JP2005220240A - Flame retardant polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that is a polyamide resin composition excellent in flame retardancy, high voltage arc tracking property, tracking resistance and rigidity, and suitable for materials for electric and electronic parts such as electromagnetic switches and breakers.
SOLUTION: Component (A): polyamide resin having ISO viscosity of 87 to 150, component (B): glass fiber having average fiber diameter of 9 to 20 μm, component (C): other than glass fiber A flame retardant polyamide resin composition characterized by comprising an inorganic filler, a component (D): a brominated flame retardant, a component (E): an antimony compound, and satisfying the following.
Formula (1) {(B) + (C)} / {(A) + (B) + (C) + (D) + (E)}
= 20-60 / 100 [parts by weight]
Formula (2) {(D) + (E)} / {(A) + (B) + (C) + (D) + (E)}
= 4-40 / 100 [parts by weight]
Formula (3) {(B) / (C)} = 1/3 to 3/1 [weight ratio]
Formula (4) 0.05 ≦ {(Sb) / (Br)} ≦ 0.4 [weight ratio]
[Selection figure] None

Description

  The present invention relates to a flame retardant polyamide resin composition having excellent electrical characteristics.

(1) Flame-retardant polyamide resin compositions are widely used in electrical and electronic equipment parts such as connectors, breakers, electromagnetic switches, switches, etc., but in recent years fires caused by ignition due to tracking have frequently occurred. Therefore, not only the conventional flame retardancy but also a material excellent in tracking resistance is desired.
In particular, for high voltage load parts such as electromagnetic switch parts, a material excellent in high voltage arc tracking property defined in UL746A is desired.
In recent years, since breakers, electromagnetic switches, and the like have a tendency to be thinner, materials with higher rigidity in addition to flame retardancy, high-voltage arc tracking properties, and tracking resistance are desired.

(2) Examples of the flame retardant used in the polyamide resin include a nitrogen-based flame retardant, a phosphorus-based flame retardant, and a halogen-based flame retardant.
The most widely used non-reinforced polyamide resin composition is nitrogen-based melamine cyanurate, which exhibits excellent flame retardancy with a small amount of blending and excellent tracking resistance. When the inorganic filler is present, the flame retardancy is extremely lowered, so that it is unsuitable for the reinforced polyamide resin composition.
Halogen-based flame retardants are most widely used in reinforced flame-retardant polyamide resin compositions, and some are slightly phosphorous-based flame retardants.
Halogen flame retardants exhibit excellent flame retardancy when used in combination with an antimony compound, but on the other hand, tracking performance is greatly reduced.
On the other hand, red phosphorus or melamine polyphosphate, which is a typical phosphoric flame retardant, is excellent in flame retardancy and tracking resistance. However, red phosphorus has a problem of generating phosphine gas having strong toxicity and metal corrosivity. Melamine has a problem that melamine sublimates during molding, clogs the gas vent of the mold, and the molding becomes unstable, and its application range is extremely limited.

  (3) Specifically, Patent Document 1 discloses a polyamide resin composition used for electrical and electronic parts such as connector breakers. Patent Document 2 and Patent Document 3 show polyamide resin compositions excellent in flame retardancy, electrical properties (high voltage arc tracking properties), and mechanical properties (rigidity, etc.). Further improvements are required for tracking and rigidity. In Patent Document 1, an acid-modified elastomer is blended, and in Patent Documents 2 and 3, an α, β-unsaturated carboxylic acid-modified polyolefin resin and a polyolefin resin are blended. It is not preferable because stability and moldability are lowered.

