WO2002024991A1

WO2002024991A1 - Flame-retardant polyamide filaments and their use

Info

Publication number: WO2002024991A1
Application number: PCT/JP2001/008144
Authority: WO
Inventors: Hiroshi Urabe; Michio Nakata; Seiji Morimoto; Morio Tsunoda
Original assignee: Mitsubishi Engineering-Plastics Corporation
Priority date: 2000-09-20
Filing date: 2001-09-19
Publication date: 2002-03-28
Also published as: EP1319739A4; EP1319739A1; AU2001290244A1; US20040076824A1

Abstract

Flame-retardant polyamide filaments which are made from 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 and have a tensile strength of 2.0 cN/dtex or above as determined in accordance with JISL1013 and in which the triazine flame retardant is dispersed in the state of particles having a mean particle diameter of less than 5νm. In particular, the polyamide multifilaments according to the invention can give polyamide BCF by crimping, and the polyamide BCF is useful in producing carpets. Additionally, the monofilaments according to the invention are useful in producing protective nets for wire harnesses, mesh sheet, or the like, and the multi-layer filaments according to the invention are also suitable for mesh sheet.

Description

Description Flame Retardant Polyamide 'Filament and Technical Fields of Use

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. In particular, 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) is used for the carpets of this kind, but it is called BCF using polypropylene or nylon resin, which has not been given flame retardance until now. 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.

In recent years, from the viewpoint of safety, there has been a social demand that carpets should also be made flame-retardant, and in such cases, halogen-based flame retardants, which are said to cause environmental pollution and health problems, should be used. Instead, there has been a demand for carpets having excellent flame retardancy. In order to make polypropylene resin flame-retardant without using halogen-based flame retardants, it has been proposed to mix magnesium hydroxide and urea, but the amount is based on 100 parts by weight of polyolefin resin. A large amount of 40 parts by weight or more is required, and the strength of the single yarn is greatly reduced. Therefore, when processed into a mat shape, it cannot be put to practical use.

On the other hand, a method of flame retarding a polyamide resin without using a halogen-based flame retardant has been proposed in Japanese Patent Publication No. 51_54655 / JP-A-11-335552. The strength required for applications such as carpets and wire harness protection nets was insufficient.

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 μm.

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

0 0 dte X exists in the monofilament, and it exists in the wire harness protection net which knits it around the electric wire. Other aspects of the present invention, 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 μm 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. In addition, 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. Hereinafter, the present invention will be described in detail.

Polyamide resin

As the polyamide resin in the present invention, various polyamides obtained by polycondensation of a lactam having three or more rings, a polymerizable ω-amino acid, a dibasic acid and diamine can be used. Specifically, the weight of ε-force prolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 91-aminononanoic acid, 1-pyrrolidone, 1-pyridone, etc. Coalescence, 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 A polymer obtained by polycondensing dicarboxylic acid such as dartal acid or a copolymer thereof; Mid 4, 6, 7, 8, 11, 12, 66, 69, 610, 61 1, 612, <o / 66, 6/12, etc., aliphatic polyamides and their copolymers, polyamide 6 Aromatic polyamides such as T, 6 / 6Τ, 6Τ / 6I, and MXD6 and copolymers thereof are listed, and a plurality of these kinds of polyamide resins can be used in combination.

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. Specifically, 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. Examples of the amine 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 μeqZg.

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. .

(1) (2)

(In the formula, 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.

Examples of the melamines 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.

In the present invention, in particular, 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. And melamine succinate is particularly preferable. Also, 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.

In the present invention, the triazine-based flame retardant dispersed in the filament has an average particle size of less than 5 μm. 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.

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. Polyamide resin composition,

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.

In addition, in the resin composition of the present invention, in addition to the triazine-based flame retardant, 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

In the present invention, 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

(Flat) Fiber etc. are also included. Among them, the present invention is excellent in application to a monofilament obtained by melt spinning or a multifilament using the same. 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. Conversely, there is also a use in a case where another fiber is used as a core material and combined with the monofilament to form a multifilament. In addition, 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

In the present invention, 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. By devising the cross-sectional shape of the spinning nozzle or the like, the spun single yarn may have various cross-sectional shapes. In particular, in the case of BCF, 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).

