WO2002024991A1 - Filaments polyamides ignifugeants et leur utilisation - Google Patents

Filaments polyamides ignifugeants et leur utilisation Download PDF

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Publication number
WO2002024991A1
WO2002024991A1 PCT/JP2001/008144 JP0108144W WO0224991A1 WO 2002024991 A1 WO2002024991 A1 WO 2002024991A1 JP 0108144 W JP0108144 W JP 0108144W WO 0224991 A1 WO0224991 A1 WO 0224991A1
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WO
WIPO (PCT)
Prior art keywords
flame
polyamide
retardant
filament
polyamide resin
Prior art date
Application number
PCT/JP2001/008144
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English (en)
Japanese (ja)
Inventor
Hiroshi Urabe
Michio Nakata
Seiji Morimoto
Morio Tsunoda
Original Assignee
Mitsubishi Engineering-Plastics Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsubishi Engineering-Plastics Corporation filed Critical Mitsubishi Engineering-Plastics Corporation
Priority to AU2001290244A priority Critical patent/AU2001290244A1/en
Priority to US10/381,063 priority patent/US20040076824A1/en
Priority to EP01970150A priority patent/EP1319739A4/fr
Publication of WO2002024991A1 publication Critical patent/WO2002024991A1/fr

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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 made of a specific polyamide resin composition having excellent flame retardancy and strength, and more particularly to a multifilament using a plurality of single yarns (monofilaments). Is related to the crimped yarn, that is, BCF (Bulked Continuous Filament). Further, the present invention relates to a carpet which is free from halogen compounds, has high safety, and has excellent flame retardancy by using the BCF. The present invention also relates to the application of the monofilament to a wire harness protection net / mesh sheet, and further relates to a specific multilayer filament suitable for the mesh sheet use and the like. Background art
  • Flame-retardant polyamide filaments are used in various applications as monofilaments or as multifilaments.
  • monofilaments are mainly used as protective nets for wire harnesses in home appliances, vehicles, aircraft, etc., and as yarns for multifilaments, especially in houses, buildings, automobiles, railway vehicles, aircraft, etc.
  • BCF Bulk-Continuous Filament
  • a multifilament that had been directly spun and stretched and crimped was used. Two to three strands of the multifilament were tufted into a base fabric, and rubber was attached to the back side and processed into a matte shape.
  • An object of the present invention is to provide a flame-retardant polyamide filament that is excellent in flame resistance without containing a halogen compound, is highly safe for the environment, and has excellent strength.
  • An object of the present invention is to provide a polyimide BCF obtained by crimping, and a carpet using the polyamide BCF. Disclosure of the invention
  • the present invention has been made to solve the above-mentioned problems, and the gist of the present invention is to provide 98 to 80 parts by weight of a polyamide resin having a relative viscosity of 2.0 to 4.0 and a triazine-based flame retardant 2 to A flame-retardant polyamide-filament comprising a polyamide resin composition containing 20 parts by weight and having a tensile strength of at least 2.0 cN / dtex according to a measurement method in accordance with JISL 1013, wherein Polyamide-present in flame-retardant polyamide 'filaments, characterized in that the average particle size of the triazine flame retardant dispersed in the filament is less than 5 ⁇ m.
  • Another gist of the present invention resides in a flame-retardant polyamide filament characterized by being a multifilament using a plurality of the above monofilaments.
  • Another gist of the present invention resides in a flame-retardant polyimide BCF (Bulk ed Continuos Filament) obtained by crimping the above-mentioned multifilament.
  • Another aspect of the present invention resides in a carpet using the above-described flame-retardant polyamide BCF.
  • Another gist of the present invention is that the polyamide filament has a fiber degree of 300 to 56 5
  • the polyamide De 'filament force? Resides in a monofilament fiber of 4 0 0 ⁇ 1 1 0 0 0 dtex, also formed by Henmo it, porosity showing a mesh There are 2 0-3 0%, weight per unit area lies in the message seeds one bets is 1 0 0 ⁇ 6 0 0 g / m 2.