JP 10-219103 A Japanese Patent Laid-Open No. 11-302535 JP-A-11-310701

  The present invention intends to provide a polyamide resin composition having excellent flame retardancy, high voltage arc tracking property, tracking resistance and rigidity, and further to materials for electric and electronic parts such as electromagnetic switches and breakers. The present invention intends to provide a suitable resin composition.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention
The following component (A), component (B), component (C), component (D), and component (E) are blended, and the blending amount and blending ratio of the components are the following (1) It exists in the flame-retardant polyamide resin composition characterized by satisfying all the formulas (4).
Component (A): Polyamide resin component with ISO viscosity in the range of 87 to 150 (B): Glass fiber component with average fiber diameter in the range of 9 to 20 μm (C): Inorganic filler component other than glass fiber ( D): Brominated flame retardant component (E): antimony compound formula (1) {(B) + (C)} / {(A) + (B) + (C) + (D) + (E)}
= 20-60 / 100 [parts by weight]
Formula (2) {(D) + (E)} / {(A) + (B) + (C) + (D) + (E)}
= 4-40 / 100 [parts by weight]
Formula (3) {(B) / (C)} = 1/3 to 3/1 [weight ratio]
Formula (4) 0.05 ≦ {(Sb) / (Br)} ≦ 0.4 [weight ratio]
(Note that (A), (B), (C), (D), and (E) in the above formula are component (A), component (B), component (C), component (D), and The amount of component (E) is shown, (Sb) is the amount of antimony, and (Br) is the amount of bromine.)

  The flame-retardant polyamide resin composition of the present invention is excellent in flame retardancy, high-voltage arc tracking properties, tracking resistance and rigidity, and is extremely useful as a material for electrical and electronic equipment parts such as electromagnetic switches and breakers. .

Hereinafter, the present invention will be described in detail.
As the polyamide resin of component (A) in the present invention, a polyamide obtained by polycondensation such as a lactam having a three-membered ring or more, a polymerizable ω-amino acid, or a dibasic acid and a diamine can be used. Specifically, polymers such as ε-caprolactam, aminocaproic acid, enanthractam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone, hexamethylenediamine, nonamethylene Obtained by polycondensation with diamines such as diamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine, and dicarboxylic acids such as terephthalic acid, isophthalic acid, adipic acid, sebacic acid, dodecanedioic acid, and glutaric acid. Polymers or copolymers thereof, for example polyamide 4, 6, 7, 8, 11, 12, 66, 69, 610, 611, 612, 6T, 6/66, 6/12, 6 / 6T, 6T / 6I, MXD6, and the like, and a plurality of types of polyamide resins can also be used. The terminal of the polyamide resin in the present invention may be sealed with a carboxylic acid or an amine also for molecular weight adjustment. Preferred polyamide resins in the present invention include polyamide 6, polyamide 66, and mixtures thereof from the viewpoint of flame retardancy, mechanical strength, and moldability.
Further, the degree of polymerization of the polyamide resin used in the present invention is 1% dissolved in 96% concentrated sulfuric acid solvent in accordance with ISO 307 and measured at 23 ° C., that is, the viscosity number is in the range of 87 to 150, Preferably it is a thing of the range of 99-138. If the viscosity number is lower than this range, the impact characteristics are deteriorated, and if the viscosity number is high, the fluidity is deteriorated.

The glass fiber in which the average fiber diameter of the component (B) in the present invention is in the range of 9 to 20 μm is not particularly limited as long as it is usually used for polyamide resins.
The inorganic filler of component (C) in the present invention is not particularly limited in terms of the average particle diameter, shape, etc. as long as it is usually used for polyamide resins. Specific examples of the inorganic filler include talc, kaolin, calcined kaolin, montmorillonite, swollen montmorillonite, mica, swellable fluoromica mineral, layered silicate, clay mineral, silica, clay, calcium carbonate, magnesium sulfate, and wolast. Examples thereof include knight, alumina, and carbon fiber. Of these, talc, mica and kaolin are preferred. Talc is particularly preferable.
The glass fiber of the component (B) and the inorganic filler of the component (C) may be used without treatment, but for the purpose of improving the interfacial adhesion with the polyamide resin and improving the dispersibility. In addition, various silane coupling agents, titanium coupling agents, higher fatty acids, higher fatty acid esters, higher fatty acid amides, higher fatty acid salts, or those having a surface treated with other surfactants can also be used.

