the polyamide monofilament has a diameter of still more preferably about 0.1 to 0.8 mm, most preferably 0.2 to 0.5 mm.
• the fineness of the polyamide monofilament is preferably in the range of 300 to 56,500 dtex though it varies depending upon applications thereof.
• the mesh sheet mainly used for construction work is frequently spread around buildings such as houses and office buildings or construction sites such as bridge construction sites for protection against dangers and accidents.
• the mesh sheet is produced by weaving or knitting the monofilaments into a net using a weaving or knitting machine.
• the mesh size of the mesh sheet is not particularly restricted as long as an appropriate air permeability is ensured.
• the mesh sheet used for building construction work has a porosity representing the mesh size of 20 to 30%.
• the mesh sheet has a basis weight of 100 to 600 g/m 2 , preferably 200 to 400 g/m 2 .
• the monofilaments to be knitted into a net are stretched, for example, at a stretch ratio of 3.5 to 5.5 times, preferably 4 to 5 times.
• the monofilament usually has a thread diameter of 0.1 to 1.5 mm, preferably 0.2 to 1.1 mm, and a fineness of 400 to 11,000 dtex.
• the flame retardant multi-layer filament of the present invention comprises an inner layer constituted of a flame retardant polyamide resin layer A made of a polyamide resin composition obtained by blending 98 to 80 parts by weight of a polyamide resin having a relative viscosity of 2.0 to 4.0 with 2 to 20 parts by weight of a triazine-based flame retardant having an average particle size of less than 5 ⁇ m under the condition dispersed in the filament; and a surface layer formed on the inner layer and constituted of any one of the flame retardant polyamide resin layer A, a polyamide resin layer B having a composition other than that of the flame retardant polyamide resin layer A and a polyolefin resin layer C, and has a tensile strength of not less than 2.0 cN/dtex as measured according to JIS L1013.
• the multi-layer filament may further comprise an intermediate layer such as an adhesive layer between the inner layer and the surface layer.
• a melting point of the polyamide resin contained in the polyamide resin layer A constituting the inner layer is higher by 5°C or more, than a melting point of the resin used in the surface layer.
• the multi-layer filament may be suitably used for production of mesh sheets without dislocation of meshes by interlacing the monofilaments or multi-filaments produced therefrom with each other into a net, and heat-fusing crossing portions of the warp and weft filaments at a surface layer thereof.
• the polyamide filament of the present invention has a tensile strength of not less than 2.0 cN/dtex as measured according to JIS L1013.
• the polyamide filament has a tensile strength of preferably not less than 2.5 cN/dtex, more preferably not less than 3.0 cN/dtex.
• the tensile strength used herein is expressed by a value obtained by dividing the applied tensile break load by the fineness of the filament, and the unit thereof is represented by cN/dtex as SI unit, wherein the tensile load cN means 1/100 x N, and the fineness dtex means grams per a length of 10,000 m.
• the tensile strength is less than 2.0 cN/dtex, the obtained filament is insufficient in strength upon practical use or strength upon knitting into a net. As a result, the filament tends to be ruptured upon twisting, setting and tufting processes during the production of BCF, or when used as products such as carpets. Meanwhile, in the case of the multi-layer filament, the tensile strength is that of the multi-layer filament as a whole, and the preferred range thereof is the same as described above.
• Oxygen index (LOI) LOI
• the flame retardant polyamide filament of the present invention preferably exhibits such a flame retardancy that an oxygen index thereof is not less than 27 as measured according to JIS K7201.
• the oxygen index thereof is represented by the value measured with respect to the multi-layer filament as a whole.
• the oxygen index means an oxygen concentration (% by volume) required to continue combustion of a sample.
• the sample is in the form of a sheet having a thickness of about 1 mm, if its oxygen index is not less than 22, it is not possible to continuously burn the sample at an oxygen concentration in atmospheric air, namely it is meant that the sample is a self-extinguishing material.
• the oxygen index of the polyamide filament is preferably not less than 27 in order to achieve much stricter flame retardancy.
• the oxygen index may vary depending upon water absorption of the polyamide resin composition.
• the oxygen index thereof is measured according to JIS K7201.
• the oxygen index thereof can be directly measured by self-supporting the BCF in a sample holder specified by the JIS.
• the flame retardant polyamide filament of the present invention preferably contains no halogen compound.
• halogen elements such as fluorine, chlorine and bromine which is measured by burning a filament or BCF obtained by processing the filament as a test sample at 900°C to capture the combustion gas, and then subjecting the gas to ion chromatographic analysis, is not more than 10 ppm, preferably not more than 5 ppm, more preferably not more than 2 ppm based on the weight of the sample.
• the content of halogen elements is the above-specified value or less, it is considered that the gas generated upon combustion of the polyamide filament contains substantially no halogen elements, and the polyamide filament can exhibit a high safety to environments.
