WO2014187152A1

WO2014187152A1 - Polyamide resin and polyamide combination formed of same

Info

Publication number: WO2014187152A1
Application number: PCT/CN2014/070028
Authority: WO
Inventors: 张传辉; 袁志敏; 蔡彤旻; 曾祥斌; 曹民; 夏世勇; 叶南飚; 陈大华
Original assignee: 金发科技股份有限公司
Priority date: 2013-05-20
Filing date: 2014-01-02
Publication date: 2014-11-27
Also published as: CN103265695A

Abstract

Disclosed is polyamide resin, which is formed of the following repeated unit components: component A: 40 mol% to 48 mol% of 1,10-diaminodecane and 2 mol% to 10 mol% of 1,6-diaminohexane; and component B: 40 mol% to 48 mol% of a terephthalic acid and 2 mol% to 10 mol% of an adipic acid, where at most 95 mol% of the adipic acid is replaced by the terephthalic acid, an isophthalic acid or other aliphatic dicarboxylic acids having a carbon atom number 2 to 14. A combination containing the polyamide resin comprises, by weight percent, the following components: 30% to 99.9% of polyamide resin; 0% to 60% of a reinforcing filler; 0% to 50% of a fire retardant; and 0.1% to 10% of other additives. The polyamide resin and the combination formed of same according to the present invention have relatively high brightness, and therefore are applicable to scenarios where product color requirement is relatively high; have high thermal resistance, and therefore are applicable to scenarios where reflow soldering temperature exceeds 270°C; and have a low water absorption rate, and therefore are applicable to scenarios where engine oil pipes and the like have relatively high requirements for the water absorption rate.

Description

Polyamide resin and polyamide composition composed thereof

The present invention relates to the field of polymeric materials, and more particularly to a polyamide wax and a polyamide composition composed thereof.

Background technique

Polyamide has good comprehensive properties, including mechanical properties, heat resistance, abrasion resistance, chemical resistance and 0 lubricity, and low friction coefficient, and has certain flame retardancy: easy to process, etc. Widely modified by ffl glass fiber and other fillers to enhance the modification, improve performance and expand the scope of application. : Semi-aromatic polyamides in recent years: Developed by T, which has better heat resistance and mechanical properties.

It is a well-known fact that polyamides are easily oxidized or decomposed at high temperatures, causing the color of the resin to be dark and severely affected. In general, improvements in resin color are generally achieved through improvements to the process. JP61188421 indicates that the low molecular weight PA46 prepolymer is washed with water and then phase-bonded to obtain a polymer having a high molecular weight and a good color; CN1622967 proposes to use nitrogen gas having a certain water vapor concentration as a solid phase viscosifying protective gas, thereby A polyamide with a color improvement can be obtained, the mechanism of which is the influence of the dew point and heat capacity of water vapor. Still others are achieved by adding a small amount of additives. For example, JP4170430 Tishan addition of bisphenylphosphine catalyst in the polymerization process is beneficial to the color of the polymerization product; CN 101432365: mentioning {1\ in processing. Process. Adding calcium stearate can improve the color of the twisted color; C 101218289 The addition of Tishan phosphate improves the molecular weight increase and color control of PA66. However, the improvement of the resin structure itself and the improvement of the color of the resin have not yet been found in the literature. SUMMARY OF THE INVENTION In order to overcome the shortcomings and deficiencies of the prior art: The first object of the present invention is to provide a polyamide resin which is high in 1⁄2 degree, high in heat resistance, and low in water absorption. :

A polyamide resin consisting of the following 3⁄4 recovery components in mole fraction ratio _:

10. A: 40-48 mol% of decane diamine and 2-10 mol% of ι diamine;

Component B: 40-48 mol%: terephthalic acid and 2-10 mol% Q diacid;

Thereafter, up to 95 niol% of adipic acid may be terephthalic acid, isophthalic acid or contain 2-14 Replacement of other aliphatic dicarboxylic acids with a carbon number.

The other aliphatic dicarboxylic acid having 2 to 14 carbon atoms is selected from the group consisting of S oxalic acid, malonic acid, succinic acid, glutaric acid, pimelic acid, suberic acid, 2-methyl suberic acid, One or more of azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, thiric acid or tetradecanoic acid.

