JP2005139245A - Polyamide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a non-halogen flame-retardant polyamide resin composition which has very high flame retardancy and a very high deflection temperature under load and exhibits excellent molding processability by incorporating melamine cyanurate and a swellable phyllosilicate. <P>SOLUTION: The polyamide resin composition comprises as the main components 100 pts. wt. of a polyamide resin and, incorporated therewith, 2-20 pts. wt. of melamine cyanurate and 1-15 pts. wt. of the swellable phyllosilicate having replaceable metal cations existing between layers replaced by organic onium ions. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a halogen-free flame retardant nylon excellent in heat resistance.

  Conventionally, polyamide resins are excellent in mechanical properties such as tensile and bending strength and elastic modulus, and also have good heat resistance, chemical resistance, and flame resistance. Widely used in parts and machine parts. However, in recent years, the demand for flame retardant plastic materials has increased mainly in the field of electrical and electronic components, and materials that comply with UL94V-0 are required in the vertical test method of the UL94 standard. In response to such demands, a resin composition in which an organic halogen flame retardant is blended with a polyamide resin as a flame retardant has been proposed, but there are problems such as generation of hydrogen halide during combustion and a large amount of smoke generation. There is a movement to regulate the use of plastic products containing some halogenated flame retardants. For this reason, a non-halogen flame retardant material has been studied.

For example, Patent Document 1 proposes a resin composition containing melamine cyanurate, which is a reaction product of melamine and cyanuric acid. Non-reinforced flame retardant nylon conforms to UL94-V0, but if a reinforcing material such as talc is blended for the purpose of improving mechanical strength, the flame retardancy is lowered and does not conform to UL94V-0. Patent Document 2 proposes that melamine phosphate and red phosphorus be used in combination, but red phosphorus exhibits a reddish brown color and cannot obtain a white or light-colored molded product, and cannot meet the demand for full color.
Japanese Patent Publication No. 58-25379 (Claim 1) Japanese Patent Laid-Open No. 11-246778 (Claim 1)

  An object of the present invention is to provide a non-halogen flame retardant polyamide resin composition having very high flame retardancy and excellent heat resistance due to melamine cyanurate and swellable layered silicate.

  Thus, as a result of intensive studies to solve the above problems, the present inventors have found that the object can be achieved as a result of blending a swellable layered silicate with a polyamide resin and melamine cyanurate, and have reached the present invention.

That is, the present invention
(1) Swellable layered silicic acid obtained by exchanging exchangeable metal cations existing between (B) melamine cyanurate and (C) layers with organic onium ions with respect to 100 parts by weight of (A) polyamide resin A polyamide resin composition comprising 1 to 15 parts by weight of a salt as a main component.

  (2) The polyamide resin composition according to (1), wherein the polyamide resin has a relative viscosity of 1.5 to 7.0.

  (3) The polyamide resin composition according to either (1) or (2), wherein the polyamide resin (A) is polyamide 66.

  (4) The polyamide resin composition according to (1) or (2), wherein the (A) polyamide resin is a copolymer of polyamide 66 units and polyamide 6I units and / or a mixed polyamide.

  (5) The interlayer distance of the swellable layered silicate obtained by exchanging exchangeable metal cations existing between layers with organic onium ions is 1.6 to 2.9 nm (1) or ( 2) The polyamide resin composition according to any one of the above.

  (6) A molded product obtained by molding the polyamide resin composition according to any one of (1) to (5) by at least one method selected from injection molding, extrusion molding, and blow molding.

(7) The molded article according to (6), which is any one selected from electrical and electronic parts, automobile parts, and building material parts.
Consists of.

  The polyamide resin composition of the present invention contains melamine cyanurate and swellable layered silicate, has very high flame retardancy, and is excellent in heat resistance.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The (A) polyamide resin used 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-trimethylcyclohexa , Bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, etc. , Cycloaliphatic, aromatic diamines, and adipic acid, peric 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. Each of nylon homopolymers or copolymers derived from It can be used alone or in the form of mixtures.

  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.

  Particularly preferred polyamide resins include nylon 66, and copolymers having hexamethylene terephthalamide units such as nylon 6I / 66, nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, and the like. It is also practically preferable to use as a mixture depending on required properties such as moldability and compatibility.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Is preferable, more preferably 1.5 to 4.0, and particularly preferably 1.8 to 3.2.

  The particle diameter of (B) melamine cyanurate of the present invention is preferably 100 μm or less. It is because tensile strength may be impaired when it exceeds 100 micrometers. In particular, those of 80 μm or less are preferable.