Also, in order to form a multifilament, a plurality of such single yarns are bundled or twisted, but in the case of a BCF, about 10 to 100 filaments are usually used, and in a general machine for manufacturing a BCF, Used by focusing 64 to 68 tubes. Flame retardant polyamide BCF

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. For example, Japanese Unexamined Patent Publication No. Hei 9-95834, "Textile Handbook Second Edition"

(For example, edited by Maruzen Co., Ltd.), for example, after spinning about 64 to 68 single yarns, immediately, for example, about 3.0 to 4.5 times, preferably 3.0 times with a hot roll. ~Four Stretched about 0 times. Immediately crimped by fluid indentation with pressurized steam, etc., relaxed and cooled, wound up on product bobbin, llll ~ 3333 dtex (1 000 ~ 3000 denier), 64 ~ Obtain a 68 F multifilament. Commercial production facilities operate at line speeds of 2000-3000 mZmin. 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. In the present invention, it is processed into a woven or knitted fabric to protect the wire harness from the viewpoint of flame retardancy and strength. Mesh curing sheet called mesh sheet used for construction of nets. Suitable for use in protective sheets.

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.保護 ^ 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.

Furthermore, 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. For example, as a mesh sheet for construction work, the porosity indicating the opening is 20 to 30%. Ma The basis weight is 100 to 600

Preferably it is 200 to 400 g / m ² . In this case, the monofilament to be knitted is, for example, stretched 3.5 to 5.5 times, preferably 4 to 5 times. Usually, 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. Polyamide '' Multilayer monofilament

In the present invention, 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. It 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. In the case of the multilayer filament, an intermediate layer such as an adhesive layer may be provided between the inner layer and the surface layer. In this case, in particular, 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. Tensile strength

In the present invention, the polyamide-filament has a tensile strength of 2.0 cN / dtex or more by a measurement method based on JISL103. For applications requiring particularly high strength, such as mesh sheets for construction work, the strength is preferably 2.5 cN / dtex or more, more preferably 3.0 cN / dteX or more. In the present invention, 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. Where 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. If 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)

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. In the case of a multilayer filament, 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. However, considering the conditions of use, the oxygen index is preferably 27 or more as a condition for achieving even more severe flame retardancy.

Since the oxygen index also changes depending on the water absorption of the polyamide resin composition, in the present invention, 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. Also, in the case of 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. In this method, 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. .

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.

Application of BCF to cars

In the present invention, 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. For example, as described in JP-A-11-285466, JP-A-10-225423 and the like, 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. Next, 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. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist of the present invention.

In Examples and Comparative Examples, the following polyamide resins and triazine-based flame retardants were used.

Ku Polyamide 6 Resin>

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 ε-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.

Then, nitrogen was introduced, the pressure was restored, the strands were drawn out, pelletized, unreacted substances were extracted and removed using boiling water, and dried. The relative viscosity of the copolymerized polyamide 6/66 resin thus obtained was 3.0, and the melting point was 202 ° C. 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.

Triazine-based flame retardant>

Triazine flame retardant A

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.

Triazine flame retardant B

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 above polyamide 6 resin and Z or copolymerized polyamide 6/66 resin and the above triazine flame retardant A or B were blended in the proportions shown in Table 1, and a twin-screw extruder with a cylinder diameter of 30 mm and vent was used. Using a kneader (TEX30, manufactured by Nippon Steel Works), the mixture was melt-kneaded at a resin temperature of 240 to 260 to obtain a polyamide resin composition pellet. Thereafter, the obtained polyamide resin composition pellet was dried under reduced pressure of 120 kPa at a pressure of 120 kPa for 6 hours, and then subjected to molding of various samples. <Production of BCF>

Examples 1 to 3 and Comparative Example 1

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,

Since the final roll speed was 190 Om / min, the draw ratio was 3.8 times o

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.

Comparative Examples 2 to 4

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.