In the present invention, the total amount {(B) + (C)} of the component (B) and the component (C) is the total amount {(A) + (B) + of the components (A) to (E). (C) + (D) + (E)} It is 20 to 60 parts by weight, preferably 30 to 55 parts by weight, based on 100 parts by weight. If it is less than this range, the rigidity is lowered, and if it is more, the fluidity and surface appearance are lowered, which is inappropriate.
The blending ratio {(B) / (C)} (weight ratio) of the component (B) to the component (C) is in the range of 1/3 to 3/1, preferably 1/2 to 2 /. 1. If it is smaller than this range, the mechanical properties are lowered, and if it is larger, the high voltage arc tracking property is lowered. In particular, in the present invention, when high rigidity is required, the blending ratio is preferably set in a preferable range.

Examples of the brominated flame retardant of component (D) in the present invention include aromatic bromine compounds, brominated epoxy resins, brominated polycarbonates, brominated aromatic vinyl copolymers, brominated cyanurate resins, brominated polyphenylene ethers, and the like. Specifically, ethylene bis (pentabromobenzene), decabromodiphenyl oxide, ethylene bistetrabromophthalimide, poly (pentabromobenzyl acrylate), tetrabromobisphenol A, oligomers of tetrabromobisphenol A, brominated bisphenol series Epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene such as polydibromostyrene, brominated cross-linked polystyrene, polydibromophenylene oxide, etc. Lom polyphenylene oxide, decabromodiphenyl diphenyl oxide bisphenol condensate and halogenated phosphoric acid esters, and the like. The bromine content in the brominated flame retardant is preferably 60% or more, more preferably 80% or more. As the brominated flame retardant having a bromine content of 80% or more, ethylene bis (pentabromobenzene) is preferable.
In the present invention, examples of the antimony compound of component (E) include antimony trioxide, antimony pentoxide, and anhydrous sodium antimonate, among which antimony trioxide is preferable.

In the present invention, the total amount {(D) + (E)} of the component (D) and the component (E) is the total amount {(A) + (B) + of the components (A) to (E). (C) + (D) + (E)} It is 4 to 40 parts by weight, preferably 10 to 25 parts by weight, based on 100 parts by weight. If the amount is less than this range, the flame retardancy is lowered, while if it is more, the fluidity and the surface appearance are lowered, and the specific gravity is increased.
The component (D) and the component (E) have an antimony blending amount (Sb) and a bromine blending amount (Br), and their ratio {(Sb) / (Br)} is 0.05 to 0.4. The range is preferably 0.1 to 0.3. If it is smaller or larger than this range, the flame retardancy and the high voltage arc tracking property are deteriorated, which is inappropriate.

  In the present invention, zinc borate may be blended as the component (F). The blending amount in this case is the total blending amount of the component (A) to the component (F) of the present invention {(A) + (B) + (C) + (D) + (E) + (F)} 100 weight. 0.5-20 weight part is preferable with respect to a part. More preferably, it is 1-10 weight part. If an appropriate amount of this zinc borate is blended, it is easy to obtain a particularly excellent flame retardant and tracking resistance.

  In the present invention, component (A) polyamide resin, component (B) glass fiber, component (C) inorganic filler other than glass fiber, component (D) brominated flame retardant, component (E) antimony compound, component (F ) Zinc borate can be blended by various known means at an arbitrary stage from the polymerization step of the polyamide resin to immediately before the final molded product is molded. As the simplest method, these components (A) to component (E) (including component (F) if necessary) are simply dry blended, and the resulting dry blend is melt-kneaded, A method of pelletizing after cooling can be used. As another method, the polyamide in the present invention can also be prepared by preparing in advance a master pellet obtained by kneading the component (A) with a larger amount of the other component than the predetermined amount, and dry blending it with the dilution polyamide resin. A resin composition can be obtained.

  In the flame-retardant polyamide resin composition of the present invention, pigments, dyes, mold release agents, lubricants, nucleating agents, thermal stability, as long as the properties such as flammability, high-voltage arc tracking properties, tracking resistance, and rigidity are not impaired. Agents, weather resistance improvers, antistatic agents, other well-known additives, and thermoplastic resins other than polyamide resins can also be blended.