  The swellable layered silicate in which the exchangeable metal cation existing between (C) layers used in the present invention is exchanged with an organic onium ion is 41 pages of clay handbook (edited by the Japan Clay Society, Gihodo (January 15, 1967) Issue)), a 2: 1 type structure in which a silicate tetrahedron sheet overlaps an upper and lower sides of an octahedron sheet containing a metal such as aluminum, magnesium, lithium, etc. to form one plate-like crystal layer. It is a compound having an exchangeable cation 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 20 to 300 meq / 100 g, preferably 40 to 110 meq / 100 g, more preferably 60 to 95 meq / 100 g. The cation exchange capacity is a value measured by a methylene blue adsorption method.

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

  In the swellable layered silicate used in the present invention, the exchangeable cation present between the layers is preferably exchanged with an organic onium ion.

  Examples of organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Among these, ammonium ions and phosphonium ions are preferable, and ammonium ions are particularly preferable. As an ammonium ion, any of a primary ammonium ion, a secondary ammonium ion, a tertiary ammonium ion, and a quaternary ammonium ion may be sufficient.

  Examples of the primary ammonium ion include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like.

  Examples of secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium.

  Examples of the tertiary ammonium ion include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium.

  Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium and benzyldimethyloctadecylammonium, and alkyls such as trimethyloctylammonium, trimethyldodecylammonium and trimethyloctadecylammonium. Examples thereof include dimethyldialkylammonium ions such as trimethylammonium ion, 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 the above ammonium ions, it is very preferable to use a quaternary ammonium ion having 15 to 30 carbon atoms. Specific examples of such quaternary ammonium ions include trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, and the like, and trioctylmethylammonium and benzyldimethyloctadecylammonium are most preferably used.

  In the present invention, a swellable layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions is produced by reacting a swellable layered silicate having exchangeable cations between layers and organic onium ions. can do. Specifically, a method of performing an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method of directly reacting a layered silicate with a liquid or molten ammonium salt may be used.

  In the present invention, the amount of organic onium ions contained in the swellable layered silicate is from the viewpoint of the dispersibility of the swellable layered silicate, the thermal stability during melting, the gas during molding, the suppression of odor generation, etc. The cation exchange capacity of the layered silicate is preferably 0.4 to 2.0 equivalents, more preferably 0.8 to 1.2 equivalents.

  In the present invention, the interlayer distance of the plate-like crystal layer of the swellable layered silicate is preferably 1.6 to 2.9 nm. Here, the interlayer distance refers to a surface interval obtained by wide-angle X-ray diffraction measurement of a dry powder of swellable layered silicate. When the interlayer distance is less than 1.6 nm or more than 2.9 nm, the dispersibility of the layered silicate may be lowered and the heat resistance may be lowered when melt-kneaded with the polyamide resin. The interlayer distance can be adjusted by the cation exchange capacity of the layered silicate to be used, the bulk height (number of carbon atoms) of the organic onium ions, and the amount of the organic onium ions. In the present invention, an organic onium ion having 27 carbon atoms and benzyldimethylstearylammonium chloride are allowed to act on Na-type montmorillonite so that the cation exchange capacity is 1.0 times, whereby the interlayer distance is 1.9 nm. Got.

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

  Particularly preferred are organosilane compounds (hereinafter referred to as silane coupling agents). Specific examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- Epoxy group-containing alkoxysilane compounds such as (3,4-epoxycyclohexyl) ethyltrimethoxysilane, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane, γ-ureidopropyltri Ureido group-containing alkoxysilane compounds such as ethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropi Trimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, etc. Isocyanato group-containing alkoxysilane compounds, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and other amino group-containing alkoxysilanes Compounds, hydroxyl-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane, γ-hydroxypropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, vinyl Trimethoxysilane, N-β- (N- vinylbenzylaminoethyl)-.gamma.-aminopropyltrimethoxysilane hydrochloride, such as carbon in - such as carbon unsaturated group-containing alkoxysilane compound. In particular, a carbon-carbon unsaturated group-containing alkoxysilane compound is preferably used.