The polyamide resin has a melting point of high 270 ° C, preferably 280 ° C - 320 ° C _{; the} melting point of the resin is too low, the article is easily deformed under high temperature treatment of turbulent soldering; the melting point of the resin is too high, resulting in processing properties decline. Moreover, the melting point is too high to be close to the decomposition temperature, and it is easy to deteriorate the performance of all aspects of the product.

After the injection molding of the polyamide resin, the 3⁄4 degree value of the color plate L is large T 75.0, preferably large T 76.0; the resin 1⁄2 degree value is too low, which causes the product to be dark and affects the final use.

The water absorption of the polyamide resin is low T lwt%, preferably low T 0.8 wt%; if the water absorption rate is too high, foaming of the product in the flow-through welding of the stalk is caused.

A polyamide composition comprising the polyamide resin, in percentage by weight, comprises the following components:

Polyamide resin 30~99.9%;

Reinforcing filler 0~60%;

Flame retardant 0~50%;

Other additives 0.1~10%;

The content of the reinforcing filler is preferably 10 to 50% by weight, more preferably 15 to 40%; the filler content is too low, resulting in poor mechanical properties of the polyamide composition; the filler content is too high, and the surface of the polyamide composition product is severely suspended , affecting the appearance of the product.

The reinforcing filler has a fibrous shape and has an average length of 0.01-20 mm, preferably 0.1 to 6 mm; and an aspect ratio of 5 to 2000:1, preferably 30 to 600:1, when the fibrous reinforcing filler content is Within the above range, the polyamide 3⁄4 compound exhibits a high heat distortion temperature and an increased high temperature rigidity, and the above dimensions can be measured by micrometers on the fibers.

The reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler;

The inorganic reinforcing filler is selected from glass fiber, potassium titanate fiber, metal clad glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal curable fiber, asbestos fiber, alumina fiber, silicon carbide fiber, gypsum One or more of fibers or boron fibers, preferably glass fibers; the use of glass fibers not only improves the moldability of the polyamide composition, but also improves mechanical properties such as tensile strength, bending The strength and flexural modulus, and the heat resistance such as the heat distortion temperature at which the thermoplastic resin is molded. The organic reinforcing filler is selected from the group consisting of aramid fibers and/or carbon fibers.

The reinforcing filler has a non-fibrous shape, such as a powder, a granule, a plate, a needle, a woven fabric or a felt, and has an average particle diameter of 0.001 to 10 μm, preferably 0.01 to 5 μm, when the average particle of the reinforcing filler is used. Small diameter - 0.001 μ ηι will result in poor melt processability of the polyamide resin; when the average particle size of the reinforcing filler is large -10 μm, it will result in poor surface appearance of the injection molded article. The average particle diameter of the above reinforcing filler is determined by an adsorption method, which may select potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, wollastonite, zeolite, sericite, kaolin, mica, talc, clay, Pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos, aluminosilicate, alumina, silica, magnesia, zirconia, cerium oxide, iron oxide, calcium carbonate, magnesium carbonate, marble, One or more of calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide. These reinforcing fillers may be hollowed out; in addition, for swellable layered silicates such as bentonite, montmorillonite, hectorite, synthetic mica, etc., the organic halide may be used for cation exchange of interlayer ions. Organic montmorillonite.

In order to obtain more excellent mechanical properties of the polyamide composition, the inorganic reinforcing filler may be functionally treated with a ffl coupling agent, and the oxime coupling agent is selected from the group consisting of S isocyanate compounds, organosilane compounds, and organic titanates. a compound, an organoborane compound, or an epoxy compound; preferably an organosilane compound; and the organosilane compound is selected from the group consisting of an alkoxysilane compound containing an epoxy group and an alkoxysilane containing a mercapto group. a compound, a ureido group-containing alkoxysilane compound, an isocyanate group-containing alkoxysilane compound, a 1⁄4 group-containing alkoxysilane compound, a hydroxyl group-containing methoxysilicone compound, and a carbon-carbon-unsaturated group. One of the methoxysilane compound and the acid anhydride group-containing alkoxysilane compound.