• the flame retardant polyamide BCF is useful as raw yarn for carpets, and can be processed into a mat shape through various known processes such as twisting, setting, tufting, backing, etc., thereby obtaining carpets.
• various known processes such as twisting, setting, tufting, backing, etc., thereby obtaining carpets.
• KAKI Japanese Patent Application Laid-Open
• BCF multi-filaments each having a total fineness of 1,408 dtex which are each composed of 64 monofilaments (fineness of each monofilament: about 22 dtex) and produced using an ordinary spinning, stretching and crimping-coupled BCF production apparatus, are twisted and then subjected to wet-heat setting process at a temperature of 120 to 130°C for about one minute, thereby obtaining a pile yarn.
• the tufted ground fabric is subjected to backing process in which a NBR rubber sheet blended with a vulcanizing agent is adhered onto a rear side thereof, and then pressed at 170°C under a pressure of 294 kPa (3 kg/cm 2 ), thereby obtaining a mat-shaped product, i.e., carpets.
• Polyamide 6 resin-1 "NOVAMID® 1015J” produced by Mitsubishi Engineering-Plastics Corporation (relative viscosity: 3.0)
• Polyamide 6 resin-2 "NOVAMID® 1020J” produced by Mitsubishi Engineering-Plastics Corporation (relative viscosity: 3.5)
• Copolyamide 6/66 resin-1 A 50% aqueous solution of a salt of adipic acid and hexamethylenediamine (hereinafter referred to merely as "AH salt”) and ⁇ -caprolactam (hereinafter referred to merely as "CL”) were respectively heated to 100°C, and 15 parts by weight of AH salt and 85 parts by weight of CL were mixed together. Then, the resultant mixture was charged into a 200 liter autoclave and then heated to 270°C while maintaining an inner pressure of the autoclave at 1,275 kPa (13 kg/cm 2 ).
• AH salt hexamethylenediamine
• CL ⁇ -caprolactam
• the inner pressure of the autoclave was gradually reduced to 49 kPa (0.5 kg/cm 2 ) while maintaining the inner temperature at 245°C and stirring the contents thereof, and the polymerization was stopped at the time at which the agitation power reached a predetermined value.
• Copolyamide 6/66 resin-2 The same procedure as described above was conducted except that the polymerization was stopped at the time at which the relative viscosity of the obtained resin reached 3.5. It was confirmed that the obtained resin had a melting point of 202°C.
• Triazine-based flame retardant A Triazine-based flame retardant A:
• Triazine-based flame retardant B Triazine-based flame retardant B:
• the pellets of the thus obtained polyamide resin composition were dried for 6 hours at 120°C under reduced pressure, i.e., under a gauge pressure of -101 kPa, and molded into respective samples.
• the polyamide resin composition shown in Table 1 was molded into a BCF multi-filament having a fineness of 1,408 dtex and a trilobal sectional shape which were composed of 64 monofilaments each having a fineness of 22 dtex using a spinning, stretching and crimping-coupled BCF production apparatus manufactured by FILTECO. Meanwhile, since the first roll speed was 500 m/min and the final roll speed was 1,900 m/min, the stretch ratio was 3.8 times.
• the thus obtained BCF was tested to measure a tensile strength thereof. Also, the monofilaments constituting the BCF were subjected to measurement of average particle size of the triazine-based flame retardant contained therein, measurement of oxygen index thereof, and elemental analysis of halogens contained therein. The results are shown in Table 1.
• the BCFs obtained in Examples 1 to 3 all were able to be molded into a mat shape through various processes including twisting, setting, tufting, backing, etc., thereby obtaining carpets containing no halogen compound and having a high safety and an excellent flame retardancy.
• the polyamide resin composition shown in Table 2 was melt-spun at a resin temperature of 254°C using a single-screw extruder having a cylinder diameter of 30 mm and a ratio L/D of 27 which was fitted with a full-flighted screw and a gear pump at a tip end thereof, and passed through a cooling water vessel whose water temperature was maintained at 10°C for cooling and solidification thereof.
• the obtained filament was sequentially subjected to wet-heat stretching at 98°C, 100% RH and a stretch ratio of 3.5 times, dry-heat stretching in dried air at 175°C and a stretch ratio of 1.34 times, and finally dry-heat annealing at 165°C and a relaxation ratio of 0.95 times, thereby obtaining a monofilament having a diameter of 0.2 mm.
• the four monofilaments thus obtained were knitted into a net around an iron core as a jig having a diameter of 12 mm to produce a guard net.
• the thus obtained guard net was fitted around a bundle of electric cables to constitute a wire harness. After the obtained wire harness was practically used for a long period of time, it was confirmed that the bundle of electric cables covered with the guard net was sufficiently protected against external stress.
