JPH11302535A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition having excellent flame retardancy and mechanical properties and excellent electrical properties. SOLUTION: (a) 100 parts by weight of a polyamide resin, (b) 5 to 300 parts by weight of an inorganic filler, (c) 5 to 125 parts by weight of a halogen-based flame retardant, and (d) metal oxides 1 to 5
0 parts by weight, (e) 3 to 100 parts by weight of a metal borate compound,
(F) A polyamide resin composition comprising 0.1 to 50 parts by weight of an α, β-unsaturated carboxylic acid-modified polyolefin resin and (g) 0.1 to 50 parts by weight of a polyolefin resin

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyamide resin composition, and more particularly, to a polyamide resin composition having excellent flame retardancy and electrical properties.

[0002]

2. Description of the Related Art In order to improve flame retardancy in a resin composition in which an inorganic filler is blended with a polyamide resin, a method of blending a halogen-based flame retardant and an antimony-based flame retardant auxiliary is known. It is also known to combine zinc borate and antimony oxide in order to enhance the flame retardant effect. On the other hand, as a method for improving electric properties such as high-voltage arc tracking properties, a method of adding a polyolefin is known, but there is a drawback that flame retardancy is reduced when a large amount is added to improve electric properties. . Therefore, it has been difficult to obtain a polyamide resin composition having excellent flame retardancy, electrical properties, and mechanical properties.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyamide resin composition having excellent flame retardancy and mechanical properties, and also having excellent electrical properties.

[0004]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and its gist is as follows.
(A) 100 parts by weight of polyamide resin, (b) 5 to 300 parts by weight of inorganic filler, (c) 5 to 5 parts of halogen-based flame retardant
125 parts by weight, (d) 1 to 50 parts by weight of metal oxide,
(E) 3 to 100 parts by weight of a metal borate compound, (f) α,
β-unsaturated carboxylic acid-modified polyolefin resin 0.1 to
50 parts by weight and (g) polyolefin resin 0.1 to 5
It is present in a polyamide resin composition containing 0 parts by weight.

Hereinafter, the present invention will be described in detail. As the polyamide resin (a) in the present invention, a lactam having three or more rings, a polymerizable ω-amino acid, or a polyamide obtained by polycondensation of a dibasic acid and a diamine can be used. Examples of lactams having three or more ring members and polymerizable ω-amino acids include ε-caprolactam, aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid,
α-pyrrolidone, α-piperidone and the like.

Examples of the diamine include hexamethylene diamine, nonamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and meta-xylylene diamine. Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecane dibasic acid, glutaric acid, and the like.

Examples of the polyamide resin include polyamide polymers and polyamide copolymers. Specific examples include nylon 4, nylon 6, nylon 7, nylon 8, nylon 11, nylon 12, nylon 6.6, and nylon 6. .9, nylon 6.10, nylon 6.11,
Nylon 6.12, nylon 6T, copolymer nylon 6 /
6.6, copolymer nylon 6/12, copolymer nylon 6 /
6T, copolymer nylon 6I / 6T and the like, and preferably, nylon 6, nylon 66, copolymer nylon 6/66 and the like. A plurality of types of polyamide resins can be used.

[0008] The relative viscosity of the polyamide resin is preferably measured at a concentration of 1% in 98% sulfuric acid at a temperature of 25 ° C.
It is 2-5.5, More preferably, it is 2.3-4.5. If the relative viscosity is too low, the mechanical properties decrease, and if it is too high, the moldability is impaired.

The terminal of the polyamide resin may be sealed with a carboxylic acid or an amine, and particularly has 6 to 22 carbon atoms.
And a polyamide resin sealed with a carboxylic acid or an amine. Examples of the carboxylic acid used for sealing include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine used for sealing include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine. The amount of the carboxylic acid or amine used for sealing is preferably about 30 μeq / g.

The inorganic filler (b) in the present invention may be any of those commonly used in polyamide resins, and there is no particular limitation on the average particle size and shape. Specific examples of the inorganic filler include glass fiber, glass flake, talc, kaolin, calcined kaolin, montmorillonite, swelled montmorillonite, mica (mica), swellable fluoromica-based mineral, layered silicate, clay mineral, silica, clay , Calcium carbonate, magnesium sulfate, wollastonite,
Examples include whiskers, alumina, asbestos, carbon fibers, and modified products thereof. The inorganic filler may be used without any treatment, but for the purpose of improving the interfacial adhesion with the polyamide resin and improving the dispersibility, various silane coupling agents, titanium coupling agents, higher fatty acids, Those whose surface has been treated with higher fatty acid esters, higher fatty acid amides, higher fatty acid salts or other surfactants can be used.