The epoxy group-containing methoxysilicone compound is selected from the group consisting of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and e-(3, 4 One or more of epoxy-cyclohexyl)ethyltrimethoxysilane;

The mercapto group-containing alkoxysilane compound is selected from the group consisting of Sγ-mercaptopropyltrimethoxysilane and/or γ-mercaptopropyltriethoxysilane;

The uret group-containing methoxysilicone compound is selected from the group consisting of γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-(2-ureidoethyl:) One or more of 3⁄4 propyltrimethoxysilane;

The isocyanate group-containing alkoxysilane compound is selected from the group consisting of γ-isocyanate propyl triethoxy group Silicon germanium, γ-isocyanatepropyltrimethoxysilane, γ-isocyanate propylmethyldimethoxysilane, γ-isocyanate propylmethyldiethoxysilane, γ-isocyanatepropyl One or more of ethyldimethoxysilane, γ-isocyanate propylethyldiethoxysilane, γ-isocyanatepropyltrichlorosilane;

The 1-group-containing methoxy silane compound is selected from the group consisting of S γ -(2-1⁄4 ylethyl) 1⁄4 propyl propyldimethoxysilane, γ -(2-1⁄4 ylethyl) 3⁄4 propyl propyltrimethyl One or more of oxysilane, γ-1,4-propyltrimethoxysilane;

The hydroxyl group-containing alkoxysilane compound is selected from the group consisting of γ-hydroxypropyltrimethoxysilane and/or γ-hydroxypropyltriethoxysilane;

The alkoxysilyl compound containing a carbon-carbon unsaturated group is selected from the group consisting of γ-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, and ^£3⁄4 -^-vinylbenzyl. One or more of 1-ylethyl)-1-ylpropyltrimethoxysilane* hydrochloride;

The acid anhydride group-containing methoxysilane compound is selected from the group consisting of 3-trimethoxysilylpropyl succinic anhydride;

The organosilicon lanthanide compound is preferably γ-methacryloxypropyltrimethoxysilane, γ-(2- 3⁄4-ylethyl)1⁄4 propylmethyldimethoxysilane, γ-( 2-3⁄4-ethylidene:) 3⁄4-propylpropyltrimethoxysilane, γ-1,4-propyltrimethoxysilane or 3-trimethoxysilylpropyl succinic anhydride.

The inorganic reinforcing filler may be surface-treated by the above-mentioned organosilane compound according to a conventional method, and then the polyamide resin may be melt-kneaded to prepare the polyamide composition; or directly in the inorganic reinforcing filler and the poly While the amide resin is melt-kneaded, the organosilicon lanthanide compound is added for in-situ blending;

The amount of the coupling agent is 0.05 to 10% by weight, preferably 0.1 to 5% by weight based on the weight of the inorganic reinforcing filler; when the amount of the coupling agent is less than 0.05% by weight, the amount of the coupling agent is not significant. The effect of improving the mechanical properties; when the amount of the ff of the coupling agent is as large as 10% by weight, the inorganic reinforcing filler is liable to agglomerate, and the risk of poor dispersion of the polyamide resin is eventually caused to decrease the mechanical properties.

The flame retardant is a flame retardant or a combination of a flame retardant and a flame retardant auxiliary agent, and the content thereof is preferably 10 to 40% by weight _{; if the} flame retardant content is too low, the flame retarding effect is deteriorated, and the flame retardant content is too high. Lead to a decrease in the mechanical properties of the material.

The flame retardant is a halogen flame retardant or a halogen free flame retardant; The halogen-based flame retardant is selected from the group consisting of brominated polystyrene, brominated polyether ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated. Bad oxygen resin, bromine One or JL species of phenoxy resin, decabromodiphenyl ether, decabromobiphenyl, brominated polycarbonate, perbrominated tricyclopentanyl or brominated aromatic crosslinked polymer, preferably preferred Brominated polystyrene;

The halogen-free flame retardant is selected from the group consisting of a nitrogen-containing flame retardant, a phosphorus-containing flame retardant, or a nitrogen or phosphorus-containing flame retardant; preferably a phosphorus-containing flame retardant.