  The treatment of the layered silicate with these silane coupling agents can be carried out by adsorbing the silane coupling agent to the layered silicate in a polar solvent such as water, methanol, ethanol, or a mixed solvent thereof, such as a Henschel mixer. Add a layered silicate into a high-speed agitator and add it to a silane coupling agent or an aqueous solution containing an organic solvent while stirring, or add a silane coupling agent directly to the layered silicate. And a method of mixing and adsorbing in a mortar or the like. When the layered silicate is treated with a silane coupling agent, it is preferable to mix water, acidic water, alkaline water and the like at the same time in order to promote hydrolysis of the alkoxy group of the silane coupling agent. In order to increase the reaction efficiency of the silane coupling agent, water such as methanol and ethanol, and an organic solvent that dissolves both the silane coupling agent may be mixed in addition to water. It is also possible to further promote the reaction by heat-treating the layered silicate treated with such a silane coupling agent.

  Instead of treating the layered silicate with the coupling agent in advance, a so-called integral blend method in which these coupling agents are added when the layered silicate and the polyamide resin are melt-kneaded may be used.

  The polyamide resin composition of the present invention needs to contain 2 to 20 parts by weight of (B) melamine cyanurate with respect to 100 parts by weight of (A) polyamide resin composition. If it is 2 parts by weight or less, the flame retardancy is impaired, and if it exceeds 20 parts by weight, the mechanical properties of the molded product are impaired. Especially preferably, it is the range of 3-10 weight part.

  (C) The swellable layered silicate obtained by exchanging exchangeable metal cations existing between layers with organic onium ions needs to be 1 to 15 parts by weight. If it is less than 1 part by weight, the heat resistance effect cannot be obtained, and if it exceeds 15 parts by weight, flame retardancy is impaired. Particularly preferred is a range of 1.5 to 6.0 parts by weight.

  As described above, a polyamide resin composition that is particularly excellent in flame retardancy and heat resistance can be obtained for the first time by a combination such as a specific blending amount of the present invention.

  The method for producing the flame-retardant polyamide resin composition of the present invention is not particularly limited, and the polyamide resin, melamine cyanurate, and swellable layered silicate are mixed with a uniaxial or biaxial extruder or a kneader such as a kneader. A method of melt kneading at a temperature of 330 ° C. may be used.

  The resin composition of the present invention can be easily molded by a usual method such as injection molding or extrusion molding, and the obtained molded product is excellent in flame retardancy and heat resistance, particularly excellent in deflection temperature under load. Suitable for electrical and electronic parts, automobile parts and building material parts.

  In addition, the polyamide resin of the present invention further includes copper-based heat stabilizers, hindered phenol-based, phosphorus-based, sulfur-based antioxidants, heat stabilizers, ultraviolet absorbers, and the like within a range that does not impair the object of the present invention. One or more usual additives such as a lubricant, a release agent, an antistatic agent, and a colorant including a dye / pigment can be added.

  The composition of the present invention can be molded into automobile parts, electric / electronic parts, building material parts, etc. by any of injection molding, extrusion molding, and blow molding.

By using the polyamide resin composition of the present invention as these parts, parts having extremely high flame retardancy and heat resistance, which could not be achieved in the past, are obtained, which is particularly suitable for these applications.
[Example]
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited by these. Measurement methods used in Examples and Comparative Examples are shown below.

(1) Flame retardancy Measured according to the method of UL94 (standard defined by Under Writer Laboratories Inc., USA).

(2) Material strength It measured according to the following standard methods.

Tensile strength: ASTM D638
(3) Deflection temperature under load It was measured according to the following standard method.

ASTM D648
(4) Odor Odor was measured using a new Cosmo Electric Co., Ltd. odor sensor XP-329. The odor indication value (154) from the odorless nylon 66 resin, the flame retardant that feels odor, and the odor indication value (587) from brominated PPO [manufactured by GLC Co., Ltd .: trade name PO64P] were used as references. The evaluation criteria are as follows.

154 or less: No odor (○)
154 to 587: Slight odor (△)
587 or more: Odor (×)
(5) Color tone A test piece was prepared according to the following method, and the color tone was measured.

  0.1% by weight of a yellow dye was dried on a nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of sulfuric acid of 2.70, prepared according to a conventional method and pellets obtained as in Examples 1 to 4 and Comparative Examples 1 to 16. By blending and using an injection molding machine PS60 manufactured by Nissei Plastic Industry Co., Ltd., under conditions of cylinder temperature 290 ° C., mold surface temperature 80 ° C., screw rotation speed 150 rpm, injection speed maximum, injection / cooling = 10/10 seconds, A square plate type test piece of 80 mm × 80 mm × 3 mmt was molded. The obtained test piece was measured for color tone (L, a, b) using a color computer SM-5 manufactured by Suga Test Instruments Co., Ltd., and the color tone difference from the yellow colored product of nylon 66 resin (Δ The color difference (ΔE) was determined from L, Δa, Δb).