  • Still another gist of the present invention is to provide a polyamide resin composition containing 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.
  • a flame-retardant polyimide resin layer A having an average particle size of less than 5 ⁇ m in a state where the triazine-based flame retardant is dispersed in a filament, and at least an inner layer thereof, and The flame-retardant multilayer filament using any of the flame-retardant polyamide resin layer A, the polyamide resin layer B having a composition other than the flame-retardant polyamide resin layer A, or the polyolefin resin layer C.
  • the difference in melting point between the polyamide resin forming the inner layer and the resin used in the surface layer is present in the multilayer filament of the polyamide resin of the inner layer which is higher by 5 ° C or more. After crossing the layer filaments in a mesh, The surface layer of the cross-section lies in heat-sealed mesh sheet.
  • polyamide resin in the present invention various polyamides obtained by polycondensation of a lactam having three or more rings, a polymerizable ⁇ -amino acid, a dibasic acid and diamine can be used. Specifically, the weight of ⁇ -force prolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 91-aminononanoic acid, 1-pyrrolidone, 1-pyridone, etc.
  • diamines such as hexamethylene diamine, nonamethylene diamine, pendecamethylene diamine, dodecamethylene diamine, metaxylylene diamine and terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid
  • Particularly preferred polyamides in the present invention include polyamide 6, copolymerized polyamide 6Z66, and polyamide 66 in view of flame retardancy, mechanical strength, and moldability.
  • the terminal of the polyamide resin in the present invention may be sealed with a carboxylic acid or an amine, and a polyamide resin sealed with a carboxylic acid or amine having 6 to 22 carbon atoms is particularly desirable.
  • the carboxylic acid used for the sealing is, for example, an aliphatic monocarboxylic acid such as cabronic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearinic acid, and behedonic acid. Is mentioned.
  • amine examples include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, normitylamine, stearylamine and behenylamine.
  • the amount of carboxylic acid or amine used for sealing is preferably about 30 ⁇ eqZg.
  • the polyamide resin used in the present invention has a degree of polymerization within a certain range, that is, a relative viscosity of 98% sulfuric acid according to JISK 6810, a value measured at a concentration of 1% in sulfuric acid and a temperature of 25 ° C. It is in the range of 0 to 4.0. If the relative viscosity is lower than 2.0, the melt viscosity is too low to make spinning difficult, and also the mechanical strength is reduced, causing breakage in the BCF processing stage. On the other hand, if the relative viscosity is higher than 4.0, not only the melt fluidity is impaired, but also stable spinning cannot be performed due to thermal deterioration due to shear heat generation, which is not preferable. Triazine flame retardant
  • Examples of the triazine-based flame retardant in the present invention include a compound represented by the following general formula (1) or (2), melamines, and a reaction product of a cyanuric acid and a melamine at a molar ratio of 1: 1. .
  • R 1 ! ⁇ Represents a hydrogen atom or an alkyl group, respectively.
  • Specific examples of the compound represented by the general formula (1) include sialic acid, trimethyl cyanurate, triethyl cyanurate, tri (n- propyl) Shianureto, methyl cyanurate, Jefferies Chi cyanurate such force? like.
  • Specific examples of the compound represented by the general formula (2) include isocyanuric acid, trimethyl isocyanate, triethyl isocyanate, tri (n-propyl) isocyanurate, getyl isocyanurate, and methyl isocyanate. Nurate, etc.
  • melamines examples include melamine, melamine derivatives, compounds having a structure similar to melamine, condensates of melamine, and the like.
  • Specific examples of the melamines include, for example, melamine, ammelide, ammeline, formoguanamine, guanylmelamine, cyanomamelamine, arylguanamine, melam, melem, melan, and the like.
  • a reaction product having a molar ratio of 1: 1 between cyanuric acid and melamine from the viewpoint of thermal stability, for example, there is no inconvenience such as blooming in which a decomposition product emerges on the surface of the molding during molding.
  • melamine succinate is particularly preferable.
