JP2010018906A - Flame-retardant polyamide fiber and fabric formed from the same - Google Patents

Abstract

Disclosed are a slow-flammable polyamide fiber and a fabric that suppress drip during combustion and have a high combustion time delay effect.
SOLUTION: (A) Polyamide-based resin 70 to 95% by weight, (B) Swellable layered silicate 0.5 to 10% by weight, (C) Diphosphinate, polyphosphate, phosphinate A flame retardant polyamide fiber comprising at least 3 to 10% by weight of at least one phosphate.
[Selection figure] None

Description

  The present invention relates to a polyamide fiber having a high combustion rate retarding effect and a fabric comprising the same, in which drip during combustion is suppressed by a synergistic effect of a swellable layered silicate and a specific phosphate.

  Conventionally, halogen flame retardants such as chlorine-containing flame retardants and bromine-containing flame retardants, or halogen flame retardants and antimony flame retardants have been included as flame retardant methods for materials such as polyamide fibers. Many materials have been proposed. However, although these materials are excellent in flame retardancy, halogen flame retardants have problems such as the possibility of generating halogenated gas during combustion, and many studies have been made to solve these problems. .

  For example, studies have been made using phosphorus compounds as flame retardants that do not contain halogen elements or antimony elements. Many materials containing phosphoric flame retardants using phosphate esters have been proposed, but the flame retardancy is lower than that of halogen and antimony flame retardants, and the flame retardant performance is insufficient. There was a problem to do.

  As non-drip forming of polyamide fiber, addition of an organically swellable layered silicate has been proposed (for example, see Non-Patent Document 1). The addition amount of the swellable layered silicate is examined in the range of 5 to 10% by weight, but 8 to 10% by weight of the swellable layered silicate must be used in order to develop the non-drip effect. There is a description that the yarn-making property is poor. The non-patent document has no description regarding the combined use with other flame retardants.

  An example in which a swellable layered silicate is used for a polyamide-based resin is disclosed (for example, see Patent Document 1). Although a phosphoric acid compound is used in combination, there is a description that the phosphorus compound may be organic or inorganic, and the purpose is to prevent coloring during injection molding of automobile fuses and to suppress the generation of cracks in a high temperature atmosphere. Is. There is no description regarding the combustion characteristics for the purpose of the non-drip of the present application.

  A flame retardant using a swellable layered silicate has been proposed (see, for example, Patent Document 2). Although the combination with general flame retardants, such as a phosphorus compound, is described, there is no description about the combustion characteristic aiming at the non-drip of the fiber and fabric of this application.

That is, the present situation is that there is no sufficient flame retardant for the purpose of manifesting the effect of suppressing non-drip and burning rate, which is the object of the present application.
Polymer Eng. and Sci. , 48, 662 pages (2008) JP 2004-95279 A JP 2004-331975 A

  An object of the present invention is to provide a polyamide fiber and a fabric in which drip at the time of combustion is suppressed and a combustion rate delaying effect is high in view of the above-described conventional technology.

In order to solve the above problems, the present invention has the following configuration.
(1) (A) 0.5 to 12 parts by weight of swellable layered silicate, and (C) at least selected from diphosphinate, polyphosphate and phosphinate with respect to 100 parts by weight of polyamide-based resin A slow-flammable polyamide fiber comprising at least 3.5 to 12 parts by weight of one phosphate.
(2) The slow-flammability polyamide fiber as described in (1) above, wherein the phosphate (C) has an average particle size of 10 microns or less.
(3) The swellable layered silicate (B) treated with 20 to 40% by weight of quaternary ammonium ions with respect to the entire swellable layered silicate is used (1) or (2) ) The slow-flammable polyamide fiber described.
(4) The slow-flammable polyamide fiber according to any one of (1) to (3), further comprising a guanidine compound.
(5) A fabric comprising the slow-flammable polyamide fiber according to any one of (1) to (4).

  According to the present invention, as a flame retardant fiber material, specifically, in industrial use, clothing use, non-clothing use, etc., it has an excellent drip suppression effect, has a slow combustion rate, and has a high production stability. Polyamide fibers and fabrics can be provided.

  Hereinafter, the slow-flammability polyamide fiber of the present invention will be described in detail.

  The slow flammability in the present invention means that the drip suppression effect during combustion is high and the combustion speed is slow.

  The fiber as used in the present invention is, for example, monofilament, multifilament, staple fiber, nanofiber, tow, high bulk tow, high bulk tow, spun yarn, blended yarn, processed yarn, false twisted yarn, modified cross-section yarn, hollow yarn, conjugate yarn, part Includes oriented yarn, drawn yarn, sliver and the like. Examples of the irregular cross-sectional shape include a flat shape, a triangular shape, a C shape, a Y shape, or a combination thereof, but are not limited thereto. In particular, it can be suitably used as a filament or staple.

  For example, as a filament for clothing, it is preferable that the single yarn fineness is in the range of 0.1 dtex to several tens of dtex, the total fineness is 50 to 300 dtex, and the number of filaments is in the range of 10 to 100. For example, as a filament for industrial use, it is preferable that the single yarn fineness is in the range of several tens of Dtex to several hundred Dtex, and the total fineness is in the range of several hundred Dtex to several thousand Dtex, and the number of filaments is in the range of 10 to 100.

