JP5750905B2 - Flame retardant polyamide resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a flame retardant polyamide resin composition excellent in flame retardancy, strength, heat resistance and water resistance, comprising a polyamide resin containing tetramethylene diamine as a main constituent and a flame retardant.

  Polyamide resins are used in a wide range of fields as engineering plastics, automobile parts, electrical / electronic parts, and mechanical parts due to their excellent thermal properties, mechanical properties, electrical properties, chemical properties, and the like. In addition, with the recent diversification of uses of plastic materials, polyamide resins are also required to have flame retardancy.

  As methods for imparting flame retardancy to a polyamide resin, Patent Documents 1 and 2 propose a method of blending a flame retardant with polyamide 46. Patent Document 1 describes the use of melamine cyanurate. However, when polyamide 46 alone and melamine cyanurate are kneaded, there is a problem that the flame retardant decomposes and excellent flame retardancy cannot be obtained. Patent Document 2 describes that brominated polystyrene is used for nylon 46, but the flame retardant polyamide resin composition of nylon 46 is excellent in strength and heat resistance, but is actually used because of its high water absorption rate. The problem was the decrease in strength and dimensional stability at the time (atmospheric equilibrium water absorption state). On the other hand, when high-grade (meaning that the number of carbon atoms) nylon represented by nylon 610 and nylon 612 is used, water absorption is low, but strength and heat resistance are low.

  Patent Document 3 describes a polyamide resin composed of a monomer composed of tetramethylenediamine and an aliphatic dicarboxylic acid having 8 to 14 carbon atoms.

JP-T-2006-509885 Japanese Patent Laid-Open No. 61-188463 International Publication No. 00/09586 Pamphlet

  This invention makes it a subject to obtain the flame-retardant polyamide resin composition excellent in a flame retardance, intensity | strength, heat resistance, and water resistance.

  The present invention employs the following means as a result of intensive studies to solve the above problems.

That is, the present invention
(1) (a) 1 to 50 parts by weight of melamine cyanurate with respect to 100 parts by weight of a polyamide resin composed of a monomer containing tetramethylenediamine and an aliphatic dicarboxylic acid having 7 or more carbon atoms as main components A flame-retardant polyamide resin composition,
(2) The sulfuric acid relative viscosity measured at 25 ° C. and a concentration of 0.01 g / ml in concentrated sulfuric acid of the (a) polyamide resin is 2.0 to 5.0, as described in (1) Flame retardant polyamide resin composition,
(3) The flame retardant polyamide according to (1) or (2), wherein the aliphatic dicarboxylic acid having 7 or more carbon atoms is at least one selected from azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid Resin composition,
(4) before Symbol (a) a flame retardant polyamide resin composition according to any one of in which the polyamide resin is prepared by melt polymerization (1) to (3),
( 5 ) The flame retardant polyamide resin composition according to any one of (1) to ( 4 ), further comprising an inorganic filler.
( 6 ) A molded article comprising the flame-retardant polyamide resin composition according to any one of (1) to ( 5 ).

  The flame-retardant polyamide resin composition of the present invention is excellent in flame retardancy, strength, heat resistance, and water resistance. Therefore, in electrical / electronic and automobile parts that require flame retardancy, strength, heat resistance, and water resistance. It can be preferably used.

  Hereinafter, the present invention will be described in detail.

  The polyamide resin composed of a monomer containing (a) tetramethylenediamine and an aliphatic dicarboxylic acid having 7 or more carbon atoms as main components used in the present invention is tetramethylenediamine and an aliphatic having 7 or more carbon atoms. It is a polyamide resin in which the total weight of the dicarboxylic acid is 70% by weight or more of the raw material monomer. More preferably, it is 80 weight% or more, More preferably, it is 90 weight% or more. Since the polyamide resin containing tetramethylenediamine as a constituent component has higher crystallinity than the polyamide resin containing hexamethylenediamine as a constituent component, it has an advantage of excellent strength and heat resistance. In addition, the polyamide resin having an aliphatic dicarboxylic acid having 7 or more carbon atoms as a constituent component has a longer hydrophobic methylene group than the polyamide resin having an aliphatic dicarboxylic acid having 6 or less carbon atoms as a constituent component. It has the advantage of excellent water resistance.

  Examples of the aliphatic dicarboxylic acid having 7 or more carbon atoms include pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, 1, Examples include 2-cyclohexanedicarboxylic acid and 1,3-cyclohexanedicarboxylic acid, and these may be used in combination of two or more. In particular, azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid, which are excellent in balance between heat resistance and melt residence stability, are preferable. More preferred is sebacic acid which is excellent in the balance of strength, heat resistance and water resistance.

  (A) As copolymer units other than tetramethylenediamine and aliphatic dicarboxylic acid having 7 or more carbon atoms constituting the polyamide resin, ethylenediamine, 1,3-diaminopropane, 1,5-diaminopentane, 1,6 -Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diamino Tridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20 -Fats such as diaminoeicosane and 2-methyl-1,5-diaminopentane Diamine, cyclohexanediamine, alicyclic diamine such as bis- (4-aminocyclohexyl) methane, aromatic diamine such as xylylenediamine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, Amino acids such as paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, oxalic acid, malonic acid, succinic acid, glutaric acid, aliphatic dicarboxylic acids such as adipic acid, and alicyclic rings such as cyclohexanedicarboxylic acid And aromatic dicarboxylic acids such as dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, and naphthalenedicarboxylic acid, and the like. At least one of these can be contained in an amount of less than 30% by weight based on the total components. .