  • some of the amino groups or hydroxyl groups in melamine cyanurate may be substituted with other substituents.
  • Melamine cyanurate can be obtained, for example, by mixing an aqueous solution of cinuric acid and an aqueous solution of melamine, reacting the mixture at 90 to 100 ° C. with stirring, and filtering the generated precipitate to obtain a white melamine. Solid and commercially available It is preferable to use as it is or to pulverize it into a fine powder. Average particle size of triazine flame retardant
  • Triazine-based flame retardants are usually in the form of agglomerates of fine powder having a submicron order particle size.
  • This average particle diameter represents the particle diameter of the dispersed particles obtained by aggregating submicron-order fine powders, and in the present invention, represents the number average particle diameter. Further, the average particle size indicates a measured value of the dispersed particles in the drawn filament when the filament is drawn.
  • 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 cross section, and measuring the size of the trace of the flame retardant by SEM observation. Can be.
  • the triazine-based flame retardant dispersed in the filament has an average particle size of less than 5 ⁇ m. If the average particle size exceeds 5 m, monofilament cutting may occur at any of the filament forming step, that is, the monofilament spinning, drawing step and crimping step.
  • the triazine-based flame retardant When the triazine-based flame retardant is blended with the polyamide resin, aggregates may be broken during the blending process and the spinning process. However, stable filament molding, that is, spinning and drawing of a monofilament, is performed. to do, it mosquitoes? preferably used in pulverized beforehand to a predetermined size.
  • the average particle size of the triazine-based flame retardant before blending can be measured with an existing powder particle size measuring device, for example, a sedimentation particle size meter, a laser diffraction type particle size meter, or a normal optical microscope.
  • the compounding amount of the triazine-based flame retardant must be 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. Triazine flame retardant the amount is less than 2 parts by weight flame retardance lowered Shasuku, 2 0 parts by weight unfavorably liable to Tan'itoryoku s cut during exceeds the BCF produce.
  • Incorporation of the triazine-based flame retardant into the polyamide resin can be performed by any of various well-known methods at any stage immediately before the spinning step in the production of BCF. Most A simple method is to pelletize a predetermined amount of a polyamide resin and a triazine-based flame retardant by melt mixing extrusion. However, if necessary, a master pellet in which a triazine-based flame retardant in an amount larger than a predetermined amount is kneaded in advance into a polyamide resin is prepared, and the master pellet is dry-blended with a polyamide resin for dilution. A resin composition can also be obtained. After the dry blending, a method of pelletizing by melt mixing extrusion may be used.
  • a pigment, a dye, a filler, a nucleating agent, a release agent, a stabilizer, an antistatic agent, and other known additives may be used. It can also be blended. Further, in the polyamide resin composition of the present invention, a thermoplastic resin other than the polyamide resin can be blended as long as the effects of the present invention are not impaired. Flame retardant polyamide filament
  • the polyamide 'filament is a monofilament (single fiber) composed of one yarn (single yarn) obtained by a usual melt-spinning process, and a plurality of those bundled or twisted. Multifilaments (multifilaments) are also included. Or, split fiber split obtained by tearing the film
  • the monofilaments include those having short fibers and long fibers, and may have irregular shapes other than those having a circular or elliptical cross section.
  • the monofilament is used as a multifilament raw yarn by being bundled or twisted, and when the monofilament is used as a core material and combined with a fiber made of another resin to form a multifilament.
  • another fiber is used as a core material and combined with the monofilament to form a multifilament.
  • monofilaments may be used as fishing line or gut, etc., or they may be processed into knitted or woven fabrics and used for wire harness protection nets or meshwork for construction work. There is. Also, multifilaments, split fibers, and split fibers can be used for similar applications as the monofilament. Or, it is processed and used for actual use. Polyamide multifilament
  • the polyamide multifilament is necessary after melting and spinning a polyamide resin composition obtained by blending a specific amount of a triazine-based flame retardant having a specific particle diameter with the above-described polyamide resin. It refers to one that has been stretched accordingly and passed through a process such as bundling and twisting.