However, acid-modified elastomers such as α, β-unsaturated carboxylic acid-modified polyolefin resins and polyolefin resins, when they are added in a large amount, reduce rigidity, dimensional stability, and moldability.
The flame-retardant polyamide resin composition of the present invention can achieve both high flame retardancy and high high-voltage arc tracking performance, and as its application, electrical and electronic equipment parts such as electromagnetic switch parts and breaker parts For example, a resin composition having a high voltage arc tracking property by UL746A of PLC0 or PLC1 and a combustibility by UL94 of V-0 with a specimen thickness of 0.8 mm is preferably used. Furthermore, in the present invention, it is also possible to obtain a resin composition having both high rigidity. Specifically, the flexural modulus according to ISO0178 can be 10 GPa or more.

  Furthermore, in producing parts for electrical and electronic equipment such as electromagnetic switch parts and breaker parts using the flame retardant polyamide resin composition of the present invention, the polyamide resin composition such as the dry blend or pellet is injected. It can be carried out by a method of supplying to various molding machines such as a molding machine, pouring into a mold, cooling and taking out.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded. In the examples described below, the characteristics of each component used and the evaluation test method of the obtained composition are as follows.

<Ingredients used in Examples>
(A-1) Polyamide 6 (hereinafter abbreviated as “PA6”) Trade name: Novamid (registered trademark) 1010J, Mitsubishi Engineering Plastics Co., Ltd. ISO viscosity number = 118
(A-2) Polyamide 66 (hereinafter abbreviated as “PA66”) Product name: Zytel FE3218, product of DuPont ISO viscosity number = 138
(B-1) Glass fiber Product name: 123D10P, OS Corning product
Fiber diameter: 10 μm, aminosilane treated product
(C-1) Talc Product name = UPN-HST0.5, Hayashi Kasei Co., Ltd. product
(C-2) Mica product name = A-21, Yamaguchi Mica Company product
(C-3) Kaolin Product Name = Kaolin 5M, Toshin Kasei Co., Ltd.

(D-1) Brominated flame retardant Product name = Saytex 8010, Br content 82 wt%
Chemical name = Ethylene bis (pentabromobenzene), Albemarle Asano company product
(D-2) Brominated flame retardant Brand name = PDBS, Br content 59wt%
Chemical name = Polydibromostyrene, Great Lakes product
(D-3) Brominated flame retardant Product name = Saytex BT-93, Br content 67.2 wt%
Chemical name = Ethylenebistetrabromophthalimide, Albemarle Asano company product
(D-4) Brominated flame retardant Product name = NP64, Br content 62 wt%
Chemical name = Poly-dibromophenylene oxide, Inui Kasei Co., Ltd. product
(D-5) Brominated flame retardant Product name = FR1025, Br content 70 wt%
Chemical name = Poly (pentabromobenzyl acrylate), Bromochem Far East,
(D-6) Brominated flame retardant Product name = SR-T7040, Br content 53%
Epoxy brominated flame retardant (end-modified product), Sakamoto Yakuhin Kogyo Co., Ltd. product

(E-1) Antimony trioxide Product name = Fire cut AT-3, Sb content 83.5%
Structural formula = Sb ₂ O ₃
(E-2) Anhydrous sodium antimonate Product name = Sun Epoch NA1070L, Sb content 63.2%
Structural formula = Sb ₂ O ₅ .Na ₂ O or NaSbO ₃
(F-1) zinc borate trade name = Fire Break ZB2335, Borax Inc. product formula _{= 2ZnO · 3B 2 O 3 ·} 3.5H 2 0
(G-1) Mold release agent Product name = EBS powder 2F, Lion Corporation Chemical name = Ethylenebisstearylamide
(G-2) Black colorant Carbon black, trade name = 44B, Mitsubishi Chemical Corporation product
(H-1) α, β-unsaturated carboxylic acid-modified polyolefin resin Product name = N Tafmer MP0610, a product of Mitsui Chemicals, Inc.
(H-2) Polyolefin resin Product name = Novatec (registered trademark) HY540, product of Nippon Polyethylene Corporation
(H-3) Carbon Black Masterbatch Product Name = PEM8080BKMB, Sumika Color

<Evaluation Method of Examples>
1) Viscosity number 1% was dissolved in 96% concentrated sulfuric acid solvent according to ISO307 and measured at 23 ° C.
2) Flammability Using a test piece having a thickness of 0.8 mm, the test was performed according to the test method UL-94.
3) High voltage arc tracking (HVTR)
The test was performed in accordance with UL-746A. This test result is shown by 5-step evaluation of PLC0 to 4, with PLC0 being the best.
4) Tracking resistance (CTI)
Measurement was performed according to the test method IEC60112 using a test piece having a thickness of 3 mm.
5) Flexural modulus Measured according to test method ISO178.