  As a method for producing the polyamide resin (a) used in the present invention, tetramethylenediamine and an aliphatic dicarboxylic acid having 7 or more carbon atoms or a salt thereof are heated to synthesize a low-order condensate, A method of increasing the degree of polymerization by phase polymerization or melt polymerization is mentioned. This method includes two-stage polymerization in which a low-order condensate is once taken out, followed by solid-phase polymerization or melt polymerization, and one-stage polymerization in which solid-phase polymerization or melt polymerization is performed in the same reaction vessel following the production process of the low-order condensate Either of these may be used. The polyamide resin obtained by melt polymerization has a narrow molecular weight distribution compared to the polyamide resin obtained by solid phase polymerization, and the content of relatively low molecular weight components is relatively small. The mechanical properties are improved, which is more preferable. The low-order condensate is defined as a polyamide resin having a sulfuric acid relative viscosity described later of 1.05-1.90. The solid phase polymerization is a step of heating in a temperature range of 100 ° C. to a melting point under reduced pressure or in an inert gas, and the melt polymerization is a step of heating to a melting point or higher under normal pressure or reduced pressure. .

In the production of the polyamide resin (a) used in the present invention, the polymerization proceeds due to volatilization of tetramethylenediamine and pyrrolidine produced by the cyclization reaction, or pyrrolidine becomes a terminal blocker. Along with this, the total amino group amount with respect to the total carboxyl group amount in the polymerization system decreases, and the polymerization rate tends to be delayed. In the present invention, in order to suppress the volatilization of tetramethylenediamine, it is preferable that the pressure in the polymerization system is high. However, when the volatilization of condensed water is suppressed, the cyclization reaction of tetramethylenediamine is promoted. In the present invention, the maximum pressure in the polymerization system is preferably 1 to 25 kg / cm ² . By setting the maximum pressure to 1 kg / cm ² (0.10 MPa) or more, the volatilization of tetramethylenediamine can be sufficiently suppressed and the equimolarity of the amino group and the carboxyl group can be maintained. 2 kg / cm ² (0.20 MPa) or more is more preferable. On the other hand, by setting the maximum pressure to 25 kg / cm ² (2.45 MPa) or less, water desorption by polycondensation can be appropriately advanced, and the degree of polymerization can be easily increased. 20kg ^/ cm 2 (1.96MPa), more preferably ^less, 15kg / cm 2 (1.47MPa), more preferably ^less, 10kg / cm 2 (0.98MPa) or less is more preferable. As the condensation reaction proceeds, condensed water is generated and the pressure in the system rises, so the pressure at the start of polymerization may be zero, but in order to minimize the volatilization of tetramethylenediamine, The pressure in the system can be adjusted to be high by a method of adding water or a method of pressurizing with an inert gas in advance at the start of polymerization.

  In addition, in order to obtain a high-molecular-weight (a) polyamide resin, it is preferable to add a specific amount of tetramethylenediamine in advance excessively and control the amount of amino groups in the polymerization system at the stage of charging the raw materials. When the mole number of tetramethylenediamine used as a raw material is A and the mole number of a dicarboxylic acid having 7 or more carbon atoms is B, the raw material composition ratio is set so that the ratio A / B is 1.005 to 1.08. It is preferable to adjust. By setting A / B to be 1.005 or more, an amino group is appropriately contained in the polymerization system, so that a higher molecular weight polymer can be easily obtained. 1.01 or more is more preferable. On the other hand, by setting A / B to 1.08 or less, a polymer having a carboxyl group in the polymerization system can be appropriately obtained, so that a higher molecular weight polymer can be easily obtained. Furthermore, volatilization of the diamine component is suppressed, which is preferable from the viewpoint of productivity and environment. 1.05 or less is more preferable.

  In the heat polycondensation for producing the polyamide resin (a) used in the present invention, in order to prevent coloration in addition to volatilization of tetramethylenediamine and suppression of cyclization by deammonia reaction, the entire polymerization process is performed. It is important to minimize the thermal history received by the polymer in order to reduce the maximum temperature reached in the polymerization system. In the present invention, when the low-order condensate is melt-polymerized, the maximum temperature reached in the polymerization system is preferably not less than the melting point of the polyamide resin and not more than 285 ° C, more preferably not less than the melting point and not more than the melting point + 30 ° C. It is. By setting the maximum reached temperature to 285 ° C. or less, volatilization and cyclization of tetramethylenediamine can be suppressed, and coloring of the resulting polyamide resin can be suppressed. In the case of increasing the degree of polymerization in the solid phase, it is preferable to perform solid phase polymerization at a melting point of −40 ° C. or higher and lower than the melting point under reduced pressure or in an inert gas atmosphere.

  The degree of polymerization of the polyamide resin (a) used in the present invention is preferably such that the relative viscosity at 25 ° C. of a 98% sulfuric acid solution of 0.01 g / ml is 2.0 to 5.0. When the relative viscosity is 2.0 or more, the toughness of the polyamide resin is further improved. 2.2 or more is more preferable, and 2.5 or more is more preferable. On the other hand, if the relative viscosity is 5.0 or less, the moldability is improved. 4.5 or less is more preferable, and 4.0 or less is more preferable.