[0011] The content of the inorganic filler is 5 to 300 parts by weight. If the content of the inorganic filler is less than 5 parts by weight, rigidity tends to decrease, and if it exceeds 300 parts by weight, toughness decreases. The content of the inorganic filler is preferably 10 to 250 parts by weight, more preferably 20 to 200 parts by weight.

The halogen-based flame retardant (c) in the present invention includes aromatic halogen compounds, halogenated epoxy resins, halogenated polycarbonates, halogenated aromatic vinyl copolymers, halogenated cyanurate resins, halogenated polyphenylene ethers and the like. Preferred are decabromodiphenyl oxide, 1,2 (pentabromophenyl) -ethane, pentabromobenzyl polyacrylate, tetrabromobisphenol A, oligomers of tetrabromobisphenol A, brominated bisphenol-based epoxy resins, and brominated bisphenol-based resins. Phenoxy resin, brominated bisphenol-based polycarbonate, brominated polystyrene, brominated cross-linked polystyrene, brominated polyphenylene oxide, polydibromophenylene oxide Decabromodiphenyl diphenyl oxide bisphenol condensate and a halogen phosphates.

The content of the halogen-based flame retardant is 5 to 125.
Parts by weight. If the content of the halogen-based flame retardant is less than 5 parts by weight, the flame retardancy tends to decrease, and if it exceeds 125 parts by weight, the electrical properties deteriorate. The content of the halogen-based flame retardant is preferably from 10 to 100 parts by weight, more preferably from 15 to 80 parts by weight.

The metal oxide (d) in the present invention is a metal oxide acting as a flame-retardant aid, such as antimony trioxide, antimony pentoxide, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, zirconium oxide. ,
Examples include tin oxide, iron oxide, titanium oxide, and aluminum oxide. The content of the metal oxide is 1 to 50 parts by weight. If the content of the metal oxide is less than 0.5 part by weight, the flame retardancy tends to decrease, and if it exceeds 50 parts by weight, the electrical properties deteriorate. The content of the metal oxide is preferably 2 to 40 parts by weight, and more preferably 3 to 30 parts by weight.

The metal compound (e) in the present invention includes zinc borate, aluminum borate, magnesium borate, and the like, and preferably zinc borate. The composition ratio of zinc borate is not particularly limited as long as it contains zinc oxide and boric acid as main components. The content of the metal borate is 3 to 100 parts by weight. If the content of zinc borate is less than 3 parts by weight, the electrical properties tend to decrease, and if it exceeds 100 parts by weight, the toughness tends to decrease. The content of the metal borate is preferably 4 to 80 parts by weight, more preferably 5 to 60 parts by weight.

The total of the content of the metal oxide and the content of the metal borate compound is preferably 4 to 120 parts by weight based on 100 parts by weight of the polyamide resin. If the total of the content of the metal oxide and the content of the metal borate compound is less than 4 parts by weight, the flame retardancy tends to decrease, and if it exceeds 120 parts by weight, the toughness tends to decrease. The total of the content of the metal oxide and the content of the metal borate compound is more preferably 5 to 100 parts by weight based on 100 parts by weight of the polyamide resin.

The (f) α, β-unsaturated carboxylic acid-modified polyolefin resin in the present invention is a polyolefin resin modified with α, β-unsaturated carboxylic acid, and is preferably composed mainly of ethylene and / or propylene. Copolymer of an olefin as a component and an α, β-unsaturated carboxylic acid or a derivative thereof, and a polymer of an olefin mainly containing ethylene and / or propylene as an α, β-unsaturated carboxylic acid or a derivative thereof And the like.

Α, β in a copolymer of an olefin having an ethylene component and / or a propylene component as a main constituent and an α, β-unsaturated carboxylic acid or a derivative thereof.
-As unsaturated carboxylic acids or derivatives thereof, for example, acrylic acid, methacrylic acid, methyl methacrylic acid,
Sodium acrylate, zinc acrylate, vinyl acetate,
Glycidyl methacrylate and the like can be mentioned. The proportion of the α, β-unsaturated carboxylic acid or its derivative in the copolymer of an olefin having an ethylene component and / or a propylene component as a main constituent and an α, β-unsaturated carboxylic acid or its derivative is preferably 40. Mol% or less.

Specific examples of the copolymer of an olefin having an ethylene component and / or a propylene component as a main component and an α, β-unsaturated carboxylic acid or a derivative thereof include, for example, an ethylene-vinyl acetate copolymer, Examples include an ethylene-acrylic acid copolymer, an ethylene-ethyl acrylic acid copolymer, and an ethylene-sodium acrylate copolymer.