ΔE = √ (ΔL ² + Δa ² + Δb ² )
(6) Relative viscosity of sulfuric acid The relative viscosity with 98% sulfuric acid was measured according to JIS-K6810.

(7) Evaluation of metal corrosiveness Terminal metal after press-fitting a metal terminal into the connector obtained as described above at an interval of 1 mm, applying 12 V in an environment of an atmospheric temperature of 60 ° C. and a humidity of 95%, and treating for 250 hours The presence or absence of corrosion was visually observed. Solder-plated products were used for the metal terminals. The evaluation criteria are as follows.
No corrosion: (○)
There is corrosion: (×).

Reference Example 1 Production of Copolymer Polyamide N66 / 6I copolymer polyamide resin having an N66 copolymerization ratio of 80% by weight was produced by the following polymerization method. The equimolar salts of hexamethylene diamine and adipic acid and the equimolar salts of hexamethylene diamine and isophthalic acid were added at a ratio of 8: 2, respectively, and the same amount of pure water as the total amount added was added. After substituting with ₂ , heating was started while stirring, and the final temperature reached 270 ° C. while adjusting the can internal pressure to a maximum of 20 kg / cm ² . The polymer discharged into the water bath was pelletized with a strand cutter. The relative viscosity of sulfuric acid was measured and found to be 2.0.

Reference Example 2 Production of swellable layered silicate by exchanging exchangeable metal cations existing between layers with organic onium ions Swellable layered silicate was produced by the following method. 100 g of Na-type montmorillonite (cation exchange capacity: 85 meq / 100 g) was stirred and dispersed in 10 liters of hot water, and this was 1. 2 liters of warm water in which 0 times was dissolved was added and stirred for 1 hour, and the resulting precipitate was filtered off and then washed with warm water (this washing and filtration were performed three times) to obtain The solid was vacuum dried at 80 ° C. to obtain a swellable layered silicate. A swellable layered silicate powder sample was measured in the range of 2θ = 2 to 20 degrees using a wide-angle X-ray diffractometer (RINT1100 manufactured by Rigaku Denki Co., Ltd.), and the interlayer distance was determined with the d (001) peak. The interlayer distance was 1.9 nm. Further, 0.1 g of the obtained swellable layered silicate was incinerated for 3 hours in an electric furnace at 600 ° C., and the amount of inorganic ash was measured to be 69% by weight.

Reference Example 3 Production of Molded Product Molded products used in Examples and Comparative Examples were produced by the following method. ASTM-D638 standard under the conditions of cylinder temperature 290 ° C., mold surface temperature 80 ° C., screw rotation speed 150 rpm, injection speed maximum, injection / cooling = 15/10 sec. A connector having a terminal interval of 1 mm was molded using the same tensile test piece under the conditions of injection / cooling = 5/5 seconds.

Example 1
100 parts by weight of a nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of 2.70 sulfuric acid, melamine cyanurate [manufactured by Nissan Chemical Industries, Ltd .: trade name: MC-440], which was produced by a conventional method on a polyamide resin, was 8.9. Part by weight of a swellable layered silicate produced by the above method with a blending prescription of 2.2 parts by weight using a twin screw extruder (manufactured by Toshiba Machine Co., Ltd .: TEM58) at a cylinder set temperature of 270 ° C. and a screw speed of 200 rpm Under conditions, nylon 66 resin, melamine cyanurate, and swellable layered silicate are top-fed (base feed), melt-kneaded, strand-shaped gut is formed, cooled in a cold bath, granulated with a cutter, and pelletized. Obtained. Molded products were obtained from the obtained pellets by the method of Reference Example 3, and various properties were examined. The results are shown in Table 1.

Example 2
A pellet and a molded product were obtained in the same manner as in Example 1 except that the 66/6 copolymer having a copolymerization ratio of 80% by weight and sulfuric acid relative viscosity of 2.0 shown in Reference Example 1 was used as the polyamide resin. Various characteristics were investigated. The results are shown in Table 1.

Examples 3, 5, and 7
Except that the blending ratio was changed, pellets and molded products were obtained in the same manner as in Example 1, and various characteristics were examined. The results are shown in Table 1.

Examples 4, 6, and 8
Except that the blending ratio was changed, pellets and molded products were obtained in the same manner as in Example 2, and various characteristics were examined. The results are shown in Table 1.