  A polymerization accelerator can be added to the (a) polyamide resin used in the present invention, if necessary. As the polymerization accelerator, for example, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid and inorganic phosphorus compounds such as alkali metal salts and alkaline earth metal salts thereof are preferable, and sodium phosphite is particularly preferable. Sodium hypophosphite is preferably used. The polymerization accelerator is preferably used in the range of 0.001 to 1 part by weight with respect to 100 parts by weight of the raw material. If the amount of the polymerization accelerator used is 0.001 part by weight or more, the effect of addition is remarkably exhibited. Moreover, if it is 1 weight part or less, the polymerization degree of the polyamide resin obtained can be suppressed moderately, and a high melt moldability can be maintained.

  The flame retardant (b) used in the present invention is not particularly limited as long as it can impart flame retardancy to the polyamide resin of the present invention. Specifically, non-halogen flame retardants that do not contain halogen atoms, such as phosphorus flame retardants, nitrogen flame retardants and metal hydroxide flame retardants, and halogen flame retardants represented by bromine flame retardants These flame retardants may be used alone or in combination.

  The amount of (b) flame retardant added in the present invention is 1 to 50 parts by weight with respect to 100 parts by weight of (a) polyamide resin. When the addition amount is less than 1 part by weight, the flame retardancy tends to be inferior. On the other hand, if it exceeds 50 parts by weight, the mechanical properties, particularly the toughness, are significantly lowered.

  The phosphorus-based flame retardant in the present invention is a compound containing a phosphorus element, specifically, polyphosphoric compounds such as red phosphorus, ammonium polyphosphate, melamine polyphosphate, (di) phosphinic acid metal salt, phosphazene. Examples thereof include compounds, aromatic phosphate esters, aromatic condensed phosphate esters, and halogenated phosphate esters.

  The (di) phosphinate is produced in an aqueous medium using, for example, phosphinic acid and a metal carbonate, metal hydroxide or metal oxide. The (di) phosphinate is essentially a monomeric compound, but depending on the reaction conditions, it may be a polymeric phosphinate having a degree of condensation of 1 to 3 depending on the environment. As phosphinic acid, dimethylphosphinic acid, ethylmethylphosphinic acid, diethylphosphinic acid, methyl-n-propylphosphinic acid, methandi (methylphosphinic acid), benzene-1,4- (dimethylphosphinic acid), methylphenylphosphinic acid and And diphenylphosphinic acid. Moreover, as a metal component (M) made to react with said phosphinic acid, the metal carbonate, a metal hydroxide, or a metal oxide containing a calcium ion, a magnesium ion, an aluminum ion, and / or a zinc ion is mentioned. Examples of phosphinates include calcium dimethylphosphinate, magnesium dimethylphosphinate, aluminum dimethylphosphinate, zinc dimethylphosphinate, calcium ethylmethylphosphinate, magnesium ethylmethylphosphinate, aluminum ethylmethylphosphinate, zinc ethylmethylphosphinate, Calcium diethylphosphinate, magnesium diethylphosphinate, aluminum diethylphosphinate, zinc diethylphosphinate, calcium methyl-n-propylphosphinate, magnesium methyl-n-propylphosphinate, aluminum methyl-n-propylphosphinate, methyl-n -Zinc propylphosphinate, calcium methylphenylphosphinate, magnesium phenylphenylphosphinate , Aluminum methylphenyl phosphinate, methyl phenyl phosphinate, zinc, calcium diphenyl phosphinate, magnesium diphenyl phosphinate, aluminum diphenyl phosphinate, and zinc diphenyl phosphinate and the like. Diphosphinic acid salts include methandi (methylphosphinic acid) calcium, methandi (methylphosphinic acid) magnesium, methandi (methylphosphinic acid) aluminum, methandi (methylphosphinic acid) zinc, benzene-1,4-di (methylphosphinic acid) Examples include calcium, benzene-1,4-di (methylphosphinic acid) magnesium, benzene-1,4-dimethylphosphinic acid) aluminum, and benzene-1,4-di (methylphosphinic acid) zinc. Among these (di) phosphinic acid salts, aluminum ethylmethylphosphinate, aluminum diethylphosphinate, and zinc diethylphosphinate are particularly preferable from the viewpoints of flame retardancy and electrical characteristics.

  The phosphazene compound is an organic compound having a —P═N— bond in the molecule, preferably at least one compound selected from the group consisting of cyclic phenoxyphosphazenes, chain phenoxyphosphazenes, and bridged phenoxyphosphazene compounds. Examples of the cyclic phenoxyphosphazene compound include hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene from a mixture of cyclic and linear chlorophosphazenes obtained by reacting ammonium chloride and phosphorus pentachloride at a temperature of 120 to 130 ° C. And compounds such as phenoxycyclotriphosphazene, octaphenoxycyclotetraphosphazene, and decaffenoxycyclopentaphosphazene obtained by removing a cyclic chlorophosphazene such as decachlorocyclopentaphosphazene and then substituting with a phenoxy group. As the chain phenoxyphosphazene compound, for example, hexachlorocyclotriphosphazene obtained by the above method is subjected to reversion polymerization at a temperature of 220 to 250 ° C., and the obtained linear dichlorophosphazene having a polymerization degree of 3 to 10,000 is converted into a phenoxy group. The compound obtained by substituting with is mentioned. Examples of the crosslinked phenoxyphosphazene compound include a compound having a crosslinked structure of 4,4′-sulfonyldiphenylene (bisphenol S residue) and a crosslinked structure of 2,2- (4,4′-diphenylene) isopropylidene group. Compounds having a crosslinked structure of 4,4′-diphenylene groups, such as compounds, compounds having a crosslinked structure of 4,4′-oxydiphenylene groups, compounds having a crosslinked structure of 4,4′-thiodiphenylene groups, etc. Is mentioned. The content of the phenylene group in the crosslinked phenoxyphosphazene compound is usually 50 to 99.9%, preferably 70 to 90%, based on the total number of phenyl groups and phenylene groups in the cyclic phosphazene compound and / or the chain phenoxyphosphazene compound. It is. The crosslinked phenoxyphosphazene compound is particularly preferably a compound having no free hydroxyl group in the molecule.