  The slow-flammable polyamide fiber of the present invention preferably has a strength of 3.0 to 7.0 cN / dtex, and preferably 4.0 to 6 cN / dtex. When it is 3.0 cN / dtex or more, it is sufficient when used as a fiber, and when it is 7.0 cN / dtex or less, the yield of yarn production is increased, fluff is suppressed, and the quality is improved.

  When the slow-flammable polyamide fiber of the present invention is a multifilament, the boiling water shrinkage is preferably 5 to 15%, and more preferably 8 to 13%.

  The polyamide fiber of the present invention comprises (A) 0.5 to 12 parts by weight of a swellable layered silicate, and (C) a diphosphinate, a polyphosphate, and a phosphinate with respect to 100 parts by weight of a polyamide-based resin. It contains at least 3.5 to 12 parts by weight of at least one selected phosphate.

  The polyamide-based resin (A) in the present invention is a polyamide mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the main constituents include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, and tetramethylenediamine. , Hexamethylenediamine, 1,5-pentanediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5 5-trimethylsick Fats such as sun, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine , Cycloaliphatic, aromatic diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. Nylon homopolymers or copolymers derived from It can be used in the form of people alone or as a mixture.

In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide. (Nylon 66), polypentamethylene adipamide (nylon 56), polytetramethylene adipamide (nylon 46), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyundecane Amide (nylon 11), polydodecanamide (nylon 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), poly Hexamethylene adipamide / poly Xamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / polydodecanamide copolymer (nylon 6T / 12), polyhexa Methylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene Examples include terephthalamide copolymer (nylon 6T / M5T), polynomethylene terephthalamide (nylon 9T), and mixtures thereof.

  In particular, nylon 6, nylon 66, and nylon 6/66 copolymers are preferred from the viewpoint of the obtained fiber characteristics.

  The degree of polymerization of the polyamide-based resin in the present invention is not particularly limited as long as it is in the range capable of spinning, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution of 1% by weight of polyamide resin is 2.0 to Those in the range of 4.0 are preferred. It is because the mechanical characteristic at the time of setting it as a fiber is preferable because it is 2.0 or more, and the spinning property becomes favorable because it is 4.0 or less. 2.5 or more is preferable and 3.0 or less is more preferable.

  The polyamide-based resin (A) in the slow-flammable polyamide fiber of the present invention is preferably 50% by weight or more of the entire fiber. The fiber which has the outstanding mechanical characteristics derived from a polyamide is obtained because it is 50 weight% or more. 60 weight% or more is preferable and 75 weight% or more is more preferable.

The slow-flammable polyamide fiber of the present invention contains 0.5 to 12 parts by weight of the swellable layered silicate (B) with respect to 100 parts by weight of the polyamide resin (A).
The swellable lamellar silicate used in the present invention is formed by laminating a silicic acid tetrahedral sheet on top and bottom of an octahedral sheet containing a metal such as aluminum, magnesium, lithium, etc. 2: It has a type 1 structure and usually has exchangeable cations between the plate crystal layers.

  The size of the single plate-like crystal is usually 0.05 to 0.5 μm in width and 6 to 15 Å in thickness. The exchangeable cation has a cation exchange capacity of 0.2 to 3 meq / g, and preferably a cation exchange capacity of 0.8 to 1.5 meq / g.

Specific examples of the swellable layered silicate include smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and soconite, various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, and titanium phosphate, Examples thereof include swelling mica such as Li-type fluorine teniolite, Na-type fluorine teniolite, Na-type tetrasilicon fluorine mica, Li-type tetrasilicon fluorine mica, and the like, which may be natural or synthesized. Among these, smectite clay minerals such as montmorillonite and hectorite, and swellable mica such as Na-type tetrasilicon fluorine mica and Li-type fluorine teniolite are preferable, and montmorillonite is most preferable.

  As the layered silicate, commercially available products are Laponite XLG (manufactured by Laport, UK, synthetic hectorite analog), Laponite RD (manufactured by Laport, UK, synthetic hectorite analog), Thermabis (manufactured by Henkel, Germany Synthetic hectorite analogs), Smecton SA-1 (Kunimine Kogyo Co., Ltd., saponite analogs), Bengel (Toyoshun Yoko Co., Ltd., natural montmorillonite), Kunipia F (Kunimine Kogyo Co., Ltd., natural montmorillonite) ), Veegum (manufactured by Vanderbilt, Inc., natural hectorite), Daimonite (manufactured by Topy Industries, Ltd., synthetic swelling mica), Somasif (manufactured by Corp Chemical Co., synthetic swelling mica), SWN (corp chemical) Co., Ltd., synthetic smectite), SWF (Coop Chemical Co., Ltd., synthetic smectite), etc. are preferably used. It is possible.

  The aspect ratio of the layered silicate is preferably 5 to 600, and more preferably 100 to 500. An aspect ratio of 5 or more is preferable because non-drip properties are improved, and an aspect ratio of 600 or less is preferable because fiber properties are improved.