  • the spun single yarn may have various cross-sectional shapes.
  • the single yarn has a cross-sectional shape such as Y-shaped; 1 dog (Y cross-section), trilobal cross-section, etc., as well as those having a hollow portion in these shapes. It is preferably a bulky continuous yarn having an irregular cross section such as a hollow cross section.
  • the thickness of such a spun single yarn is appropriately determined depending on the use of the multifilament, and is not particularly limited. However, when used for BCF, the single yarn (monofilament) ranges from 4 to 90 dtex. When the cross section is round, the single yarn diameter is preferably in the range of 0.02 mm to 0.1 mm, and the total multifilament is preferably in the range of 111 1 to 3333 dte (1000 to 3000 denier).
  • the flame-retardant polyamide BCF (Bulk Content FI 1 anament) of the present invention is generally used frequently for the purpose of improving the covering property of carpets and the like and the antifouling property.
  • Spinning, drawing and winding are usually performed using conventional BCF manufacturing equipment, using a polyamide resin composition composed of a bulky continuous processed yarn having an irregular cross-section such as a hollow cross-section and blending the above flame retardant. It can be manufactured through three steps of shrinkage.
  • the BCF includes a BCF made of such a 64- to 68-F multifilament (which may be referred to as a BCF ply yarn) and further twisted by about 2 to 4 yarns (this is called a BCF pile yarn). Sometimes referred to as). Polyamides and monofilaments ''
  • the polyamide monofilament of the present invention can be used as it is, for example, because it has a certain strength such as fishing line and gut.
  • it is processed into a woven or knitted fabric to protect the wire harness from the viewpoint of flame retardancy and strength.
  • the wire harness protection net is a tube made of densely woven monofilament to protect the wires used in home appliances, car rain, aircraft, etc. from harnesses (electric wires and signal cables) from external impact and stress. ⁇ ⁇ protection net
  • the polyamide 'monofilament used for this purpose is, for example, drawn 3.5 to 5.0 times, and preferably drawn 3.5 to 4.5 times.
  • Such a monofilament preferably has a diameter of from 0.01 to 3 mm, more preferably from 0.02 to 2.5 mm, and more preferably from 0.0 to! 0.8 mm as a wire harness protection net.
  • the thickness is of the order of magnitude, most preferably 0.2 to 0.5 mm.
  • the degree of fiber depends on the application, but is preferably from 300 to 56500 dtex.
  • mesh sheets mainly used for construction work are often spread around construction sites such as houses and buildings and construction sites such as bridges to prevent and protect against danger. And knitted by a knitting machine.
  • the mesh opening is not particularly limited as long as it is in a range having air permeability.
  • the porosity indicating the opening is 20 to 30%.
  • Ma The basis weight is 100 to 600
  • it is 200 to 400 g / m 2 .
  • the monofilament to be knitted is, for example, stretched 3.5 to 5.5 times, preferably 4 to 5 times.
  • the monofilament has a yarn diameter of 0.1 to 1.5 mm, preferably 0.2 to 1.1 mm, and a fiber degree of 400 to: L l OOO dtex.
  • 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 flame retardant is used.
  • the flame retardant polyamide resin layer A having an average particle diameter of less than 5 zm in a state where the triazine flame retardant is dispersed in the filament is used as at least an inner layer, and the flame retardant polyamide resin is formed on the surface layer.
  • a flame-retardant multilayer filament using any one of the resin layer A, the polyamide resin layer B having a composition other than the flame-retardant polyamide resin layer A, or the polyolefin resin layer C, and the JISL of the multilayer filament is used.
  • the multilayer filament can also be used as a flame-retardant multilayer filament having a tensile strength of 2.0 cN / dtex or more according to a measurement method in accordance with 113.
  • an intermediate layer such as an adhesive layer may be provided between the inner layer and the surface layer.