  Aromatic phosphates are a group of compounds produced by the reaction of phosphorus oxychloride and phenols or a mixture of phenols and alcohols. Aromatic phosphate esters include triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, or t-butylphenyl diphenyl phosphate, bis- (t-butylphenyl) phenyl Examples thereof include butylated phenyl phosphates such as phosphate, tris- (t-butylphenyl) phosphate, propylated phenyl phosphates such as isopropylphenyl diphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate, and the like.

  The aromatic condensed phosphate ester is a reaction product of phosphorus oxychloride, a divalent phenolic compound, and phenol (or alkylphenol). Examples of the aromatic condensed phosphate ester include resorcinol bis-diphenyl phosphate, resorcinol bis-dixylenyl phosphate, bisphenol A bis-diphenyl phosphate, and the like.

  Halogenated phosphoric acid esters are produced by reacting alkylene oxide and phosphorus oxychloride in the presence of a catalyst. Examples of halogenated phosphate esters include tris (chloroethyl) phosphate, tris (β-chloropropyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2 chloroethyl) dichloroisopentyl diphosphate, polyoxyalkylene bis (dichloroalkyl) phosphate Etc.

  The addition amount of the phosphorus flame retardant in the present invention is 1 to 50 parts by weight, preferably 2 to 40 parts by weight, and more preferably 3 to 35 parts by weight with respect to 100 parts by weight of the (a) polyamide resin. .

  Examples of the nitrogen-based flame retardant in the present invention include compounds that form triazine-based compounds and cyanuric acid or isocyanuric acid salts. A triazine compound and a salt of cyanuric acid or isocyanuric acid are adducts of a triazine compound and cyanuric acid or isocyanuric acid, usually 1 to 1 (molar ratio), sometimes 2 to 1 (molar ratio). ). Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded. Among the salts with cyanuric acid or isocyanuric acid, examples of particularly preferred triazine compounds include melamine, mono (hydroxymethyl) melamine, di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2 -A salt of amide-4,6-diamino-1,3,5-triazine is mentioned, and a salt of melamine, benzoguanamine or acetoguanamine is particularly preferable. Specific examples of salts of triazine compounds with cyanuric acid or isocyanuric acid include melamine cyanurate, mono (β-cyanoethyl) isocyanurate, bis (β-cyanoethyl) isocyanurate, tris (β-cyanoethyl) isocyanurate, etc. Among them, melamine cyanurate is particularly preferable.

  The addition amount of the nitrogen-based flame retardant in the present invention is 1 to 50 parts by weight, preferably 3 to 30 parts by weight, more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the (a) polyamide resin. .

Examples of the metal hydroxide flame retardant in the present invention include magnesium hydroxide and aluminum hydroxide, and magnesium hydroxide is more preferable. These are usually commercially available and are not particularly limited, such as particle diameter, specific surface area, and shape, but preferably have a particle diameter of 0.1 to 20 im, a specific surface area of 3 to 75 m ² / g, and a shape. Is preferably spherical, needle-shaped or platelet-shaped. The surface treatment of the metal hydroxide flame retardant may or may not be performed. Examples of the surface treatment method include treatment methods such as coating formation with a thermosetting resin such as a silane coupling agent, an anionic surfactant, a polyfunctional organic acid, and an epoxy resin.

  The addition amount of the metal hydroxide flame retardant in the present invention is 1 to 50 parts by weight, preferably 10 to 50 parts by weight, and more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the (a) polyamide resin. Part.

  The brominated flame retardant used in the present invention is not particularly limited as long as it is a compound containing bromine in the chemical structure, and generally known flame retardants can be used. For example, hexabromobenzene, pentabromotoluene, hexabromobiphenyl, decabromobiphenyl, hexabromocyclodecane, decabromodiphenyl ether, octabromodiphenyl ether, hexabromodiphenyl ether, bis (pentabromophenoxy) ethane, ethylene-bis (tetrabromophthalimide) , Monomeric organic bromine compounds such as tetrabromobisphenol A, brominated polycarbonates (for example, polycarbonate oligomers produced from brominated bisphenol A or copolymers thereof with bisphenol A), brominated epoxy compounds (for example, brominated bisphenols) By reaction of diepoxy compounds and brominated phenols produced by the reaction of A with epichlorohydrin and epichlorohydrin Monoepoxy compound), poly (brominated benzyl acrylate), brominated polyphenylene ether, brominated bisphenol A, condensate of cyanuric chloride and brominated phenol, brominated (polystyrene), poly (brominated styrene), crosslinked Examples include brominated polystyrene such as brominated polystyrene, and halogenated polymer bromine compounds such as crosslinked or non-crosslinked brominated poly (α-methylstyrene). Among them, ethylene bis (tetrabromophthalimide), brominated epoxy polymer Brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are preferred, brominated polystyrene, crosslinked brominated polystyrene, brominated polyphenylene ether and brominated polycarbonate are most preferred. Can be used.

  The addition amount of the brominated flame retardant in the present invention is 1 to 50 parts by weight, preferably 10 to 50 parts by weight, more preferably 20 to 50 parts by weight with respect to 100 parts by weight of the (a) polyamide resin. .