  In the present invention, the exchangeable cation existing between the layers of the swellable layered silicate is preferably an organic onium ion.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used.

  Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

  Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium.

  Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.

  Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium and benzyldimethyloctadecylammonium, and alkyltrimethyls such as trimethyloctylammonium, trimethyldodecylammonium and trimethyloctadecylammonium. Examples thereof include ammonium ions, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium, and trialkylmethylammonium ions such as trioctylmethylammonium and tridodecylmethylammonium.

  Besides these, it is derived from aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. And ammonium ions.

  Among these ammonium ions, preferred are quaternary ammonium ions such as trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, and ammonium ions derived from 12-aminododecanoic acid. Most preferred are octylmethylammonium and benzyldimethyloctadecylammonium.

  In the present invention, the swellable layered silicate in which the exchangeable cation existing between the layers is exchanged with the organic onium ion is obtained by reacting the layered silicate having the exchangeable cation between the layer and the organic onium ion by a known method. Can be manufactured. Specific examples include, but are not limited to, a method by ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting liquid or molten ammonium ions with layered silicate.

  In the present invention, the amount of the organic onium ion relative to the layered silicate is the total amount of the layered silicate that has been organized in terms of the dispersibility of the layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. It is preferable that it is 20-40 wt% with respect to.

  Further, the organic onium ions may be removed from the polymer in any step from kneading to final product. The removal method includes, but is not limited to, extraction with an organic solvent or an aqueous solution.

  In addition to the above organic onium ions, these layered silicates are preferably used after pretreatment with a coupling agent having a reactive functional group in order to obtain better mechanical strength. Examples of such coupling agents include isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds.

  Particularly preferred are organosilane compounds, and specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyl. Epoxy group-containing alkoxysilane compounds such as trimethoxysilane, γ-mercaptopropyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxy Silane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane and other ureido group-containing alkoxysilane compounds, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyana Isocyanato group-containing alkoxysilane compounds such as topropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, and γ-isocyanatopropyltrichlorosilane Amino group-containing alkoxysilane compounds such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-hydroxypropyltri Hydroxyl-containing alkoxysilane compounds such as methoxysilane and γ-hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, N-β- (N-bi And carbon-carbon unsaturated group-containing alkoxysilane compounds such as (nylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride. In particular, a carbon-carbon unsaturated group-containing alkoxysilane compound is preferably used.

  The treatment of the layered silicate with these coupling agents can be performed by adsorbing the coupling agent on the layered silicate in a polar solvent such as water, methanol, ethanol, or a mixed solvent thereof, or by high-speed stirring such as a Henschel mixer. A method in which the coupling agent solution is dropped and adsorbed while stirring the layered silicate in the mixer, and further, by adding the silane coupling agent directly to the layered silicate and mixing and adsorbing in a mortar or the like Any of the methods may be used. When the layered silicate is treated with a coupling agent, it is preferable to mix water, acidic water, alkaline water, etc. at the same time in order to promote hydrolysis of the alkoxy group of the coupling agent. In order to increase the reaction efficiency of the coupling agent, in addition to water, water such as methanol and ethanol, and an organic solvent that dissolves both the coupling agent may be mixed. It is also possible to further accelerate the reaction by heat-treating the layered silicate treated with such a coupling agent. When the composition of the present invention is produced by melt-kneading the layered silicate and the polyamide resin, the layered silicate and the polyamide resin are melt-kneaded without performing the treatment with the layered silicate coupling agent in advance. In addition, a so-called integral blend method in which these coupling agents are added may be used.

  The order of the treatment of the layered silicate with the organic onium ion and the treatment with the coupling agent is not particularly limited, but it is preferable to first treat with the organic onium ion and then perform the coupling agent treatment.

  In the polyamide fiber used in the present invention, it is preferable that the layered silicate is uniformly dispersed at a single layer level in the polyamide fiber as a matrix. The state of being uniformly dispersed at the level of a single layer means that the layered silicate is in the state of about a single layer to 10 layers and is dispersed throughout the matrix resin without secondary aggregation. This state can be confirmed by cutting a section from the polyamide fiber and observing it with an electron microscope.

  The compounding quantity of the swellable layered silicate (B) in the present invention is 0.5 to 12 parts by weight with respect to 100 parts by weight of the polyamide resin. This is because the non-drip effect at the time of combustion of the slow-flammable polyamide fiber is great at 0.5 parts by weight or more, and the fiber characteristics of the slow-flammable polyamide fiber become good at 12 parts by weight or less. 4 parts by weight or more and 8 parts by weight or less is preferable because the moldability and non-drip property during combustion are improved.

  The slow-flammable polyamide fiber of the present invention comprises at least one phosphate selected from diphosphinates, polyphosphates and phosphinates in an amount of 3.5 to 12 parts by weight with respect to 100 parts by weight of the polyamide resin (A). Use. It is because sufficient slow-flame property is acquired by using 3.5 weight part or more, and a fiber physical property does not fall by using 12 weight part or less. 4 parts by weight or more is more preferable, and 8 parts by weight or less is more preferable.