Examples 4 to 6 and Comparative Examples 5 to 8

The polyamide resin composition shown in Table 2 was applied to an extruder with a full-flight screw with a cylinder diameter of 3 Omm and L / D = 27, and an extruder equipped with a gear pump at the tip of a single-screw extruder. Melt spinning at a temperature of 254 ° C, passing through a cooling water bath with a water temperature of 10 ° C, solidifying it by cooling, stretching it 3.5 times at 98 ° C and 100% RH, and then drawing it at 175 ° C The film was stretched in dry air by 1.34 times and finally subjected to dry heat annealing at 165 ° C at a relaxation rate of 0.95 times to obtain a monofilament having a diameter of 0.2 mm.

The oxygen index, tensile strength and the like of the obtained monofilament were measured. Table of evaluation results See Figure 2.

Furthermore, using the obtained four monofilaments, a protective net was knitted around a 12 mm diameter iron core which was a jig. In Examples 4 to 6, 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.

Examples 7 to 8 and Comparative Examples 9 to: 1 2

The resin temperature of the polyamide resin composition shown in Table 2 was measured using an extruder equipped with a gear pump at the tip of a single-screw extruder equipped with a full-flight screw with a cylinder diameter of 40 mm and L / D = 27. After melt-spinning at 47 ° C and passing through a cooling water bath with a water temperature of 12 ° C to solidify by cooling, in 98, it was stretched by 3.4 times under 100% RH, and then hot-drawn. In dry air at 180 ° C, dry heat stretching was performed by a factor of 1.3, and finally, at 170 ° C, dry heat annealing was performed at a relaxation rate of 0.95 times to obtain a diameter of 2.0. mm monofilament was obtained. The oxygen index, tensile strength and the like of the obtained monofilament were measured. Table 2 shows the evaluation results.

Furthermore, using the obtained four monofilaments, a protective net was knitted around a 75 mm diameter iron core which was a jig. In Examples 7 and 8, 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.

Comparative Examples 13 and 14

In Examples 5 and 8, the same operation as in Examples 5 and 8 was performed except that the triazine-based flame retardant A was replaced with the triazine-based flame retardant B in the composition, respectively. Was not obtained.

Example 9 and Comparative Example 15: L 7

The resin temperature of the polyimide resin composition shown in Table 3 was measured using an extruder equipped with a gear pump at the tip of a single-screw extruder equipped with a full flight screw with a cylinder diameter of 30 mm and LZD = 27. After melt-spinning at ° C and passing through a cooling water bath at a water temperature of 10 to cool and solidify, it is stretched 3.5 times at 98 ° C and 100% RH, and then stretched by 17%. 5 ° C In hot air stretched 1.43 times in dry air, and finally dried at 165 ° C at 0.95 times dry heat to obtain a fiber density of 2060 dte X (diameter approx. .48 mm) monofilament was obtained. The oxygen index and tensile strength of the obtained monofilament were measured.

Further, using the obtained monofilament, a plain woven mesh sheet having a lmX lm and a basis weight of 400 gZm ² was knitted.

Example 10 and Comparative Examples 18-20

Melt spinning of the polyamide resin composition shown in Table 4 at a resin temperature of 247 ° C using a single-screw extruder equipped with a gear pump at the tip of a single-screw extruder equipped with a full flight screw with a cylinder diameter of 40 mm and L / D = 27 After passing through a cooling water bath with a water temperature of 12 ° C to be cooled and solidified, it is subjected to wet heat drawing at 98% under 100% RH by 3.8 times, and then in dry air at 180 ° C at 1. 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.

Further, using the obtained monofilament, a plain woven mesh sheet having lmX lm and a basis weight of 400 g / m ² was knitted.

Examples 11 to: I 2 and Comparative Example 2 '1 to 24

The inner layer extruder is a single-screw extruder equipped with a gear pump at the tip and a full flight screw with L / D = 27, and the surface extruder is a cylinder diameter 20 mm with a gear pump at the tip and L / D = 27. 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. 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.

Using the obtained monofilament, 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.

It should be noted that, this time, in the comparative example 22, by using the obtained monofilament, tried to cane a mesh sheet net weaving, could not be obtained finished product force ^s of Shimare ,, Messhushi over door is broken at the time of net weaving Was. Further, in Comparative Examples 23 and 24, during the formation of the multilayer monofilament, the filament was broken in the stretching step, and a filament having a desired fiber degree could not be obtained.