  In addition, it is also preferable to add a flame retardant aid used synergistically to improve flame retardancy by using in combination with the above brominated flame retardant, for example, antimony trioxide, antimony tetraoxide, pentoxide. Antimony, antimony deoxydioxide, crystalline antimonic acid, sodium antimonate, lithium antimonate, barium antimonate, antimony phosphate, zinc borate, zinc stannate, basic zinc molybdate, calcium zinc molybdate, molybdenum oxide, zirconium oxide Zinc oxide, iron oxide, red phosphorus, swellable graphite, carbon black and the like can be exemplified. Of these, antimony trioxide and antimony pentoxide are more preferable. The blending amount of the flame retardant aid is 0.2 to 30 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the polyamide resin (a) from the viewpoint of flame retardant improvement effect. .

  The flame retardant action of melamine cyanurate that can be used in the present invention is that the melamine cyanurate reacts with the amide group in the polyamide by combustion to decompose at the amide group and suppress heat accumulation, and as a fire extinguishing agent. This is due to the formation of a working nitrogen-containing compound. For example, the polyamide 410 resin containing tetramethylene diamine as a constituent component shown in the examples has a higher amide group concentration than the polyamide 610 resin containing hexamethylene diamine as a constituent component, so that the polymer decomposes during combustion. It is easy to think that heat accumulation is suppressed and flame retardancy is improved.

  In addition, the flame-retardant polyamide resin composition of the present invention contains a polyamide resin other than the above-mentioned (a) polyamide resin or other polymers according to the required properties within a range not impairing the object of the present invention. be able to. Specifically, polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polypentamethylene adipamide (nylon 56), polypentamethylene sebaca Mido (nylon 510), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene Adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), Such Riki silylene adipamide (nylon XD6), and mixtures or copolymers thereof. Among them, preferred examples include nylon 6, nylon 66, nylon 610, nylon 6/66 copolymer, nylon 6/12 copolymer and the like.

  The flame-retardant polyamide resin composition of the present invention includes other components such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and These substitutes, copper halides, iodine compounds, etc.), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (fatty alcohols, aliphatic amides, fats) Group bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, aniline black, etc.), crystal nucleating agents (talc, silica, kaolin, clays, etc.), plasticizers (p -Octyl oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic (Alkyl sulfate type anionic antistatic agent, quaternary ammonium salt type antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), filler ( Graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, copper, iron, stainless steel, glass fiber, carbon Fibers, aramid fibers, bentonite, montmorillonite, synthetic mica particles, fiber, needle, plate filler), other polymers (other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide) , Crystal polymer, polysulfone, polyether sulfone, ABS resin, may be added SAN resin, polystyrene, etc.) at any time.

  The method for preparing the flame retardant polyamide resin composition of the present invention is not limited to a specific method, but as a specific and efficient example, a raw material polyamide resin, a mixture of flame retardant, a single-screw or twin-screw extruder, Examples thereof include a method of supplying to a known melt-kneader such as a Banbury mixer, a kneader, and a mixing roll, and melt-kneading at or above the melting point of the polyamide resin used.

  The flame-retardant polyamide resin composition thus obtained can be molded by a generally known method, and can be formed into a molded article such as a molded article such as injection molding, extrusion molding or compression molding, sheet or film. The flame-retardant polyamide resin composition of the present invention is an electrical or electronic component (coil bobbin, connector, relay, disk drive chassis, transformer, electromagnetic switch, switch component, outlet component, socket, plug, capacitor, taking advantage of its excellent characteristics. , Various cases, resistors, metal terminals or parts used in places where conductors are incorporated, etc.), household electrical appliance parts (for example, general household appliance housings, parts related to computers or peripheral equipment, lighting parts) , Telephone / facsimile equipment related parts, air conditioner parts, parts for home audiovisual equipment (TV, digital versatile disc player, VCR, etc.), office automation (OA) equipment parts (computer related parts, acoustic parts, lighting parts) , Telegraph or telephone equipment related Products, facsimile parts, copier parts, air conditioning parts, optical equipment parts, etc.), mechanical mechanism parts (various gears, various bearings, motor parts, etc.) and automotive parts (automotive ignition device parts, automotive connectors, and various types) This is useful for automobile electrical parts.

  The present invention will be described more specifically with reference to the following examples. The characteristic evaluation was performed according to the following method.

[Sulfuric acid relative viscosity (ηr)]
Measurement was performed using an Ostwald viscometer at a concentration of 0.01 g / ml in 25% sulfuric acid in 98% sulfuric acid.

[Tensile properties]
In accordance with ASTM D638, a tensile tester Tensilon UTA2.5T (Orientec Co., Ltd.) was used to conduct a tensile test on a 1/8 inch thick ASTM No. 1 dumbbell specimen at a crosshead speed of 10 mm / min. The breaking strain was determined.

[Bending characteristics]
In accordance with ASTM D790, a bending tester Tensilon RTA-1T (Orientec Co., Ltd.) was used to conduct a bending test on a 1/4 inch thick rod-shaped test piece at a crosshead speed of 3 mm / min. Asked. In addition, the bending characteristic at the time of water absorption performed the water absorption process so that the polyamide resin component in a composition might become the air equilibrium water absorption shown below, and performed the same measurement.
N410: 2.0 wt%
N610: 1.5 wt%
N66: 2.5 wt%
N46: 4.0 wt%
N49: 2.5 wt%
N412: 1.4 wt%
N612: 0.9 wt%.