  • the difference in melting point between the polyamide resin in the polyamide resin layer A of the inner layer and the resin used in the surface layer is considered to be higher than that of the polyamide resin in the inner layer by 5 ° C or more. It is suitable for obtaining mesh sheets without misalignment by crossing the obtained multifilaments in a mesh shape and then heat-sealing the surface layer at the intersection.
  • the polyamide-filament has a tensile strength of 2.0 cN / dtex or more by a measurement method based on JISL103.
  • the strength is preferably 2.5 cN / dtex or more, more preferably 3.0 cN / dteX or more.
  • the tensile strength is represented by a value obtained by dividing the tensile breaking load by the fiber degree of the filament.
  • the unit is represented by SI unit, cN / dteX.
  • the tensile load c N is 1Z of N It means 100, and the fiber degree dtex (decitex) means the number of grams per 10,000m in length.
  • the tensile strength is less than 2.0 c / dtex, the practical strength and the strength at the time of knitting will be insufficient. It breaks when used as a product and is not preferred. In the case of a multi-layer filament, it refers to the tensile strength in the dog state of the multi-layer filament, and the preferred range is the same.
  • Oxygen index (LP I) is the tensile strength in the dog state of the multi-layer filament, and the preferred range is the same.
  • the flame-retardant polyamide 'filament of the present invention preferably has a flame retardancy of 27 or more as an oxygen index by a measuring method based on JIS K7201.
  • the measured value is shown as the state of the multilayer filament.
  • the oxygen index the sample is required oxygen concentration order to continue combustion (volume 0/0), for example, if a 1 mm thickness of approximately sheet-like sample, if the oxygen index 22 or more, the air At a medium oxygen concentration, combustion cannot be continued, meaning that it is a self-extinguishing material.In the present invention, however, it is processed as carpets, wire harness protection nets, construction mesh sheets, etc.
  • the oxygen index is preferably 27 or more as a condition for achieving even more severe flame retardancy.
  • the measurement sample is kept at 23 ° C. and 65% RH for 24 hours or more, and then measured according to the above JISK 7201. I do.
  • BCF when it is made to be a normal diameter, it is a so-called multi-filament, in which about 64 single yarns of about 20 to 100 m are bundled, so that it can stand alone on the sample holder specified by JIS above. Can be measured. Contains halogen compounds
  • the flame-retardant polyamide filament of the present invention preferably does not contain a halogen compound.
  • a sample obtained by burning a filament or BCF obtained by processing it at 900 ° C is collected and analyzed by ion chromatography.
  • Means that the content of the halogen element, that is, fluorine, chlorine or bromine, determined by the following, is 10 ppm or less, preferably 5 ppm or less, more preferably 2 ppm or less, based on the weight of the sample. .
  • halogen element If the content of halogen element is below the specified value, even if incinerated, the combustion gas does not contain haematogen element, and it can be said that it is highly safe for the environment.
  • the flame-retardant polyamide BCF is useful as a raw yarn for carpet, and is formed into a mat shape through various known processing steps such as twisting, setting, tufting, and backing. It can be processed to obtain carpets.
  • a total formed by a conventional spinning, drawing and crimping direct connection type BCF production apparatus is used. Twist two to four multifilament BCFs of 1408 dtex and 64 F (single fiber degree is about 22 dtex), and then apply a moist heat setting at 120 to 130 ° C for about 1 minute to make pile yarn. Get.
  • the pile yarn was tufted to a base fabric using a tufting machine, and a backing, that is, an NBR rubber sheet containing a vulcanizing agent was applied to the back side, and the temperature was 170 ° C and the pressure was 294 kPa (3 kg / Pressed in cm 2 ) and processed into matte to obtain carpets.
  • a backing that is, an NBR rubber sheet containing a vulcanizing agent
  • Polyamide 6 resin 1-1 Novamid 1015J (relative viscosity: 3.0) manufactured by Mitsubishi Engineering-Plastics Corporation was used.