The phosphorus-containing flame retardant is selected from the group consisting of aryl phosphate monophosphate, aryl phosphate bisphosphate, dimethyl alkylphosphonate, triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, and propyl phosphate. One or more of a benzene phosphate, a butyl benzene phosphate or a hypophosphite; preferably a hypophosphite;

The hypophosphite has a hypophosphite of the following formula (I) -

Wherein R ¹ and R ^{2 are the} same or different and are represented by a straight or branched alkyl group having 1 to 6 atoms of an alkyl group and/or an aryl group or a phenyl group; Μ is Mg, Ca, Al, Zi B Mn, Na, K or a nitrogenous base that has been protonated; m is 1-3. ■

The other auxiliary agent is selected from the group consisting of a plasticizer, a thickener, an antistatic agent, a mold release agent, a toner, a dye, or a nucleating agent.

Compared with the prior art, the invention has the following beneficial effects -

1) The polyamide resin of the present invention is obtained by a specific repeating unit, and the brightness value L of the color plate obtained after injection molding is more than 75.0, which has high brightness and can be applied to a case where the color requirement of the product is high;

2) The polyamide resin of the present invention has a melting point higher than 27 (C, and has high heat resistance, and can be applied to a case where the reflow soldering temperature exceeds 27 (fC);

3) The polyamide resin of the present invention has a water absorption rate of 0.2 to 0.5% by weight, has a low water absorption rate, and can be used in applications where the low water absorption rate of the product is high;

4) The polyamide composition obtained by the polyamide resin of the present invention also has high brightness, high heat resistance and low water absorption, and can also be applied to a field which requires high color, heat resistance and low water absorption of the product. Contains. detailed description The present invention will be described by way of specific embodiments, and the following examples are preferred embodiments of the invention, but the embodiments of the invention are not limited by the following examples.

Test method for relative viscosity of the obtained prepolymerized product and polyamide: Refer to GB12006. 1-89, polyamide viscosity number determination method; specific test method is: 98% concentrated barium sulfate at 25 ± 0.01 °C measured concentration is 0.25 The relative viscosity nr of the polyamide of g/dl;

Test Method for Melting Point of Polyamide: Refer to ASTM D3418-2003, Standard Test Method for Transition Temperatures of Polymers By Differential Scanning Calorimetry; The specific test method is '· Test the melting point of the sample with a Perkin Elmer Dimond DSC Analyzer; Nitrogen atmosphere, flow rate is 40mL / min; test first 10 ° C / min to 340 ° C, 340 ° C for 2 min, then 10 ° C / min to 50 ° C, then 10 ° C / min to 340 ° C , the endothermic peak temperature at this time is set as the melting point T _{m ;}

Test method for the content of the polyamide end 1⁄4 base: titrate the content of the sample end with a commercial potentiometric titrator; take 0.5g of polymer, add 45mL of phenol and 3mL of anhydrous methanol, heat the turbulent flow, observe the sample after the dissolution , to room temperature, titration of the 1⁄4 base content with a standard hydrochloric acid standard solution;

The test method for the carboxyl group content of the obtained polyamide is as follows: the carboxyl group content of the sample is titrated by a S-potential titrator; 0.5 g of the polymer is added, 50 mL of o-cresol is added, the turbulent flow is dissolved, and 400 uL of the formaldehyde solution is quickly added after cooling. Titration of the terminal carboxyl group content with a calibrated KOH-ethanol solution;

Test Method for 3⁄4 Degree L Value of Polyamide Resin: Using a standard color plate mold, 3000 g of polymer particles were injection molded to obtain a smooth swatch. The color plate is set on the color-Eye7000A computer color measuring instrument to obtain a value of 3⁄4 degrees L value;

Water absorption test: According to ISO 62, the test conditions were 23 ° C for 24 h.

Examples 1 to 9 and Comparative Examples 1 to 13

In an autoclave equipped with a magnetic coupling agitation, a condenser, a gas phase port, a feed port, and a pressure explosion port, the reaction raw materials are added in the proportion of the table; then benzoic acid, sodium hypophosphite and deionized water are added; the amount of the benzoic acid substance is The amount of the total amount of the diamine, the diacid, the lactam, and the monobasic acid is 2.5%, and the amount of the sodium hypophosphite is 0.1%, and the weight of the deionized water is the total weight of the feed. 30%; vacuum-filled with high-purity nitrogen as a shielding gas, and the temperature was raised to 220 ° C within 2 hours under stirring. The reaction mixture was stirred at 220 ° C for 1 hour, and then the temperature of the reactant was raised to under stirring. 230 ° C _{; the} reaction was continued for 2 hours at a mild 2.2 MPa pressure of 230 ° C for 3 hours, and the pressure was maintained by removing the formed water. The post-branched material should be completed, and the prepolymer was vacuum dried at 80 ° C for 24 hours to obtain a prepolymerized product which was solid-phase-bonded at 250 ° C under a vacuum of 50 Pa for 10 hours to obtain a polyamide. The relative viscosity, melting point and 1⁄2 degree value of the polyamide, water absorption rate of the din - Table 1~3 屮.