[High load DTUL]
Using an HDT-TESTER manufactured by Toyo Seiki Co., Ltd., and using a 1 / 4-inch-thick bar-shaped test piece, the deflection temperature under load at a stress of 18.5 kgf / cm ² (1.82 MPa) applied to the test piece is measured according to ASTM D648-. Evaluation was performed according to 82.

[Flame retardance]
The flame retardance was evaluated according to the evaluation standard defined in UL94, using a test piece for flame retardancy evaluation having a thickness of 1/32 inch defined in UL94. The flame retardancy level decreases in the order of V-0>V-1>V-2> HB.

Reference Example 1 (Production of tetramethylene sebacamide salt)
300.0 g (1.483 mol) of sebacic acid (Tokyo Kasei) was added to 2375 g of methanol, and it was dissolved by being immersed in a 60 ° C. water bath. A solution prepared by dissolving 130.75 g (1.483 mol) of tetramethylenediamine (Guangei Chemical Industry) in 554 g of methanol was added dropwise over 2 hours. After stirring for 3 hours, the mixture was left standing at room temperature to precipitate the precipitated salt. Thereafter, filtration and ethanol washing were performed, followed by vacuum drying at 50 ° C. for 24 hours to obtain nylon 410 salt.

Reference Example 2 (Production of tetramethylene adipamide salt)
To 3 L of ethanol, 280.7 g (1.92 mol) of adipic acid (Tokyo Kasei) was added and dissolved at 60 ° C. A solution prepared by dissolving 169.3 g (1.92 mol) of tetramethylenediamine (Guangei Chemical Industry) prepared in advance in 1 L of ethanol was added dropwise thereto over 2 hours. After stirring for 3 hours, the mixture was left standing at room temperature to precipitate the deposited salt. Thereafter, filtration and ethanol washing were performed, followed by vacuum drying at 50 ° C. for 24 hours to obtain a nylon 46 salt.

Reference Example 3 (Production of polytetramethylene sebacamide (melt polymerization))
700 g of nylon 410 salt prepared in Reference Example 1, 2.12 g of tetramethylenediamine (1.00 mol% with respect to nylon 410 salt), 0.3065 g of sodium hypophosphite (0.05 wt% with respect to the weight of the produced polymer) ) Was charged into a 3 L pressure vessel, sealed, and purged with nitrogen. Start the heating, after the can internal pressure reaches 5.0kg ^/ cm 2 (0.49MPa), the can internal pressure while releasing moisture out of the system 5.0kg ^/ cm 2 (0.49MPa) Hold for 1.5 hours. Thereafter, the internal pressure of the can was returned to normal pressure over 10 minutes, and the reaction was further continued for 1.5 hours under a nitrogen flow to complete the polymerization. Thereafter, the polymer was discharged from the polymerization can in a gut shape and pelletized, and this was vacuum dried at 80 ° C. for 24 hours to obtain nylon 410 having ηr = 2.84.

Reference Example 4 (Production of polytetramethylene sebacamide (solid phase polymerization))
700 g of nylon 410 salt prepared in Reference Example 1, 4.25 g of tetramethylenediamine, 0.3065 g of sodium hypophosphite monohydrate, and 70 g of ion-exchanged water are charged into a pressure vessel with an internal volume of 3 L equipped with a stirrer. And then purged with nitrogen. Heating was started with the pressure vessel sealed, and after reaching an internal temperature of 223 ° C. and 15.0 kg / cm ² (1.47 MPa), the internal pressure of the can was reduced to 15.0 kg / cm while releasing moisture out of the system. ² (1.47 MPa) for 30 minutes. Thereafter, the contents were discharged from the reaction vessel onto a cooling belt. The low-order condensate obtained by vacuum drying this at 80 ° C. for 24 hours was subjected to solid phase polymerization at 220 ° C. and 100 Pa for 24 hours to obtain nylon 410 (ηr = 3.06).

Reference Example 5 (Production of polytetramethylene adipamide (solid phase polymerization))
700 g of nylon 46 salt prepared in Reference Example 2, 5.27 g of tetramethylenediamine, 0.2962 g of sodium hypophosphite monohydrate, and 70 g of ion-exchanged water were charged into a pressure vessel with an internal volume of 3 L equipped with a stirring blade. Sealed and purged with nitrogen. Heating was started with the pressure vessel sealed, and after reaching an internal temperature of 225 ° C. and 15.0 kg / cm ² (1.47 MPa), the internal pressure of the can was reduced to 15.0 kg / cm ² while releasing moisture out of the system. (1.47 MPa) for 30 minutes. Thereafter, the contents were discharged from the reaction vessel onto a cooling belt. The low-order condensate obtained by vacuum drying at 80 ° C. for 24 hours was subjected to solid phase polymerization at 260 ° C. and 100 Pa for 20 hours to obtain nylon 46 (ηr = 3.10).

Reference Example 6 (Production of tetramethylene azelamide salt)
200.0 g (1.06 mol) of azelaic acid (Emerox 1144 manufactured by Cognis) was added to 1 L of methanol, and the mixture was immersed in a 60 ° C. water bath and dissolved. Here, a solution prepared by dissolving 93.7 g (1.06 mol) of tetramethylenediamine (Kanto Chemical Co., Inc.) prepared in advance in 200 ml of methanol was added dropwise over 1 hour. After stirring for 3 hours, the mixture was concentrated with an evaporator to precipitate a salt. Thereafter, filtration and washing with methanol were performed, followed by vacuum drying at 50 ° C. for 24 hours to obtain nylon 49 salt.