  • Polyamide 6 resin 1-2 Novamid 1020 J (relative viscosity: 3.5) manufactured by Mitsubishi Engineering-Plastics Corporation was used. ⁇ Copolymerized polyamide 6 Z 66 resin>
  • Copolymerized polyamide 6/66 resin 1-1 50% aqueous solution of a salt of adipic acid and hexamethylenediamine (hereinafter abbreviated as AH salt) and ⁇ -force prolactam (hereinafter abbreviated as CL) ) was heated to 100 ° C and mixed in a ratio of 15 parts by weight of AH salt and 85 parts by weight of CL, then charged in a 200 liter autoclave, and the internal pressure was 1275 kPa (13 kg). After raising the temperature to 270 ° C at Z cm 2), maintaining the internal temperature at 245 ° C, gradually reduced to stirring 49 k P a (0. 5 kg / cm 2), stirring power force s When the predetermined value was reached, the polymerization was stopped.
  • AH salt a salt of adipic acid and hexamethylenediamine
  • CL ⁇ -force prolactam
  • Copolymerized Polyamide 6 Z66 Resin 1-2 Polymerization was stopped in the same manner as in 1 above when the relative viscosity of the resin became 3.5. Melting point was 202 ° C.
  • Melamine Cyanurate MCA-C0 (equimolar reaction product of Cyanuric acid and melamine) manufactured by Mitsubishi Chemical Corporation was pulverized by a tabletop ball mill. The average particle diameter of this crushed product was measured using an automatic sedimentation particle sizer manufactured by Shimadzu Corporation and found to be 2.5 m.
  • Melamine Cyanurate MC A—C 0 (equimolar reaction product of Cyanuric acid and melamine) manufactured by Mitsubishi Chemical Corporation was classified using a 50-mesh sieve. The average particle size of this classified product was measured to be 80 m using an automatic sedimentation particle size meter manufactured by Shimadzu Corporation.
  • the polyamide resin composition shown in Table 1 was spun, drawn, and crimped directly connected to FI LTE (manufactured by 0 company 8.? Production equipment, 64F at 1408 dtex, single yarn fiber degree 22 dtex, trilobal ( A BCF multifilament having a trilobal cross section was formed. The first roll speed was 50 Om / min,
  • the tensile strength of the obtained BCF was measured, and the average particle size, oxygen index, and halogen element analysis of the triazine-based flame retardant in the single yarn were measured.
  • the results are shown in Table 1.
  • Each of the BCFs obtained in Examples 1 to 3 was processed into a mat form through various known processing steps such as twisting, setting, tufting, and backing, and was processed into a mat shape. However, it was possible to obtain carpets having excellent flame retardancy.
  • the polyamide resin composition shown in Table 1 was spun, drawn and crimped directly into a FI LTE ⁇ 0 company 8 ⁇ manufacturing equipment at 64 F at 1408 dtex, 22 dtex single yarn fiber density, and Trilon® (The force s when the BCF was formed (trilobe cross section) and thread breakage occurred frequently in the stretching process, and a sample (BCF) could not be obtained.
  • a protective net was knitted around a 12 mm diameter iron core which was a jig.
  • a wire harness in which the obtained protective net was attached around a bundle of electric wires was configured and put to practical use. After long-term use, it was confirmed that the wire bundle with the protective net was sufficiently protected against external stress.
  • a protective net was knitted around a 75 mm diameter iron core which was a jig.
  • a wire harness in which the obtained protection net was attached around a bundle of electric wires was configured and put to practical use. After long use, it was confirmed that the wire bundle with the protection net was sufficiently protected against external stress.
  • Dry heat drawing was performed three times, and finally dry heat annealing was performed at 170 ° C at a relaxation rate of 0.95 times to obtain a monofilament having a fiber degree of 8950 dte X (diameter of about 1.0 mm).
  • the oxygen index and tensile strength of the obtained monofilament were measured.
  • a single-screw extruder with a D 25, a multi-layer monofilament extruder connected to the multi-layer monofilament die from the gear pump at the end of each extruder, and the polyamide resin for the inner layer as shown in Table 5
  • the composition and the polyamide resin or polyamide resin composition for the surface layer are put into each extruder, and the multilayer and monolayer are melt-spun at a molding temperature of 250 ° C for both the inner layer and the surface layer, and passed through a cooling water bath having a water temperature of 10 ° C.