Examples of the olefin polymer in the graft polymer obtained by grafting an α, β-unsaturated carboxylic acid or a derivative thereof to an olefin polymer containing ethylene and / or propylene as a main component include, for example, polyethylene and polypropylene. , Ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-ethylacrylic acid copolymer, ethylene-sodium acrylate copolymer And the like.

The α, β-unsaturated carboxylic acids or derivatives thereof grafted in the graft polymer include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, anhydrides of these acids, and those acids. Examples thereof include esters with tetrahydrofurfuryl alcohol and the like, and preferably include maleic anhydride. The graft amount is preferably 0.05% of the olefin polymer.
~ 1.5% by weight.

The graft polymerization is carried out by mixing both components and melting them at a resin temperature of 150 to 300 ° C. according to a conventional method. In the graft polymerization, α, α'-bis-
An organic peroxide such as t-butylperoxy-p-diisopropylbenzene is added to the polyolefin at 0.00
When the amount is 1 to 0.05% by weight, the reaction can be efficiently performed.

The content of the α, β-unsaturated carboxylic acid-modified polyolefin resin is 0.1 to 50 parts by weight. If the content of the modified polyolefin resin is less than 0.1 part by weight or exceeds 50 parts by weight, the flame retardancy is reduced. The content of the α, β-unsaturated carboxylic acid-modified polyolefin resin is preferably 1 to 40 parts by weight, more preferably 2 to 3 parts by weight.
0 parts by weight.

The polyolefin resin (g) in the present invention is a polyolefin having an ethylene component and / or a propylene component as a main component, and examples thereof include polyethylene, polypropylene, ethylene-propylene copolymer, and ethylene-butene-1 copolymer. Unmodified polyolefin resins such as a polymer, an ethylene-vinyl acetate copolymer, an ethylene-acrylic acid copolymer, an ethylene-ethylacrylic acid copolymer, and an ethylene-sodium acrylate copolymer are exemplified.

The content of the polyolefin resin is 0.1 to 5
0 parts by weight. The content of polyolefin resin is 0.1
If the amount is less than 50 parts by weight, the flame retardancy is reduced. The content of the polyolefin resin is preferably 1
-40 parts by weight, more preferably 2-30 parts by weight. The total of the content of the α, β-unsaturated carboxylic acid-modified polyolefin resin and the content of the polyolefin resin is preferably 1 to 75 parts by weight, more preferably 2 to 60 parts by weight, based on 100 parts by weight of the polyamide resin. is there.
If the total of the content of the α, β-unsaturated carboxylic acid-modified polyolefin resin and the content of the polyolefin resin is less than 1 part by weight or exceeds 75 parts by weight, the flame retardancy is reduced.

As a method of blending an inorganic filler, a halogen-based flame retardant, a metal oxide, a metal borate compound, an α, β-unsaturated carboxylic acid-modified polyolefin resin and a polyolefin resin with a polyamide resin, a final molded article is formed. It can be carried out by any known means at any stage immediately before the step. The simplest method is a method of simply dry blending the polyamide resin and the above-mentioned additive, and the obtained dry blend is formed into pellets by melt mixing extrusion. Alternatively, a resin composition having a desired ratio can be obtained by preparing in advance a master pellet in which an additive larger than a predetermined amount is kneaded, and dry blending the master pellet with a polyamide resin for dilution. Further, the polyamide resin, the inorganic filler, the modified polyolefin resin, the halogen-based flame retardant, the metal oxide and the metal borate compound are dry-blended and then melt-mixed and extruded into pellets, and then the other additives are dry-blended to obtain a desired resin composition. You can also get

The polyamide resin composition of the present invention may be kneaded with a pigment, a dye, a release agent, a nucleating agent, a stabilizer, an antistatic agent and other known additives. Further, in the polyamide resin composition of the present invention, a thermoplastic resin other than the polyamide resin can be blended within a range that does not impair the effects of the present invention. The molded product obtained by molding the polyamide resin composition of the present invention is obtained by supplying the dry blend or the pellet to various molding machines such as injection molding, extrusion molding, blow molding, and compression molding, and molding the molded product according to a conventional method. Can be obtained by

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Various evaluations in the following Examples and Comparative Examples were performed according to the following methods. (1) Flexural modulus: performed in accordance with ASTM-D790. (2) Izod impact test: performed according to ASTM-D256. (3) Flame retardancy: Performed according to UL-94. (4) HVTR (high voltage arc tracking test):
Performed in accordance with UL-746A. The test result is P
It is indicated by a five-level evaluation of LC0 to 4, and PLC0 is considered to be the best.