  In the present invention, by using the phosphate (C) in combination with the swellable layered silicate (B), a higher non-drip effect and delayed flame effect can be obtained than when used alone. The reason is not clear, but since the swellable layered silicate (B) and phosphate have a strong interaction, phosphate (C) enters between the swellable layered silicate (B) dispersed in the polyamide. By forming a carbonized layer at the time of combustion, the effect of blocking the transmission of combustion heat is higher than when the swellable layered silicate (B) is used alone, and it is considered that a high flame retardant effect can be obtained even in a small amount. .

  In the present invention, the average particle size of the phosphate (C) is preferably 20 microns or less. It is preferable that the average particle size is 10 microns or less because a decrease in mechanical properties of the fiber of the present invention can be suppressed. It is preferably 0.2 microns or more, and more preferably 5 microns or less. An average particle diameter can be calculated | required as a weight average value using the particle size distribution measuring apparatus of a laser beam diffraction method.

  The phosphate (C) having the above particle diameter can be obtained by a method such as dry classification after pulverization by means such as a ball mill. The pulverization includes, but is not limited to, wet pulverization and dry pulverization.

  As the phosphate used in the present invention, at least one selected from diphosphinate, polyphosphate, and phosphinate is used.

  The diphosphinate, polyphosphate and phosphinate used in the present invention are compounds represented by the following general formulas (1) to (3).

_{R 1, R 2, R 4} , R 5 , although it may be the same or different, is preferably a straight-chain or branched alkyl or aryl group having 1 to 6 carbon atoms, methyl, ethyl, n It is more preferably at least one selected from -propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and phenyl.

R ₃ is preferably a linear or branched alkylene, arylene, alkylarylene, or arylalkylene having 1 to 10 carbon atoms, methylene, ethylene, n-propylene, isopropylene, n-butylene, tertiary butylene, n More preferred are -pentylene, n-octylene or n-dodecylene, phenylene and naphthylene.

  M is preferably an alkali metal such as lithium, sodium or potassium, an alkaline earth metal such as magnesium, calcium or strontium, a metal such as manganese, titanium, zirconium, zinc or aluminum, or a cationic species such as an ammonium salt. Or zinc and an ammonium salt are more preferable.

  In the present invention, the phosphate (C) may be a coated one. The coating is preferably inorganic oxide fine particles and thermosetting resin, and can be selected according to the purpose.

  As the thermosetting resin to be coated, melamine resin, urea resin, urea resin, urethane resin, and phenol resin are preferable. In particular, a melamine resin that improves flame retardancy by a synergistic effect is more preferable.

  The slow-flammable polyamide fiber in the present invention can contain one or more nitrogen-containing flame retardants such as triazine, guanidine, cyanurate, and isocyanurate. It is preferable because a high flame retardant effect is exhibited by the synergistic action with the phosphate. Of the nitrogen-containing flame retardants, guanidine compounds are particularly preferable.

  A preferred triazine is represented by the following formula:

Wherein R ₆ , R ₇ and R ₈ are each independently C1-C12 alkyl, C1-C12 alkoxyl, C6-C12 aryl, amino, C1-C12 alkyl substituted amino or hydrogen. Particularly preferred triazines include 2,4,6-triamine-1,3,5-triazine (melamine), melamine derivatives, melam, melem, melon, amelin, ammelide, 2-ureidomelamine, acetoguanamine, benzoguanamine and the like. It is done. Salts or adducts of these compounds with sulfuric acid, boric acid or phosphoric acid can also be used in the composition. Specific examples include melamine pyrophosphate, melamine polyphosphate, and melamine sulfate. Preferred cyanurate and isocyanurate compounds include salts or adducts of triazine compounds and cyanuric acid, such as melamine cyanurate and melamine salt mixtures.

  Preferred guanidine compounds include guanidine, aminoguanidine, and the like, salts and adducts thereof with boric acid, carbonic acid, phosphoric acid, nitric acid, sulfuric acid, and the like, and mixtures containing one or more of these guanidine compounds.

  In the present invention, a metal borate salt can be contained. The boric acid metal salt is not particularly limited, but it is preferable to use a borate such as zinc borate and magnesium borate.

  The boric acid metal salt is preferably contained in an amount of 1 to 6 parts by weight with respect to 100 parts by weight of the polyamide resin (A). By containing 1 part by weight or more, flame retardance can be effectively expressed, and by using 6 parts by weight or less, the dispersibility of the flame retardant is preferable. 2 parts by weight or more is preferable, and 3 parts by weight or less is preferable.

  In the present invention, flame retardants other than those described above can be used. In this invention, it can select from the compound generally used as a flame retardant. Specifically, a hydrated metal flame retardant such as magnesium hydroxide can be used, but is not limited.

  In the polyamide fiber of the present invention, various additives other than the flame retardant can be appropriately blended depending on the purpose within a range not impairing the characteristics. Examples of the additive include an antioxidant, an ultraviolet absorber, a stabilizer, a light stabilizer, a compatibilizer, a lubricant, a filler, an adhesion aid, and a rust inhibitor.