• the polyamide resin composition shown in Table 2 was melt-spun at a resin temperature of 247°C using a single-screw extruder having a cylinder diameter of 40 mm and a ratio L/D of 27 which was fitted with a full-flighted screw and a gear pump at a tip end thereof, and then passed through a cooling water vessel whose water temperature was maintained at 12°C for cooling and solidification thereof.
• the obtained filament was sequentially subjected to wet-heat stretching at 98°C, 100% RH and a stretch ratio of 3.4 times, dry-heat stretching in dried air at 180°C and a stretch ratio of 1.3 times, and finally dry-heat annealing at 170°C and a relaxation ratio of 0.95 times, thereby obtaining a monofilament having a diameter of 2.0 mm.
• the four monofilaments thus obtained were knitted into a net around an iron core as a jig having a diameter of 75 mm to produce a guard net.
• the thus obtained guard net was fitted around a bundle of electric cables to constitute a wire harness. After the obtained wire harness was practically used for a long period of time, it was confirmed that the bundle of electric cables covered with the guard net was sufficiently protected against external stress.
• the polyamide resin composition shown in Table 3 was melt-spun at a resin temperature of 254°C using a single-screw extruder having a cylinder diameter of 30 mm and a ratio L/D of 27 which was equipped with a full-flighted screw and a gear pump at a tip end thereof, and then passed through a cooling water vessel whose water temperature was maintained at 10°C for cooling and solidification thereof.
• the obtained filament was sequentially subjected to wet-heat stretching at 98°C, 100% RH and a stretch ratio of 3.5 times, dry-heat stretching in dried air at 175°C and a stretch ratio of 1.43 times, and finally dry-heat annealing at 165°C and a relaxation ratio of 0.95 times, thereby obtaining a monofilament having a fineness of 2,060 dtex (diameter of about 0.48 mm).
• the oxygen index and tensile strength of the thus obtained monofilament were measured.
• the obtained monofilaments were knitted into a net to form a plain-woven mesh sheet having a size of 1 m x 1 m and a basis weight of 400 g/m 2 .
• the polyamide resin composition shown in Table 4 was melt-spun at a resin temperature of 247°C using a single-screw extruder having a cylinder diameter of 40 mm and a ratio L/D of 27 which was equipped with a full-flighted screw and a gear pump at its tip end, and then passed through a cooling water vessel whose water temperature was maintained at 12°C for cooling and solidification thereof.
• the obtained filament was sequentially subjected to wet-heat stretching at 98°C, 100% RH and a stretch ratio of 3.8 times, dry-heat stretching in dried air at 180°C and a stretch ratio of 1.3 times, and finally dry-heat annealing at 170°C and a relaxation ratio of 0.95 times, thereby obtaining a monofilament having a fineness of 8,950 dtex (diameter of about 1.0 mm).
• the oxygen index and tensile strength of the thus obtained monofilament were measured.
• the obtained monofilaments were knitted into a net to form a plain-woven mesh sheet having a size of 1 m x 1 m and a basis weight of 400 g/m 2 .
• an extruding apparatus for forming a multi-layer monofilament comprising a single-screw extruder for an inner layer having a cylinder diameter of 30 mm and a ratio L/D of 27 and being equipped with a gear pump at its tip end and a full-flighted screw, and a single-screw extruder for a surface layer having a cylinder diameter of 20 mm and a ratio L/D of 25 and being equipped with a gear pump at its tip end both of which were connected to a common die for forming the multi-layer monofilament through the respective gear pumps, the polyamide resin composition shown in Table 5 for forming the inner layer, and the polyamide resin or polyamide resin composition for forming the surface layer, were charged into the respective single-screw extruders, and melt-spun into a multi-layer monofilament using the same molding temperature of 250°C for both the layers.
• the thus melt-spun multi-layer monofilament was passed through a cooling water vessel whose water temperature was maintained at 10°C for cooling and solidification thereof. Then, the obtained multi-layer monofilament was sequentially subjected to wet-heat stretching at 98°C, 100% RH and a stretch ratio of 3.5 times, dry-heat stretching in dried air at 175°C and a stretch ratio of 1.43 times, and finally dry-heat annealing at 165°C and a relaxation ratio of 0.95 times, thereby obtaining a monofilament having a fineness of 2,060 dtex (diameter of about 0.48 mm).
• the thus obtained monofilament was sliced along its cross-sectional direction by a razor.
• the resultant section of the monofilament was observed by an optical microscope to measure a thickness of the surface layer thereof. Further, the oxygen index and tensile strength of the monofilament were measured.
• the obtained monofilaments were knitted into a net to form a plain-woven mesh sheet having a size of 1 m x 1 m and a basis weight of 400 g/m 2 .
• the thus obtained mesh sheet was heated to 210°C by a hot-air heating device to heat-fuse crossing portions of the warp and weft filaments.