Comparative Example 1
100 parts by weight of nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of 2.70 sulfuric acid, 27 parts by weight of brominated PPO [manufactured by GLC Co., Ltd .: trade name: PO64P], antimony trioxide. [Nippon Seiko Co., Ltd .: Trade name: PATOX-M] With 9.6 parts by weight of the formulation, pellets and molded products were obtained in the same manner as in Example 1, and various characteristics were examined. The results are shown in Table 2.

Comparative Example 2
A pellet and a molded product were obtained in the same manner as in Example 1 except that the 66/6 copolymer having a copolymerization ratio of 80% by weight and sulfuric acid relative viscosity of 2.0 shown in Reference Example 1 was used as the polyamide resin. Various characteristics were investigated. The results are shown in Table 2.

Comparative Example 3
100 parts by weight of nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of sulfuric acid of 2.70 produced by a conventional method on polyamide resin, 8.7 weight of red phosphorus [manufactured by Rin Chemical Industry Co., Ltd .: trade name: Nova Excel 140] In the same manner as in Example 1, pellets and molded products were obtained and the various characteristics were examined. The results are shown in Table 2.

Comparative Example 4
Pellets and molded articles were obtained in the same manner as in Comparative Example 3 except that the 66 copolymer shown in Reference Example 1 having a copolymerization ratio of 80 wt% and sulfuric acid relative viscosity of 2.0 was used as the polyamide resin. Various characteristics were investigated. The results are shown in Table 2.

Comparative Example 5
A blended formulation of polyamide resin 100 parts by weight of nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of sulfuric acid of 2.70, 5.3 parts by weight of melamine cyanurate, prepared in a conventional manner. The product was obtained and various characteristics were investigated. The results are shown in Table 2.

Comparative Example 6
A pellet and a molded product were obtained in the same manner as in Comparative Example 5 except that the 66 copolymer shown in Reference Example 1 having a copolymerization ratio of 80% by weight and a sulfuric acid relative viscosity of 2.0 was used as the polyamide resin. Various characteristics were investigated. The results are shown in Table 2.

Comparative Examples 7, 9, 11, 13
Except that the blending ratio was changed, pellets and molded products were obtained in the same manner as in Example 1, and various characteristics were examined. The results are shown in Table 3.

Comparative Examples 8, 10, 12, 14
Except that the blending ratio was changed, pellets and molded products were obtained in the same manner as in Example 2, and various characteristics were examined. The results are shown in Table 3.

Comparative Example 15
100 parts by weight of nylon 66 resin having a melting point of 265 ° C. and a relative viscosity of 2.70 sulfuric acid, 6.5 parts by weight of melamine cyanurate, talc [trade name: PK- manufactured by Hayashi Kasei Co., Ltd.] C] Pellets and molded products were obtained in the same manner as in Example 1 with a formulation of 2.2 parts by weight, and various characteristics were examined. The results are shown in Table 3.

Comparative Example 16
A pellet and a molded product were obtained in the same manner as in Comparative Example 15 except that the 66 copolymer shown in Reference Example 1 had a copolymerization ratio of 80% by weight and a sulfuric acid relative viscosity of 2.0 was used as the polyamide resin. Various characteristics were investigated. The results are shown in Table 3.

  The polyamide resin compositions of Examples 1 to 8 obtained by blending polyamide resin, melamine cyanurate, and swellable layered silicate from Examples 1 to 8 and Comparative Examples 1 to 16 have high flame retardancy. It was confirmed that a material excellent in the deflection temperature under load can be obtained.

Claims (7)

(A) 2 to 20 parts by weight of (B) melamine cyanurate with respect to 100 parts by weight of polyamide resin, (C) swellable layered silicate 1 to 1 in which exchangeable metal cations existing between layers are exchanged with organic onium ions A polyamide resin composition comprising 15 parts by weight as a main component. (A) The polyamide resin composition according to claim 1, wherein the polyamide resin has a relative viscosity of 1.5 to 7.0. 3. The polyamide resin composition according to claim 1, wherein the polyamide resin is polyamide 66. 3. The polyamide resin composition according to claim 1, wherein the (A) polyamide resin is a copolymer of polyamide 66 units and polyamide 6I units and / or a mixed polyamide. (C) The interlayer distance of the swellable layered silicate obtained by exchanging exchangeable metal cations existing between layers with organic onium ions is 1.6 to 2.9 nm. Polyamide resin composition. A molded article obtained by molding the polyamide resin composition according to any one of claims 1 to 5 by at least one method selected from injection molding, extrusion molding, and blow molding. The molded article according to claim 6, wherein the molded article is any one selected from electrical and electronic parts, automobile parts, and building material parts.