  In order to prevent the weather-resistant deterioration and heat-resistant strength deterioration of the slow-flammable polyamide fiber of the present invention, the polyamide fiber preferably further contains 10 to 500 ppm of a copper compound as a copper metal amount. When the amount of copper metal is 10 ppm or more, the effect of improving the weather resistance and heat resistance by the copper compound becomes good, and when the amount of copper metal is 500 ppm or less, the copper compound becomes a foreign substance and the risk of deterioration of the yarn-making property is reduced. The amount of copper metal contained is preferably 20 to 300 ppm, more preferably 30 to 250 ppm, and the addition amount is selected depending on the use and purpose of the flame-retardant polyamide fiber. Examples of the copper compound include, but are not limited to, copper iodide, copper chloride, copper bromide and the like, and conventionally known inorganic and organic copper salts and simple copper metals can be used.

  The polyamide fiber may further contain another heat-resistant agent. Examples of the heat-resistant agent include amine compounds, mercapto compounds, phosphorus compounds, hindered phenol compounds, halogen compounds, alkali metal halides, alkaline earth metal halides, etc., but are not limited thereto, A combination of two or more of these may be used. Examples of amine compounds include N, N′-diphenyl-p-phenylenediamine, diallyl-p-phenylenediamine, and di-β-naphthyl-p-phenylenediamine. Examples of mercapto compounds include 2- Mercaptobenzimidazole and 2-mercaptothiazole can be exemplified, and examples of phosphorus compounds include, but are not limited to, organic and inorganic phosphoric acids such as stearyl phosphate, phosphorous acid or salts thereof. The copper compound and the heat-resistant agent may be added separately or may be added after forming a complex. As the heat-resistant agent added together with the copper compound, a mercapto compound is particularly preferable, and 2-mercaptobenzimidazole is particularly preferably combined. At this time, the addition amount of the mercapto compound is preferably 300 to 3000 ppm from the viewpoints of thermal oxidative degradation prevention and yarn-forming properties.

  Antioxidants usable in the present invention include 2,6-di-tert-butyl-4-methylphenol and n-octadecyl-3- (3 ′, 5′-di-tert-butyl-4-hydroxyphenyl). ) Propionate, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 4 , 4′-butylidenebis- (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8 10-tetraoxaspiro [5,5] undecane, 4,4-thiobis- (2-tert-butyl-5-methylphenol), 2,2-methylenebis- (6-tert-butyl-methylphenol), 4, 4-methylenebis- (2,6-di-t-butylphenol), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tris Nonylphenyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, distearyl pentaerythritol phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol phosphite, bis (2, 6-di-t-butyl-4-methylphenyl) pentaerythritol phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) Nyl) octyl phosphite, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene-di-phosphonite, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′- Thiodipropionate, pentaerythritol tetrakis (3-laurylthiopropionate), 2,5,7,8-tetramethyl-2 (4,8,12-trimethyldecyl) chroman-2-ol, 5,7- Di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2-one, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4 , 6-Dipentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate , Tetrakis (methylene) -3- (dodecylthiopropionate) methane and the like.

  Stabilizers that can be used in the present invention include lithium stearate, magnesium stearate, calcium laurate, calcium ricinoleate, calcium stearate, barium laurate, barium ricinoleate, barium stearate, zinc laurate, zinc ricinoleate, stearin Various metal soap stabilizers such as zinc acid, various organic tin stabilizers such as laurate, malate and mercapto, various lead stabilizers such as lead stearate and tribasic lead sulfate, and epoxy compounds such as epoxidized vegetable oil Phosphite compounds such as alkylallyl phosphite and trialkyl phosphite, β-diketone compounds such as dibenzoylmethane and dehydroacetic acid, hydrotalcites and zeolites.

  Examples of light stabilizers that can be used in the present invention include benzotriazole-based UV absorbers, benzophenone-based UV absorbers, salicylate-based UV absorbers, cyanoacrylate-based UV absorbers, oxalic anilide-based UV absorbers, and hindered amine-based light stabilizers. Agents and the like.

  The slow-flammable polyamide fiber of the present invention can further contain 0.1 to 1.0% by weight of an organic or inorganic pigment or dye. Polyamide fibers can also be made into an original, and in this case, there is no need for dyeing, which is preferable. The amount of organic or inorganic pigment or dye added is preferably 0.02 to 0.08% by weight.

  Preferred pigments and dyes include zinc white, titanium oxide, bengara, titanium yellow, zinc-iron brown, titanium-cobalt green, cobalt green, cobalt blue, copper-iron black, ultramarine, Inorganic pigments such as calcium carbonate, manganese violet, carbon black, aluminum powder, bronze powder, titanium-coated mica, and copper phthalocyanine blue, copper phthalocyanine, brominated copper phthalocyanine, dianthraquinone red, Examples thereof include organic pigments such as beryllens scarlet, beryllen red, beryllen marne, dioxane violet, isoindolinone yellow, and metal complex salt azomethine.

  As the black pigment, carbon black, iron oxide black, spinel black, manganese block, cobalt black and the like are used, and carbon black is particularly preferable.