Example 13 and Comparative Example 25

The resin temperature of the polyamide resin composition shown in Table 6 was measured using an extruder equipped with a gear pump at the tip of a single-screw extruder equipped with a full flight screw with a cylinder diameter of 3 Omm and LZD = 27. Melt spinning at 250 ° C, cooling and solidifying through a cooling water bath with a water temperature of 10 ° C, stretching 3.5 times at 98 ° C and 100% RH, and then drawing at 175 ° C In the air, dry-heat stretched 1.43 times, and finally subjected to dry-heat annealing at a relaxation rate of 0.95 times at 165 ° C to a fiber density of 18 10 dte X (diameter approximately 0.45 mm). Was obtained.

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.

Using the obtained monofilament, 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 evaluations performed in this example and comparative examples were based on the following criteria.

(1) Relative viscosity

Measured at 25 ° C, 98% sulfuric acid, resin concentration 1% according to JIS K6810 did.

(2) Melting point

Measure the melting peak temperature when 1 Ommg of the sample was heated at 10 ° CZ using a DSC20 manufactured by SEIKO ELECTRONICS INDUSTRIES CO., LTD.

(3) Average particle size of triazine flame retardant dispersed in monofilament

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.

(4) Oxygen index

After the sample was allowed to stand for 24 hours or more in a room at 23 ° C. and 65% RH, the oxygen index was measured using a D-type candle-burning tester manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K 7201.

(5) Halogen element analysis

05 mg of the sample was burned at 900 C using a sample combustion device QF-02 type manufactured by Dia Instruments Co., Ltd., and the combustion gas was introduced into a 0.3% concentration of hydrogen peroxide and trapped. . The trap solution was subjected to quantitative analysis of fluorine, chlorine, and bromine with an ion chromatograph C 7000 E manufactured by Yokogawa Analytical Systems Co., Ltd.

(6) Tensile strength

After the sample was left in a room at 23 ° C and 65% RH for 48 hours or more, the tensile strength was measured in accordance with JISL1013. The unit was expressed in SI units cNZd tex. table 1

(ND: not detected)

* 1: The shape of the flame retardant is not recognized.

* 2: Samples could not be obtained due to frequent yarn breakage during the drawing process _c Table 1 (continued)

2: The sample was not obtained due to frequent yarn breakage in the stretching step.

Table 2

Example .

4 5 6 7 8 HOLIAMI 6 Resin-2 (parts by weight) ■ O

Po

A Copolymer e. Riamide 6/66 resin _2 c

ヽ o y i c Π

DO Cheung

Satoguchi 1

Tree

Fat “Trian-based flame retardant A (parts by weight) 5 8 6 6 5

Success

Thorium flame retardant B (parts by weight)

Monofilament diameter (mm) 0.2 0.2 0.2 2.0 2.0 8

Monofilament fiber degree (dtex) 360 360 360 36000 36000 Tensile strength (cN / dtex) 4.2 4.3 4.0 3.5 3.4 Average particle size of flame retardant μm 0.8 0.8 0.8 1.2 1.2 Valency oxygen index (%) 27 30 28 28 27 Protection Net knitting good good good good good good

F ND ND ND ND ND Bread (ppm) C 1 <2 <2 <2 <2 <2

ND ND ND ND Table 2 (continued 1)

Comparative example

5 6 7 8 9 e. Lamide 6 resin-2 (parts by weight) w.V 1 R

Re

A Copolymer e. Riamide 6/66 resin-2 on

, 丄 14 A Dy.

, Village!

Sato Ell

Do

Tree

Fatty triane flame retardant A (parts by weight) 0.5 25 "0.4 30 0.4

Success

Material Trian flame retardant B (parts by weight) Monofilament diameter (mm) 0.2 0.2 0.2 0.2 2.0 Monofilament fiber degree (dtex) 360 360 360 360 36000 Tensile strength (cN / dtex) 7

丄. Ί A

丄 O .O Average particle size of flame retardant μm) 0.8 0.8 0.8 0.8 1.2

Π Monovalent oxygen index (%) 24 36 24 37 24 At the time of knitting At the time of knitting Protective net knitting property Good Good Good Break Break

F ND ND ND ND ND Haloke Elemental analysis (ppm) C 1 <2 <2 <2 <2 <2

B r ND ND ND ND ND Table 2 (continued 2)

* 3: The film was broken in the stretching step, and a monofilament having a diameter of 0.2 mm was not obtained.