Reference Example 7 (Production of tetramethylene dodecamide salt)
To 2 L of methanol, 200.0 g (0.868 mol) of dodecanedioic acid (Ube Industries) was added and dissolved by being immersed in a 60 ° C. water bath. A solution prepared by dissolving 76.6 g (0.868 mol) of tetramethylenediamine (Kanto Chemical) prepared in advance in 200 ml of methanol was added dropwise over 1 hour. After stirring for 3 hours, the mixture was left standing at room temperature to precipitate the precipitated salt. Thereafter, filtration and washing with methanol were performed, followed by vacuum drying at 50 ° C. for 24 hours to obtain a nylon 412 salt.

Reference Example 8 (Production of polytetramethylene azelamide (melt polymerization))
Nylon 49 salt 700 g obtained in Reference Example 6, tetramethylenediamine 7.836 g (3.51 mol% based on nylon 49 salt), sodium hypophosphite monohydrate 0.3065 g (0 based on the weight of the produced polymer) 0.05 wt%) was charged into a 3 L pressure vessel, sealed, and purged with nitrogen. Heating was started by setting the heater temperature to 285 ° C., and after the internal pressure of the can reached 5.0 kg / cm ² (0.49 MPa), the internal pressure of the can was reduced to 5.0 kg while releasing moisture out of the system. / Cm ² (0.49 MPa) for 1.5 hours. Thereafter, the internal pressure of the can was returned to normal pressure over 10 minutes, and the reaction was further continued for 1.5 hours under a nitrogen flow to complete the polymerization. At this time, the inside temperature of the can reached 275 ° C. Thereafter, the polymer was discharged from the polymerization can in a gut shape and pelletized, and this was vacuum dried at 80 ° C. for 24 hours to obtain nylon 49 having ηr = 2.69.

Reference Example 9 (Production of polytetramethylene dodecamide (melt polymerization))
Except for using 700 g of the nylon 412 salt obtained in Reference Example 7 and 6.783 g of tetramethylenediamine (3.50 mol% with respect to the nylon 412 salt), the same method as in Reference Example 8 was used, and ηr = 2.81. Nylon 412 was obtained.

(Examples 1-2 , 10, Reference Examples 3-6, Comparative Examples 1, 8)
Using a TEX30 type twin screw extruder manufactured by Nippon Steel Works set to a cylinder setting temperature of 270 ° C. and a screw rotation speed of 200 rpm, the polytetramethylene sebacamide resin obtained in Reference Example 3, a flame retardant, and a flame retardant aid are shown. After dry blending at each ratio described in 1-2, the side is supplied from the main feeder, and the inorganic filler is installed at a position of about 0.35 when viewed from the upstream side when the total length of the screw is 1.0. The mixture was supplied from a feeder and melt kneaded. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 265 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, heat resistance, and flame retardancy of each sample are as shown in Tables 1-2.

(Example 7)
Using a TEX30 type twin screw extruder manufactured by Nippon Steel Works set to a cylinder set temperature of 270 ° C. and a screw speed of 200 rpm, the polytetramethylene sebacamide resin and flame retardant obtained in Reference Example 4 are listed in Table 1. After dry blending at a ratio, the mixture was supplied from the main feeder and melt kneaded. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 265 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, heat resistance, and flame retardancy of each sample are as shown in Table 1.

(Examples 8 and 9)
Polytetramethylene azamide resin obtained in Reference Example 8 and polytetramethylene dodeca obtained in Reference Example 9 using a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set at a cylinder setting temperature of 260 ° C. and a screw rotation speed of 200 rpm After dry blending the mid resin and the flame retardant at each ratio shown in Table 1, they were supplied from the main feeder and melt kneaded. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 255 ° C., mold temperature 80 ° C.). The results of evaluating the mechanical properties, heat resistance, and flame retardancy of each sample are as shown in Table 1.

(Comparative Examples 2 and 3)
Using a TEX30 type twin screw extruder manufactured by Nippon Steel Works with a cylinder set temperature of 250 ° C. and a screw rotation speed of 200 rpm, a nylon 610 resin (CM 2001 manufactured by Toray Industries, Inc.) having a relative viscosity of sulfuric acid of 2.70 and a flame retardant are displayed. After dry blending at each ratio described in 2, it was supplied from an extruder main feeder and melt kneaded. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 250 ° C., mold temperature 80 ° C.). Table 2 shows the results of evaluating the mechanical properties, heat resistance, and flame retardancy of each sample.

(Comparative Example 4)
Table 2 shows Nylon 66 resin (CM3001 manufactured by Toray Industries, Inc.) and flame retardants having a relative viscosity of 2.78 using a TEX30 type twin screw extruder manufactured by Nippon Steel Works with a cylinder set temperature of 280 ° C. and a screw rotation speed of 200 rpm. After dry blending at each ratio described in 1., the mixture was supplied from an extruder main feeder and melt kneaded. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 280 ° C., mold temperature 80 ° C.). Table 2 shows the results of evaluating the mechanical properties, heat resistance, and flame retardancy of each sample.

(Comparative Example 5)
Each of the polytetramethylene adipamide resins and flame retardants obtained in Reference Example 5 are listed in Table 2 using a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set at a cylinder setting temperature of 310 ° C. and a screw speed of 200 rpm. After dry blending at a ratio, the mixture was supplied from the main feeder and melt kneaded. However, when melt kneading is performed at 310 ° C., melamine cyanurate itself decomposes to generate decomposition gas, so that the gut discharged from the die foams violently and cannot be pelletized and cannot be molded.