  In the present invention, a small amount of a thermoplastic resin, for example, an olefin polymer such as polycarbonate, polyester, polyphenylene oxide, polypropylene, polyethylene, ethylene / propylene copolymer, ethylene / 1-, as long as the object of the present invention is not impaired. Olefins such as butene copolymers, ethylene / propylene / non-conjugated diene copolymers, ethylene / ethyl acrylate copolymers, ethylene / glycidyl methacrylate copolymers, and ethylene / propylene-g-maleic anhydride copolymers Copolymers, polyether ester elastomers, polyester elastomers and the like can also be added.

  In the present invention, a fabric using the above-mentioned slow-flammable polyamide fiber is preferable.

  Moreover, the fabric in this invention includes what is generally recognized as fiber bodies, such as a woven fabric, a knitted fabric, a nonwoven fabric, a string, a rope, felt, paper, a net | network, containing the slow-flammability polyamide fiber mentioned above.

  It is preferable to contain 70% or more of the above-mentioned polyamide fiber by weight ratio with respect to the total amount of the fabric, but this is not the only case, and the drip suppression effect, slow flame retardancy, physical properties of the resin composition and processing properties are reduced. It can be blended with other fibers or blended as long as there is not.

When the fiber is a filament, for example, it can be obtained by weaving into a woven fabric such as a triple structure or a change structure that is a single structure, a weft double structure or a vertical structure that is a double structure, and a fiber structure. In addition, the mass of the fiber structure at this time is in the range of 50 g / m ² or more and 500 g / m ² or less when used for clothing, and the mass is 300 g / m ² or more and 1500 g when used for industrial purposes. / M ² or less is preferable.

  The fabric comprising the slow-flammable polyamide fiber of the present invention is a textile product that requires a drip-suppressing effect and slow-flammability, such as vehicle interior materials such as car seats and car mats, curtains, carpets, chair upholstery, etc. It can be suitably used as a textile product in which drip is suppressed by an interior material, a clothing material, and the like, and also exhibits slow flame retardancy.

  Next, the method for producing the fiber and fabric of the present invention will be described in detail.

  First, regarding polyamide fibers, examples of methods for imparting flame retardants such as swellable layered silicate (B) and phosphate (C) to polyamide fibers include swellable layered silicate (B) and phosphate (C ) And other flame retardants during the polymerization of polyamide, and a polyamide resin chip and a flame retardant such as a swellable layered silicate (B) and phosphate (C) are kneaded in a kneader such as a twin screw extruder. Or a method of adding a flame retardant such as a swellable layered silicate (B) or a phosphate (C) at the time of spinning of a polyamide-based resin. If salt (C) can be provided to polyamide, it will not be restricted to these. In the case of kneading, it is preferable to knead the swellable layered silicate (B) and then the phosphate (C) to the polyamide resin (A).

  As a method for producing a polyamide fiber containing at least the polyamide-based resin (A), the swellable layered silicate (B), and the phosphate (C), a normal yarn making process and a drawing process can be employed. In addition, a high-speed spinning and composite spinning can be used in the spinning process, and a method in which the spinning process and the stretching process are continuously performed in the stretching process can be used.

  The fabric using the polyamide fiber in the present invention can be produced by a known method. For example, in the case of a non-woven fabric, it may be directly connected to the spinning process, and in the case of a woven or knitted fabric, a fiber form required by a known method may be used after spinning.

  The obtained fiber can also be obtained as a fiber composite obtained by knitting, knitting, knitting yarn, mixed yarn or the like with other fibers.

  As a method for imparting a flame retardant component to fibers and fabrics, a method of copolymerizing and blending with a polyamide fiber, a method of imparting by high-order processing after yarn production, and the like can be used. Good.

  The fabric of the present invention can be subjected to various post-processing. For example, functions such as water repellency, hydrophilicity, antistatic properties, deodorizing properties, antibacterial properties, and deep color properties are imparted by processing in the bath, exhaustion processing, coating processing, pad-dry processing, pad-steam processing, etc. be able to.

  In particular, flame retardants that are liable to be thermally decomposed due to the heat history before fiberization, such as guanidine compounds in nitrogen-containing flame retardants, are preferable because they can be applied without being decomposed by post-processing.

Hereinafter, the present invention will be described in more detail with reference to examples. Each characteristic value in the examples is obtained by the following method.
A. Relative viscosity A polymer sample was dissolved in 98% sulfuric acid at a concentration of 1% by weight, measured at 25 ° C. using an Ostwald viscometer, and determined according to the following formula.
Sulfuric acid relative viscosity (ηr) = (sample solution dropping time) / (sulfuric acid solution dropping time)
Each sample was measured twice and the average value was adopted.
B. Fineness The fineness was measured by the method of JIS L1017 (2002) 8.3.
C. Fiber properties (strength / elongation)
It measured by the method of JIS L1017 (2002) 8.5.
A strength of 2.5 cN / dtex or more was rated as “◯”, a strength of 2.0 or more and less than 2.5 cN / dtex as “Δ”, and a strength of less than 2.0 cN / dtex as “x”.
D. Boiling water shrinkage was measured according to JIS L1017 (2002).
E. Combustion test A fiber structure of a knitted fabric is produced from the drawn yarn obtained with a cylindrical knitting machine, and 2 g / L of sodium carbonate, 0.2 g / L of a surfactant (Gran-up US30, manufactured by Sanyo Chemical Industries, Ltd.), treatment temperature / After scouring at a time of 60 ° C./30 minutes, setting was performed at 180 ° C. for 2 minutes with dry heat.