Table 1

Table 2

table 3

Adipic acid / mol 11 9 6 10 0.5 0 7 6 0.5 2 1 9 11 癸 diamine / mol 0 0 14 10 24.5 25 24.5 25 1 8 14 10 16 19 hexamethylenediamine / mol 20 20 6 10 0.5 0 0.5 0 7 6 10 4 1 End 気 base / mol / t 40 38 41 48 39 45 40 32 38 42 37 34 46 terminal carboxyl / mol / t 82 71 95 101 98 88 101 95 97 91 85 96 89

2.23 2.22 2.23 2.20 2.23 2.27 2.22 2.26 2.25 2.26 2.28 2.24 2.21 Relative viscosity

3 8 8 1 2 1 3 3 9 0 0 6 5 Melting point /°c 292 311 251 240 311 316 275 277 301 289 304 269 255

6 70.3 68.5

Resin brightness (L) 70.2 71.1 69.3 70.2 66.7 68.2 67.5 66.9 67.6 69.0

7.9

吸宇./% 1.5 1 .3 1 .0 1.2 1.4 1.5 1.3 1 .0 1 .2 1.5 1.3 1.1 1.2 From the comparison of Examples 1 to 9 and Comparative Examples 1 to 13, it can be seen that the implementation of the present invention The 3T value of the 10T resin obtained in the example was all above 78, while the L value of the comparative 6T resin was about 70, which was much lower than the T example resin. In the case of the comparative example 10T/66屮, when the content of 66 is more than 30%, the melting point of the polymer is lowered to below 250 °C, which means that the heat resistance is lowered, and the place where the heat resistance is not high, such as When the turbulent soldering temperature exceeds 270 °C. Examples 10-16 and Comparative Examples 14~20

According to the formula of Table 4, the polyamide resin, the flame retardant and other auxiliaries are uniformly mixed in the high-mixing machine, and then the twin-screw squeezing machine is added through the mash feeding port to enhance the filling of the filler through the side feeding scale. The polyamide was cooled by water, granulated and dried to obtain the polyamide. In other words, the mountain temperature is 330 °C.

The following table is the weight of the formula

Implementation implementation implementation implementation implementation implementation

Example 10 case 1 1 case 12 case 13 case 14 case 15 case 16

Polyamide resin

Example 2 Case 2 Case 4 Case 4 Case 9 Case 2 Case 2

Resin amount 70 50 70 50 50 30 99.9 Glass fiber 29 30 29 30 30 60 0 Phosphate flame retardant 0 15 0 15 15 5 0 Polybutene 0 2 0 2 2 2 0 Dipentaerythritol 0 1 0 1 1 1 0

Zinc borate 0 1 0 1 1 1 0 Phenolic antioxidant 0.5 0.5 0.5 0.5 0.5 0.5 0.05 Polyethylene wax 0.5 0.5 0.5 0.5 0.5 0.5 0.05 Water absorption /% 0.3 0.5 0.3 0.4 0.3 0.2 0.3 Resin brightness (L ) 77.5 76.2 78.1 76.7 76.1 78.4 78.5

Continued Table 4

From the comparison of Examples 10-16 and Comparative Examples 14 to 20 of Table 4, it can be seen that the composition prepared by the polyamide resin of the examples of the present application has a better 3⁄4 degree L value than the composition prepared by the comparative example. And lower water absorption.

Claims

Claim

A polyamide resin characterized by a percentage of T and a molar percentage, which is obtained by repeating the following 屮-yuan-

3⁄4 minutes A: 40-48 mol% of decanediamine and 2-10 mol% of hexamethylenediamine;

La points B: 40-48 mol% of terephthalic acid and 2-10 mol% of adipic acid;

Thereafter, up to 95 mol% of adipic acid is substituted with terephthalic acid, isophthalic acid or other aliphatic dicarboxylic acid having 2 to 14 carbon atoms.