  • the film After being cooled and solidified, the film is subjected to wet heat stretching 3.5 times at 98 ° (:, 100% RH), and then subjected to dry heat stretching 1.43 times in dry air of 1751: After that, a dry heat ring was applied at a relaxation rate of 0.95 times at 165 ° C. As a result, a monofilament having a fiber degree of 2060 dte X (about 0.48 mm in diameter) was obtained. The cross section of the obtained monofilament was sliced with a force razor, the surface layer thickness was measured with an optical microscope, and the oxygen index and the tensile strength were measured.
  • a plain woven mesh sheet having a lmX lm and a basis weight of 400 g / m 2 was knitted.
  • the obtained mesh sheet was heated to 210 ° C. by a hot wind D heat device to fuse the intersection of the processes.
  • the obtained single-layer monofilament was coated on the surface layer of LLDPE at a resin temperature of 180 ° C. using a single-screw press equipped with a cross-head die for coating to obtain a multilayer monofilament.
  • the cross section of the obtained multilayer monofilament was sliced with a force razor, the surface layer thickness was measured with an optical microscope, and the oxygen index and tensile strength were measured.
  • a plain weave mesh sheet having a lmXl ni and a basis weight of 400 g / m 2 was knitted.
  • the obtained mesh sheet was heated to 160 ° C. by a hot-air heating device to fuse the intersection between the courses.
  • the monofilament (in the case of BCF, the monofilament was taken out) was notched with a force razor and split under liquid nitrogen.
  • the single yarn containing the obtained cross section was subjected to ultrasonic cleaning at room temperature in an n-hexane bath for 30 minutes to remove the triazine-based flame retardant from the cross section. Thereafter, platinum vapor deposition was performed on the cross section, and SEM observation was performed at a magnification of 5000 times, the major axis of the trace of removal of the triazine-based flame retardant was measured, and the average of 100 points was defined as the average particle diameter.
  • the oxygen index was measured using a D-type candle-burning tester manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K 7201.
  • Fatty triane flame retardant A (parts by weight) 0.5 25 "0.4 30 0.4
  • the present invention it is possible to obtain a polyamide 'filament excellent in flame retardancy and excellent in strength. In particular, even when a halogen-based flame retardant is not used, such an effect can be obtained.
  • the polyamide filaments are used as multifilaments in carpet yarns and can provide safe flame retardant BCF and carpets, and are also used as monofilaments. It is suitable for various applications such as wire-harness protection nets and meshes. Further, it is suitable for a batting sheet or the like as a multilayer filament.

Abstract

L'invention concerne des filaments polyamides ignifugeants obtenus à partir d'une composition de résine polyamide qui comprend 98 à 80 parties en poids d'une résine polyamide présentant une viscosité relative de 2,0 à 4,0, et 2 à 20 parties en poids d'un ignifugeant triazine. Les filaments polyamides ignifugeants de l'invention présentent une résistance à la traction d'au moins 2,0 cN/dtex déterminée selon la norme JISL1013. L'ignifugeant triazine est dispersé à l'état de particules dont le diamètre moyen des particules est inférieur à 5 νm. En particulier, les multifilaments polyamides de l'invention peuvent donner, par crêpage, des Bcf polyamides utiles pour la production de tapis. De plus, les monofilaments de l'invention sont utiles pour la production de filets de protection pour harnais à fils, feuilles à mailles, ou analogues, et les filaments multicouches conviennent pour la production de feuilles à mailles.