The raw materials used in the examples and comparative examples are as follows. (5) Polyamide 6 resin: manufactured by Mitsubishi Engineering-Plastics Corporation, grade name 1010J, relative viscosity 2.
5. (6) Polyamide 66 resin: DuPont, grade name FE3218, relative viscosity 2.8. (7) Glass fiber: T28, manufactured by NEC Corporation
3. (8) Halogen-based flame retardant: trade name SAYTEX8010 manufactured by Albemarle Asano Co. (Hereinafter, halogen-based flame retardant A
It may be called. (9) Halogen flame retardant: PO64P, manufactured by Great Lakes Chemical Company. (Hereinafter, it may be referred to as halogen-based flame retardant B.)

(10) Metal oxide: antimony trioxide,
MIC-3 manufactured by Morirokusha. (11) Metal borate compound: Zinc borate, manufactured by BORAX, trade name ZINC BORATE 2335. (12) α, β-unsaturated carboxylic acid-modified polyolefin resin: manufactured by Mitsui Petrochemical Co., Ltd., trade name N Tuffmer MP061
0. (Hereinafter, it may be referred to as modified polyolefin A.) (13) Polyolefin resin: Novatec HY540, manufactured by Nippon Polychem Co., Ltd. (Hereinafter, it may be referred to as polyolefin A.) (14) Polyolefin resin: HIWAX410P manufactured by Mitsui Petrochemical Co., Ltd. (Hereinafter, it may be referred to as polyolefin B.)

Examples 1-4 After blending the various components shown in Table 1 in the amounts shown in Table 1, Nippon Steel Corp.
Was melt-mixed at a set temperature of 275 ° C. using a TEX30C type twin screw extruder to obtain pellets of the polyamide resin composition. The pellets are injection-molded according to each molded article, and the flexural modulus, Izod impact value, flammability, HVTR
Was evaluated. Table 1 shows the evaluation results.

[0032]

[Table 1]

[Comparative Examples 1 to 6] After blending the various components shown in Table 2 in the amounts shown in Table 2, pellets were prepared in the same manner as in Example 1, and various evaluations were performed in the same manner as in Example 1. Table 2 shows the evaluation results.

[0034]

[Table 2]

[0035]

Industrial Applicability The polyamide resin composition of the present invention has excellent flame retardancy, electrical properties and mechanical properties, and is useful for electric / electronic parts, automobile parts, various industrial parts, etc.
It is particularly suitable for electromagnetic switch parts and the like.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C08K 5/136 C08K 5/136 // (C08L 77/00 101: 04 23:26 23:00) (72) Inventor Masami Suzuki 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering Plastics Co., Ltd. Technology Center

Claims (8)

[Claims] 1. (a) 100 parts by weight of a polyamide resin, (b) 5 to 300 parts by weight of an inorganic filler, (c) 5 to 125 parts by weight of a halogen-based flame retardant, and (d) 1 to 5 parts of a metal oxide.
0 parts by weight, (e) 3 to 100 parts by weight of a metal borate compound,
(F) A polyamide resin composition containing 0.1 to 50 parts by weight of an α, β-unsaturated carboxylic acid-modified polyolefin resin and (g) 0.1 to 50 parts by weight of a polyolefin resin. 2. The method according to claim 1, wherein (a) the polyamide resin is nylon 6,
The polyamide resin composition according to claim 1, which is nylon 66 or copolymerized nylon 6/66. (3) The polyamide resin has a relative viscosity of 9
8% sulfuric acid concentration 1%, measured at a temperature of 25 ℃ 2.2-
The polyamide resin composition according to claim 1, wherein the composition is 5.5. 4. The group of (d) a metal oxide comprising antimony trioxide, antimony pentoxide, copper oxide, magnesium oxide, zinc oxide, molybdenum oxide, zirconium oxide, tin oxide, iron oxide, titanium oxide, and aluminum oxide. The polyamide resin composition according to claim 1, which is a metal oxide selected from the group consisting of: 5. The polyamide resin composition according to claim 1, wherein (e) the metal borate compound is zinc borate. 6. The (f) α, β-unsaturated carboxylic acid-modified polyolefin resin is a copolymer of an olefin having ethylene and / or propylene as a main constituent and an α, β-unsaturated carboxylic acid or a derivative thereof. 2. A graft polymer obtained by grafting an α, β-unsaturated carboxylic acid or a derivative thereof to a polymer of an olefin containing ethylene and / or propylene as a main component. Polyamide resin composition. 7. The total of the content of the metal oxide (d) and the content of the metal borate (e) is 4 to 120 parts by weight based on 100 parts by weight of the polyamide resin (a). The polyamide resin composition according to claim 1, wherein 8. The sum of the content of (f) the α, β-unsaturated carboxylic acid-modified polyolefin resin and the content of (g) the polyolefin resin is 1 to 75 parts by weight based on 100 parts by weight of the polyamide resin (a). 2. The method according to claim 1, wherein
The polyamide resin composition according to the above.