* 4: Broken in the stretching step, and no monofilament with a diameter of 2.0 mm was obtained. Table 3

: Broken in the drawing process, monofilament with a fiber degree of 2060 dtex could not be obtained _c

Table 4

6: Broken in the drawing process, monofilament with a fiber degree of 8950 dtex was not obtained

Table 5

* 7: The film was broken during the stretching process, and a multilayer monofilament with a fiber degree of 2060 dtex was not obtained. Table 6

According to 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 rutsch sheet or the like as a multilayer filament.

Claims

The scope of the claims

1. Relative viscosity 2. A polyamide resin composition containing 98 to 80 parts by weight of a polyamide resin having a viscosity of 4.0 to 4.0 and 2 to 20 parts by weight of a triazine-based flame retardant is used.

Flame-retardant polyamide 'filaments having a tensile strength of 2.0 cN / dtex or more measured according to L 1013, and the average of triazine-based flame retardants dispersed in the polyamide' filaments Flame-retardant polyamide 'filaments having a particle size of less than 5 µm.

2. The flame-retardant polyamide according to claim 1, which does not contain a halogen compound.

3. The flame-retardant polyamide filament according to claim 1 or 2, wherein the triazine-based flame retardant is an equimolar reaction product of cyanuric acid and melamines.

4. The flame-retardant polyamide 'filament according to any one of claims 1 to 3, having an oxygen index (L0I) of 27 or more according to a measurement method in accordance with JISK 7201.

5. The flame-retardant polyamide filament according to any one of claims 1 to 4, which is a multifilament comprising a plurality of monofilaments.

6. The flame-retardant polyamide 'filament according to claim 5, wherein the monofilament has a fiber degree of 4 to 90 dtex.

7. The flame-retardant polyamide 'filament according to any one of claims 1 to 4, wherein the filament is a monofilament having a fiber degree of 300 to 56500 dtex.

8. The flame-retardant polyamide 'filament according to any one of claims 1 to 4, which is a monofilament having a fiber degree of 400 to 11000 dtex.

9. A flame-retardant polyamide BCF (Bulk ed c con nti n u o u s f i a la me n t n), which is obtained by crimping the flame-retardant polyamide ′ which is a multifilament according to claim 5.

10. A power plant comprising the flame-retardant polyamide BCF according to claim 9.

11. A wire harness protection net, wherein the flame-retardant polyamide filament according to claim 7 is woven in a tube shape around an electric wire.

12. The flammable polyamide filament according to claim 8, which is knitted, has a porosity indicating opening of 20 to 30%, and a basis weight of 100 to 600 gZm ^2. A mesh sheet, characterized in that:

13. 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 is used. A flame-retardant polyamide resin layer A having an average particle diameter of less than 5 μm in a state where the flame-retardant is dispersed in filaments is used at least as an inner layer, and the flame-retardant polyamide resin is used as a surface layer. A flame-retardant multilayer filament using any one of a layer A, a polyamide resin layer B having a composition other than the flame-retardant polyamide resin layer A, and a polyolefin resin layer C, and A flame-retardant multilayer filament characterized by having a tensile strength of 2.0 cN / dtex or more as measured according to JISL 101 3.

14. The flame-retardant multilayer filament according to claim 13, having an oxygen index (L0I) of 27 or more as measured by a measurement method based on JISK7201.

15. The difference between the melting point of the polyamide resin in the polyamide resin layer A forming the inner layer and the melting point of the resin used in the surface layer of the boriamid resin in the inner layer is higher by 5 ° C. or more. 14. The flame-retardant multilayer filament according to 14.

16. A mesh sheet obtained by intersecting the multi-layered filaments according to claim 15 in a mesh shape, and then heat-sealing a surface layer at a weft intersection.