PCT/JP2001/008144 2000-09-20 2001-09-19 Filaments polyamides ignifugeants et leur utilisation WO2002024991A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU2001290244A AU2001290244A1 (en) 2000-09-20 2001-09-19 Flame-retardant polyamide filaments and their use
US10/381,063 US20040076824A1 (en) 2000-09-20 2001-09-19 Flame-retardant polyamide filaments and their use
EP01970150A EP1319739A4 (fr) 2000-09-20 2001-09-19 Filaments polyamides ignifugeants et leur utilisation

Applications Claiming Priority (4)

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JP2000284996 2000-09-20
JP2000-284996 2000-09-20
JP2001-32149 2001-02-08
JP2001032149 2001-02-08

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EP1460646B1 (fr) * 2003-03-17 2006-05-24 Nexans Câble flexible à gaine résistant à l'usure
JP2005205157A (ja) * 2003-12-26 2005-08-04 Uniplas Shiga Kk 難燃ナイロンカーペットおよびその製造方法
WO2012040332A2 (fr) * 2010-09-23 2012-03-29 Invista Technologies S.A R.L. Fibres ignifugeantes, fils, et tissus composés de ceux-ci
JP6355351B2 (ja) * 2013-09-30 2018-07-11 Ｋｂセーレン株式会社 合成繊維
US20190322805A1 (en) * 2018-04-18 2019-10-24 Invista North America S.A R.L. Flame-retardant polyamide composition
WO2020198668A1 (fr) 2019-03-28 2020-10-01 Southern Mills, Inc. Tissus ignifuges
US11891731B2 (en) 2021-08-10 2024-02-06 Southern Mills, Inc. Flame resistant fabrics

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JPS4891314A (fr) * 1972-03-03 1973-11-28
JPS56107012A (en) * 1980-01-31 1981-08-25 Asahi Chem Ind Co Ltd Flame-retardant fiber
US4321188A (en) * 1979-01-05 1982-03-23 Snia Viscosa Societa Nazionale Industria Applicazioni Viscosa S.P.A. Process for producing synthetic flame resisting polyamides, flame resisting filaments and fibres and products obtained by using the same
JPS57190990U (fr) * 1981-05-29 1982-12-03
JPH01105863A (ja) * 1987-01-14 1989-04-24 Kuroda Henshoku Kk メッシュシート及びその製造方法
US5604007A (en) * 1992-03-06 1997-02-18 Basf Corporation Method for producing polyamide carpet fibers with improved flame retardancy
JP2000303257A (ja) * 1999-04-14 2000-10-31 Unitika Ltd 防炎性人工芝用ヤーン及び防炎性人工芝

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JPS5817539B2 (ja) * 1978-09-18 1983-04-07 旭化成株式会社 メラミンシアヌレ−ト含有ポリアミド組成物の製造方法
DE50000303D1 (de) * 1999-08-30 2002-08-29 Ciba Sc Holding Ag Verfahren zum Färben oder Bedrucken von polyamidhaltigen Materialien
DE10038030A1 (de) * 2000-08-02 2002-02-14 Basf Ag Flammhemmende Garne und daraus hergestellte Gewebe
US20030056297A1 (en) * 2001-03-30 2003-03-27 University Of California Multifunctional textiles

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JPS4891314A (fr) * 1972-03-03 1973-11-28
US4321188A (en) * 1979-01-05 1982-03-23 Snia Viscosa Societa Nazionale Industria Applicazioni Viscosa S.P.A. Process for producing synthetic flame resisting polyamides, flame resisting filaments and fibres and products obtained by using the same
JPS56107012A (en) * 1980-01-31 1981-08-25 Asahi Chem Ind Co Ltd Flame-retardant fiber
JPS57190990U (fr) * 1981-05-29 1982-12-03
JPH01105863A (ja) * 1987-01-14 1989-04-24 Kuroda Henshoku Kk メッシュシート及びその製造方法
US5604007A (en) * 1992-03-06 1997-02-18 Basf Corporation Method for producing polyamide carpet fibers with improved flame retardancy
JP2000303257A (ja) * 1999-04-14 2000-10-31 Unitika Ltd 防炎性人工芝用ヤーン及び防炎性人工芝

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US20040076824A1 (en) 2004-04-22
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AU2001290244A1 (en) 2002-04-02

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