2. The polyamide resin according to claim 1, wherein the other aliphatic dicarboxylic acid having 2 to 14 carbon atoms is selected from the group consisting of oxalic acid, malonic acid, and succinic acid. , glutaric acid, pimelic acid, suberic acid, 2-methyl suberic acid, azelaic acid, azelaic acid, undecylic acid, dodecanoic acid, thiric acid or tetradecanoic acid Kind or several.

The polyamide resin according to claim 1, wherein the polyamide resin has a high melting point of 270 ° C, preferably 280-330. C.

4. The polyamide resin according to claim 1, wherein the polyamide resin has a 3⁄4 degree L value of T 75.0, preferably more than 76.0, after the injection molding.

The polyamide resin according to claim 1, wherein the polyamide resin has a water absorption ratio of less than 1% by weight.

6. A polyamide compound comprising the polyamide resin according to any one of claims 1 to 5, which comprises, in terms of a percentage by weight, of the following components - polyamide resin 30 to 99.9%;

Reinforcing filler 0~60%;

Flame retardant 0~50%;

Other additives 0.1~10%;

7. The polyamide composition according to claim 6, wherein the reinforcing filler has a fibrous shape and has an average length of 0.01 to 20 mm, preferably 0.1 to 6 mm; and an aspect ratio of 5 to 2000: 1, preferably 30 to 600: 1; the reinforcing filler is contained in an amount of 10 to 50% by weight.

8. The polyamide composition according to claim 7, wherein the reinforcing filler is an inorganic reinforcing filler or an organic reinforcing filler, and the inorganic reinforcing filler is selected from the group consisting of glass fibers, potassium titanate fibers, and metal clad layers. Glass fiber, ceramic fiber, wollastonite fiber, metal carbide fiber, metal solidified fiber, stone One or more of cotton fibers, alumina fibers, silicon carbide fibers, gypsum fibers or boron fibers, preferably glass fibers; the organic reinforcing filler is selected from the group consisting of aramid fibers and/or carbon fibers.

The polyamide composition according to claim 6, wherein the reinforcing filler has a non-fibrous shape and has an average particle diameter of θ: 01 to 10 μm, preferably 0.01 to 5 μη, selected from the group consisting of titanic acid. Potassium whiskers, zinc oxide whiskers, aluminum borate whiskers, wollastonite, zeolites, sericite, kaolin, mica, talc, sticks, pyrophyllite, bentonite, montmorillonite, hectorite, synthetic mica, asbestos , aluminosilicate, alumina, silica, magnesia, zirconia, titania, iron oxide, calcium carbonate, magnesium carbonate, dolomite, calcium sulfate, barium sulfate, magnesium hydroxide, calcium hydroxide, aluminum hydroxide One or more of glass beads, ceramic beads, boron nitride, silicon carbide or silicon dioxide.

The polyamide composition according to claim 6, wherein the flame retardant is a halogen-based combusticide or a halogen-free flame retardant, and the halogen-based flame retardant is selected from brominated polystyrene. , brominated poly: phenyl ether, brominated bisphenol A type epoxy resin, brominated styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, One or more of decabromobiphenyl, brominated polycarbonate, perbromotricyclopentadecane or brominated aromatic crosslinked polymer, preferably brominated polystyrene; said halogen-free flame retardant The agent is selected from one or more of a nitrogen-containing flame retardant, a phosphorus-containing flame retardant or a nitrogen and phosphorus-containing flame retardant; preferably a phosphorus-containing resist; and the resist is preferably contained in an amount of 10 to 40% by weight.

The polyamide composition according to claim 10, wherein the phosphorus-containing flame retardant is selected from the group consisting of aryl phosphate monophosphate, aryl phosphate bisphosphate, dimethyl alkylphosphonate, ' Triphenyl phosphate, tricresyl phosphate, tris(xylylene) phosphate, propyl benzene phosphate, butyl benzene: one or more of a phosphate, a hypophosphite; preferably having the following structural formula (I) Hypophosphite -

Wherein R ¹ and R ^{2 are the} same or different, and are represented by a straight or branched alkyl group having 1 to 6 carbon atoms and/or an aryl group or a phenyl group; M is Mg, Ca, Al, Zn, Bi, Mn, Na, K or the protonated nitrogenous base Ϊ m is 1-3 ₀