A knitted fabric was piled up and stitched so as to have a length of 10 cm, a width of 1.5 cm, and a basis weight of 300 g / m ² to obtain a sample for a combustion test.

The upper end of the sample was stopped and made vertical, and a flame was ignited at the lower end for 10 seconds, and then the combustion test was performed by moving away from the sample. When the drip stopped and the fabric stopped burning, the lower end of the remaining sample was ignited again.
F. Non-drip property When the number of non-drip times during combustion was 0, the non-drip property ◯ was used.
G. Delayed Flammability Combustion time was defined as the period from the start of ignition until the combustion of the fire stopped. When drip and the combustion of the fabric stopped, the total combustion time was defined as the combustion time.
30 seconds or more were marked with ◯, 20 seconds or more but less than 30 seconds with Δ, and less than 20 seconds with x.
H. Out of the three evaluations of overall evaluation strength (spinning property), non-drip property, and slow-flammability, all were evaluated as ◯. Although there is at least one of the three evaluations, the overall evaluation was set to x. The others were marked with Δ.
○ is no problem.

Reference example 1
100 g of Na-type montmorillonite (Kunimine Industries: Kunipia F, cation exchange capacity 120 meq / 100 g) was dispersed in 10 liters of hot water, and 2 L of hot water in which 50 g of benzyldimethyloctadecyl ammonium chloride was dissolved was added and stirred for 1 hour. did. The resulting precipitate was filtered off and washed with warm water. This washing and filtering operation was performed three times to obtain an undried solid. Thereafter, the obtained solid was vacuum-dried at 80 ° C. and pulverized to obtain a swellable layered silicate. The amount of inorganic ash of the obtained swellable layered silicate was measured (determined by heating loss at the time of holding at 600 ° C. for 3 hours in an air atmosphere using TG-DTA) and found to be 69% by weight.

Example 1
7 weights of organically swellable layered silicate (refer to Reference Example 1, Organizer: benzyldimethyloctadecylammonium (31%)) per 100 parts by weight of nylon 6 having a relative viscosity of 2.8 as polyamide (A) Part, 5.5 parts by weight of aluminum phosphinate (OP935 manufactured by Clariant, average particle size 2 microns) as a phosphate is extruded in a biaxial manner under the conditions of L / D: 32.5, kneading temperature 240 ° C., screw rotation speed 300 rpm. After kneading using a machine to obtain a resin composition, it was cut into a 3 mm square chip. It was found that the chip surface was smooth, the dispersibility of the flame retardant was good, and the kneadability was excellent. The obtained chip was dried at 120 ° C. for 12 hours and 2 Torr in a vacuum dryer, and then a die having a spinning temperature of 270 ° C., a spinning speed of 800 m / min, a die diameter of 0.23 mm, a hole depth of 0.15 mm, and a hole number of 24. Spinning was performed under the condition of a discharge amount of 32 g / min. The spinning performance was good, and the production stability was excellent. Next, using a drawing machine, drawing was performed at a drawing ratio such that the fineness of the drawn yarn was 128 dtex-24 filaments under the conditions of a processing speed of 120 m / min, a drawing temperature of 90 ° C., and a set temperature of 130 ° C. to obtain a drawn yarn. The properties of the drawn yarn were good with a strength of 3.1 cNd / tex, an elongation of 33%, and a boiling water shrinkage of 10.1%.

  Subsequently, a combustion test was performed using the obtained drawn yarn. As a result, the number of non-drip times was 0 and the burning speed was 40 seconds. Both the non-drip property and the slow flame retardance were good. The results are shown in Table 1.

Example 2
An aqueous solution (Bigorge NS manufactured by Daikyo Chemical Co., Ltd.) containing a guanylsulfamide compound as a main component was applied to the fabric of Example 1, then dried at 100 ° C. and heat set at 150 ° C. for 2 minutes.
A combustion test was conducted in the same manner as in Example 1 using the obtained fabric. The application amount of guanylsulfamide is 5.5 parts by weight with respect to 100 parts by weight of the polyamide resin (A). As a result, both the non-drip property and the slow flame retardancy were good. In addition, a large amount of carbide was generated during combustion. The results are shown in Table 1.

Example 3
A swellable lamellar silicate (organizing agent: benzyldimethyltetradecylammonium, 31% by weight of organic content) obtained as the swellable lamellar silicate (B) in the same manner as in Reference Example 1 was added to the polyamide resin (A) 100. 5.5 parts by weight with respect to parts by weight, 4.5 parts by weight of ammonium polyphosphate (manufactured by Budenheim, average particle size 7 microns) as phosphate (C), 4.5 parts by weight of zinc borate (manufactured by Mizusawa Chemical Co., Ltd.) Kneading, spinning, and stretching were performed in the same manner as in Example 1 except that parts by weight were used.