(Comparative Example 6)
Using a TEX30 type twin screw extruder manufactured by Nippon Steel Works, set at a cylinder set temperature of 310 ° C. and a screw speed of 200 rpm, the polytetramethylene adipamide resin obtained in Reference Example 5, a flame retardant, and a flame retardant aid are shown. After being dry blended in the proportions described in 2, the main feeder is used to supply the inorganic filler from the side feeder installed at a position of about 0.35 when viewed from the upstream side when the total length of the screw is 1.0. The mixture was supplied and melt kneaded. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 265 ° C., mold temperature 80 ° C.). Table 2 shows the results of evaluating the mechanical properties, heat resistance, and flame retardancy of each sample.

(Comparative Example 7)
Using a TEX30 type twin screw extruder manufactured by Nippon Steel Works with a cylinder set temperature of 240 ° C. and a screw rotation speed of 200 rpm, nylon 612 resin (DuPont Zytel 151L) and flame retardant were dried in the proportions shown in Table 2. After blending, the mixture was supplied from an extruder main feeder and melt kneaded. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, cylinder temperature 240 ° C., mold temperature 80 ° C.). Table 2 shows the results of evaluating the mechanical properties, heat resistance, and flame retardancy of each sample.

The flame retardant (b) used in the examples and comparative examples is as follows.
(B-1): Melamine cyanurate (MC-4000 manufactured by Nissan Chemical Industries)
(B-2): Red phosphorus (Nova Excel 140 manufactured by Phosphor Chemical Industries)
(B-3): Brominated polystyrene resin (GLC, product name: PDBS)
(B-4): Magnesium hydroxide (Kisuma 5E manufactured by Kyowa Chemical Industry)
(B-5): Melamine polyphosphate, melem, melam compound (PMP-200 manufactured by Nissan Chemical Industries)
Similarly, the flame retardant aid (c) is as follows.
(C-1): Antimony trioxide (ATOX manufactured by Nippon Seiko Co., Ltd.)
Similarly, (d) inorganic filler is as follows.
(D-1): Glass fiber (T289 manufactured by Nippon Electric Glass).

  This example was superior to Comparative Example 1 in tensile strength, toughness (tensile fracture strain), water resistance, and heat resistance (high load DTUL).

  In comparison with Example 2 and Example 7, the polyamide resin produced by melt polymerization as a raw material was used for the tensile strength, toughness (tensile fracture strain), and heat resistance (high load DTUL) of the polyamide resin composition. Excellent.

  From the comparison between Examples 1 and 2 and Comparative Examples 2 and 3, polyamide 410 is superior in bending characteristics at the time of atmospheric equilibrium water absorption and excellent in water resistance in spite of higher atmospheric equilibrium water absorption rate than polyamide 610. Excellent flame retardancy. Further, it has high crystallinity and is excellent in tensile strength and heat resistance (high load DTUL).

  From the comparison between Example 2 and Comparative Example 4, the polyamide 410 has the same level of bending strength and bending elastic modulus as the polyamide 66, but has lower heat resistance (high load DTUL) and water resistance than the polyamide 66. It was also excellent in properties.

  From the comparison between Example 4 and Comparative Example 6, the polyamide 410 was superior to the polyamide 46 in bending characteristics at the time of water absorption and excellent in water resistance.

  From a comparison between Example 9 and Comparative Example 7, polyamide 412 was superior to polyamide 612 in flame retardancy, and excellent in tensile strength, toughness (tensile fracture strain), water resistance, and heat resistance (high load DTUL). .

  In Comparative Example 1, a flame retardant in an amount equal to or greater than that specified in the present invention was blended, so that the tensile strength, toughness (tensile fracture strain), and heat resistance (high load DTUL) were inferior. Moreover, since the comparative example 8 mix | blended the flame retardant of less than the quantity prescribed | regulated by this invention, it was inferior to heat resistance (high load DTUL) and a flame retardance.

  The flame-retardant polyamide resin composition of the present invention can be molded by any method such as commonly known injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, and various molded products. Can be processed and used. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, various films such as uniaxially stretched and biaxially stretched, sheets, various fibers such as unstretched yarn, stretched yarn, and superstretched yarn. . In particular, in the present invention, it is possible to process various electric / electronic parts, automobile parts and the like by taking advantage of excellent flame retardancy, strength and water resistance.

Claims (6)

(A) 1-100 parts by weight of melamine cyanurate is blended with 100 parts by weight of a polyamide resin composed of a monomer containing tetramethylenediamine and an aliphatic dicarboxylic acid having 7 or more carbon atoms as main components. A flame retardant polyamide resin composition. 2. The flame retardancy according to claim 1, wherein the relative viscosity of sulfuric acid measured at 25 ° C. and a concentration of 0.01 g / ml in concentrated sulfuric acid of the (a) polyamide resin is 2.0 to 5.0. Polyamide resin composition. The flame retardant polyamide resin composition according to claim 1 or 2, wherein the aliphatic dicarboxylic acid having 7 or more carbon atoms is at least one selected from azelaic acid, sebacic acid, undecanedioic acid, and dodecanedioic acid. The flame-retardant polyamide resin composition according to claim 1, wherein the (a) polyamide resin is produced by melt polymerization. Furthermore, the flame-retardant polyamide resin composition in any one of Claims 1-4 formed by mix | blending an inorganic filler. The molded article which consists of a flame-retardant polyamide resin composition in any one of Claims 1-5.