Examples 1-14 and Comparative Examples 1-9
After blending the polyamide resin and various additives in the compounding amounts shown in Tables 1 to 3 (units are parts by weight), a TEX30HCT type twin screw extruder manufactured by Nippon Steel Works was used. Examples 9 and 10 had a resin temperature of 280 ° C., others All were melt-mixed at a resin temperature of 250 ° C. to obtain polyamide resin composition pellets. The obtained pellets were injection molded into each test piece and evaluated for flammability, high voltage arc tracking (HVTR), tracking resistance (CTI), and flexural modulus. The evaluation results are shown in Tables 1 to 3 below.

In Comparative Examples 1 to 6, flame retardancy (V-0) and high voltage arc tracking properties (PLC 0 to 1) were not compatible.
Comparative Examples 7, 8, and 9 have the same composition as Examples 1 and 3 of JP-A-11-302535 and Example 1 of JP-A-11-310701, respectively, but all have HVTR of PLC1 and bending. The elastic modulus was about 9 GPa.
On the other hand, Examples 1 to 14 according to the present invention have V-0 flame retardance in thin-walled molded articles, have excellent tracking resistance (CTI), and have high voltage arc tracking (HVTR). When PLC is PLC0 or PLC1, it shows extremely high rigidity with a flexural modulus of 10.6 GPa or more, balancing excellent performance suitable for electrical and electronic parts such as electromagnetic switch parts and breaker parts. It is clear that the resin composition has a good content.

Claims (8)

The following component (A), component (B), component (C), component (D), and component (E) are blended, and the blending amount and blending ratio of the components are the following (1) A flame retardant polyamide resin composition satisfying all of the formulas (4).
Component (A): Polyamide resin component with ISO viscosity in the range of 87 to 150 (B): Glass fiber component with average fiber diameter in the range of 9 to 20 μm (C): Inorganic filler component other than glass fiber ( D): Brominated flame retardant component (E): antimony compound formula (1) {(B) + (C)} / {(A) + (B) + (C) + (D) + (E)}
= 20-60 / 100 [parts by weight]
Formula (2) {(D) + (E)} / {(A) + (B) + (C) + (D) + (E)}
= 4-40 / 100 [parts by weight]
Formula (3) {(B) / (C)} = 1/3 to 3/1 [weight ratio]
Formula (4) 0.05 ≦ {(Sb) / (Br)} ≦ 0.4 [weight ratio]
(Note that (A), (B), (C), (D), and (E) in the above formula are component (A), component (B), component (C), component (D), and The amount of component (E) is shown, (Sb) is the amount of antimony, and (Br) is the amount of bromine.) The flame retardant polyamide resin composition according to claim 1, wherein the high voltage arc tracking property according to UL746A is PLC0 or PLC1, and the flammability according to UL94 is V-0 at a specimen thickness of 0.8 mm. . The flame-retardant polyamide resin composition according to claim 1 or 2, wherein the flexural modulus according to ISO0178 is 10 GPa or more. The flame retardant polyamide resin composition according to any one of claims 1 to 3, wherein the component (A) is polyamide 6, polyamide 66, or a mixture thereof. The flame retardant polyamide resin composition according to any one of claims 1 to 4, wherein the component (C) is talc. The component (A) is polyamide 6, the component (C) is talc, the component (D) is ethylenebis (polybromobenzene), and the component (E) is antimony trioxide. Item 6. The flame retardant polyamide resin composition according to any one of Items 1 to 5. The zinc borate as the component (F) is blended in the range of 0.5 to 20 parts by weight in 100 parts by weight of the total composition of the components (A) to (F). The flame-retardant polyamide resin composition according to any one of the above. An electromagnetic switch part or a breaker part using the flame retardant polyamide resin composition according to any one of claims 1 to 7.