  The physical properties of the obtained fiber were good.

  Moreover, the flame retardance test was done using the extended | stretched thread | yarn. As a result, both the non-drip property and the slow flame retardancy were good. The results are shown in Table 1.

Example 4
Nylon 66 and swellable layered silicate (organizing agent: benzyldimethyloctadecylammonium, organic amount 28 wt%) obtained in the same manner as in Reference Example 1 as polyamide (A) and swellable layered silicate (B) Kneading, spinning, and stretching were performed in the same manner as in Example 1 except that 7 parts by weight with respect to 100 parts by weight of the polyamide-based resin (A) and 5.5 parts by weight of aluminum phosphinate as the phosphate (C) were used. The physical properties of the obtained fiber were good.

  Moreover, the flame retardance test was done using the extended | stretched thread | yarn. As a result, both the non-drip property and the slow flame retardancy were good. The results are shown in Table 1.

Example 5
As a swellable layered silicate (B), a swellable layered silicate obtained in the same manner as in Reference Example 1 (organizing agent: benzyldimethyloctadecylammonium, organic amount 28 wt%) was added to a polyamide resin (A) 100 weights. Kneading, spinning and stretching were carried out in the same manner as in Example 1 except that 6 parts by weight, 6 parts by weight of aluminum phosphinate as the phosphate (C), and 6 parts by weight of melamine cyanurate as the nitrogen-containing compound were used. It was. The physical properties of the obtained fiber were good.

  Moreover, the flame retardance test was done using the extended | stretched thread | yarn. As a result, both the non-drip property and the slow flame retardancy were good. In addition, a large amount of carbide was generated. The results are shown in Table 1.

Example 6
Kneading, spinning, and stretching were performed in the same manner as in Example 1 except that ExolitOP1230 (particle size: 35 microns) manufactured by Clariant was used as the phosphate (C). Although an increase in the filtration pressure was observed during spinning and yarn breakage was observed during drawing, the fiber properties were good.

  Moreover, the flame retardance test was done using the extended | stretched thread | yarn. As a result, both the non-drip property and the slow flame retardancy were good. The results are shown in Table 1.

Comparative Example 1
Kneading, spinning, and stretching were performed in the same manner as in Example 1 except that the phosphoric acid metal salt (C) was not used. Although the physical properties of the fiber were good, the number of drips was 2 as a result of the combustion test, and the non-drip property was inferior. The results are shown in Table 2.

Comparative Example 2
Kneading, spinning, and stretching were performed in the same manner as in Example 2 except that the swellable layered silicate (B) was not used. Although the physical properties of the fiber were good, as a result of the combustion test, although the formation of carbides was observed, the number of drips was as high as 4 and there was no non-drip property. In addition, the burning time was 21 seconds, and the delayed burning effect was inferior. The results are shown in Table 2.

Comparative Example 3
7 parts by weight of polyamide (A) and swellable layered silicate (B) with respect to 100 parts by weight of polyamide resin (A), 13 parts by weight of ammonium polyphosphate as phosphate (C), and melamine as nitrogen-containing compound Kneading was performed in the same manner as in Example 1 except that 8 parts by weight of cyanurate and 8 parts by weight of zinc borate were used as other flame retardants. The polymer obtained was very brittle.

  Further, although it was made into a fiber, its strength was low and the non-drip property was low in the result of the combustion test. The results are shown in Table 2.

Comparative Example 4
Kneading / spinning / stretching was performed in the same manner as in Example 1 except that 13 parts by weight of the swellable layered silicate (B) was used with respect to 100 parts by weight of the polyamide-based resin (A) and the phosphate (C) was not used. went. The strength of the yarn after drawing was low.
As a result of the combustion test, good non-drip property and slow-flammability were obtained. The results are shown in Table 2.

Comparative Example 5
The swellable layered silicate (B) and phosphate (C) were not used, and kneading, spinning and stretching were performed in the same manner as in Example 1 using only nylon 6 as the polyamide (A). The physical properties of the obtained drawn yarn were good. At the time of knitting, post-processing was performed using guanylsulfoamide in the same manner as in Example 2.

  As a result of the flame retardant test, both the non-drip property and the slow flame retardance were inferior. The results are shown in Table 2.

Claims (5)

(A) 0.5 to 12 parts by weight of (B) swellable layered silicate and (C) at least one phosphorus selected from diphosphinate, polyphosphate and phosphinate with respect to 100 parts by weight of the polyamide-based resin A slow-flammable polyamide fiber comprising at least 3.5 to 12 parts by weight of an acid salt. 2. The flame retardant polyamide fiber according to claim 1, wherein the phosphate (C) has an average particle size of 10 μm or less. 3. Slow flammability according to claim 1 or 2, wherein the swellable layered silicate (B) organically treated with 20 to 40% by weight of quaternary ammonium ions is used with respect to the entire swellable layered silicate. Polyamide fiber. The flame retardant polyamide fiber according to any one of claims 1 to 3, further comprising a guanidine compound. A fabric comprising the slow-flammable polyamide fiber according to any one of claims 1 to 4.