• Comparative Example 22 although it was attempted to form a mesh sheet by knitting the obtained monofilaments into a net, the monofilaments were ruptured upon knitting into a net, thereby failing to obtain the mesh sheet as a final product. Also, in Comparative Examples 23 and 24, during the production of the multi-layer monofilament, the filament was ruptured upon stretching, thereby failing to obtain a filament having the aimed fineness.
• the polyamide resin composition shown in Table 6 was melt-spun at a resin temperature of 250°C by a single-screw extruder having a cylinder diameter of 30 mm and a ratio L/D of 27 and being equipped with a full-flighted screw and a gear pump at its tip end, and then passed through a cooling water vessel whose water temperature was maintained at 10°C for cooling and solidification thereof.
• the obtained filament was sequentially subjected to wet-heat stretching at 98°C, 100% RH and a stretch ratio of 3.5 times, dry-heat stretching in dried air at 175°C and a stretch ratio of 1.43 times, and finally dry-heat annealing at 165°C and a relaxation ratio of 0.95 times, thereby obtaining a single-layer monofilament having a fineness of 1,810 dtex (diameter of about 0.45 mm).
• LLDPE was extrusion-molded at a resin temperature of 180°C using a single-screw extruder equipped with a cross head die for coating to form a surface layer on the thus obtained single-layer monofilament, thereby obtaining a multi-layer monofilament.
• the thus obtained multi-layer monofilament was sliced along its cross-sectional direction by a razor.
• the resultant section of the multi-layer monofilament was observed by an optical microscope to measure a thickness of the surface layer thereof. Further, the oxygen index and tensile strength of the multi-layer monofilament were measured.
• the obtained multi-layer monofilaments were knitted into a net to form a plain-woven mesh sheet having a size of 1 m x 1 m and a basis weight of 400 g/m 2 .
• the thus obtained mesh sheet was heated to 160°C by a hot-air heating device to heat-fuse crossing portions of the warp and weft filaments.
• the relative viscosity was measured with respect to a 1% solution of the resin in 98% sulfuric acid at 25°C according to JIS K6810.
• the monofilament (in the case of BCF, monofilament removed therefrom) was notched by a razor, and broken along the notched line by using a liquid nitrogen.
• the resultant section of the monofilament was subjected to ultrasonic cleaning in n-hexane bath at ordinary temperature for 30 minutes to remove the triazine-based flame retardant from the section.
• platinum was vapor-deposited on the section of the monofilament, and the vapor-deposited section was observed by SEM at a magnification of 5,000 times to measure a major axis length of each of traces on the section which were formed after removal of the triazine-based flame retardant therefrom.
• An average value of the thus measured 100 lengths was calculated and determined to be an average particle size of the triazine-based flame retardant.
• the oxygen index of the sample was measured by a D-model candle-type flammability tester manufactured by Toyo Seiki Co., Ltd., according to JIS K7201.
• 0.05 mg of a sample was burned at 900°C by a sample combustion device "QF-02 Model” manufactured by Dia Instrument Co., Ltd.
• the resultant combustion gas was introduced into a 0.3% aqueous hydrogen peroxide solution and trapped therein.
• the obtained solution was subjected to quantitative analysis for fluorine, chlorine and bromine using an ion chromatographic analyzer "IC7000E” manufactured by Yokogawa Analytical Systems Co., Ltd.
• Triazine-based flame retardant A (wt. part) 10 5 0.5 30 - 0.5 Triazine-based flame retardant B (wt. part) - - - - 10 - Composition of outer layer Copolyamide 6/66 resin-1 (wt. part) 100 95 100 90 100 90 Triazine-based flame retardant A (wt. part) - 5 - 10 - - Triazine-based flame retardant B (wt.
• Triazine-based flame retardant A (wt. part) 10 0.5 Composition of outer layer LLDPE (wt. part) 100 100 Evaluation Multi-layer monofilament fineness (dtex) 1980 1980 Multi-layer monofilament diameter (mm) 0.48 0.48 Outer layer thickness ( ⁇ m) 30 30 Average particle size of flame retardant ( ⁇ m: inner layer) 0.8 0.8 Oxygen index (%) 26 21 Monofilament tensile strength (cN/dtex) 3.8 3.8 Netting ability for forming mesh sheet Good Good Fusibility at crossing portions of warp and weft filaments Good Good Good
• the polyamide filament having not only excellent flame retardancy but also excellent strength.
• the polyamide filament can exhibit the same flame retarding effect.
• the polyamide filament in the form of a multi-filament is usable as raw yarn for carpets, and can provide safe BCF or carpets having an excellent flame retardancy.
• the polyamide filament in the form of a monofilament is suitably used in various applications such as guard nets for wire harness, meshes, etc.
• the polyamide filament in the form of a multi-layer filament is suitably used for production of mesh sheets, etc.

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• 2001
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