JPH11172101A - Nylon resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a nylon resin composition excellent in electric properties such as tracking resistance, having excellent flame resistance, mechanical properties, heat resistance and moldability, and useful as an electric part, an electronic part, an automobile electric or electronic part or the like by compounding a nylon resin, a brominated flame retardant, an antimony compound, magnesium hydroxide and glass fiber. SOLUTION: This composition is obtained by compounding (A) a nylon resin (e.g. nylon 6) preferably in an amount of 100 pts.wt. with (B) 5-50 pts.wt. of a brominated flame retardant (e.g. polydibromostyrene), (C) 2-15 pts.wt. of an anitomony compound (e.g. antimony trioxide), (D) 20-50 pts.wt. of magnesium hydroxide and (E) 10-100 pts.wt. of glass fiber, and preferably further, (F) 0.01-5 pts.wt. of a fluororesin and (G) 0.01-3 pts.wt. of a hindered phenol-based stabilizer. The bromine content of the component B is preferably >=60 wt.%. Further, the aspect ratio of the component E is preferably 15-45.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a reinforced nylon resin composition having excellent electrical properties such as tracking resistance and also excellent flame retardancy, mechanical properties, heat resistance and moldability, and electric equipment obtained therefrom. The present invention relates to molded parts.

[0002]

2. Description of the Related Art Reinforced nylon resins have good properties as engineering plastics, such as excellent heat resistance, electrical insulation, mechanical properties, and moldability. Used for applications such as machine parts and automobile parts. On the other hand, reinforced nylon resin is inherently flammable, so that it is required to be flame-resistant, that is, flame-retardant in addition to general balance of chemical and physical properties, in order to be used as an industrial material. Often. Furthermore, in recent years, with the internationalization of the electric and electronic industries, the power supply of electric and electronic
From 0V to 240V is required, and stricter electrical insulation is required along with flame retardancy. On the other hand, tracking resistance is required for electrical and electronic components that are exposed to moisture and dust in an unsealed state and are subjected to a high voltage. Tracking here means that a spark is partially generated on the surface due to the influence of a small amount of deposits or moisture on the material surface, and the heat at that time induces carbonization of the material, eventually resulting in dielectric breakdown. .

[0003] As a method of imparting flame retardancy to a reinforced nylon resin, there is known a method of compounding a brominated flame retardant as a flame retardant and compounding the compound, and further blending an antimony compound as a flame retardant auxiliary. General. However, this method has a disadvantage that the tracking resistance is significantly impaired. When the amount of the bromine organic compound is reduced, the tracking resistance is improved, but the flame retardancy is significantly impaired.

On the other hand, as a method for making a reinforced nylon flame-retardant without using such a brominated flame retardant, adding red phosphorus is disclosed in JP-A-58-108248 and JP-A-59-108248.
No. 81351, JP-A-5-78560, JP-A-5-5-2
95164 and the like. However, the addition of red phosphorus has the disadvantage that not only the red coloring by red phosphorus cannot be colored to other colors, but also the high flame retardant effect is insufficient. Japanese Patent Laid-Open No. 7-18 / 1990 discloses a method for improving tracking resistance by blending a polyolefin.
No. 8529. However, when the polyolefin is added, the thermal stiffness is significantly reduced, the flammability is reduced depending on the compounding amount, the burning time is prolonged, and it is necessary to increase the flame retardant in order to shorten the burning time. Tracking resistance is reduced,
It was difficult to achieve both flame retardancy and tracking resistance.

[0005]

Accordingly, the present invention provides a reinforced nylon resin having excellent rigidity and toughness with high flame retardancy without impairing the tracking resistance, and provides good mechanical properties and fluidity. An object of the present invention is to obtain a nylon resin composition having both of the above.

[0006]

Means for Solving the Problems In view of the above situation, the present inventors have made intensive studies on resin compositions in order to solve the above-mentioned problems, and as a result, have reached the present invention. That is, the present invention provides (A) a nylon resin, (B) a brominated flame retardant, (C)
A nylon resin composition containing an antimony compound, (D) magnesium hydroxide, and (E) glass fiber, and a molded article for an electric device component comprising the above nylon resin composition, and a preferable resin composition is (A) (B) 5 to 50 parts by weight of a brominated flame retardant, (C) 2 to 15 parts by weight of an antimony compound, (D)
A nylon resin composition containing 20 to 50 parts by weight of magnesium hydroxide and 10 to 100 parts by weight of (E) glass fiber;
The above-mentioned nylon resin composition in which the brominated flame retardant has a bromine content of 60% by weight or more, and the glass fiber has an aspect ratio of 15 or more.
The above-mentioned nylon resin composition, which is 45 to 45, and the fluorine resin are preferably used in an amount of 0.01 to 100 parts by weight of nylon.
The above-mentioned nylon resin composition, which is blended with 〜5 parts by weight, and the above-mentioned nylon resin composition, which further comprises 0.01 to 3 parts by weight of a hindered phenol-based stabilizer, preferably 100 parts by weight of nylon.

[0007]

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

The (A) nylon resin used in the present invention is a nylon containing amino acids, lactams or diamines and dicarboxylic acids as main components. Representative examples of the main components include 6-aminocaproic acid, 11
-Aminoundecanoic acid, 12-aminododecanoic acid, amino acids such as paraaminomethylbenzoic acid, lactams such as ε-aminocaprolactam, ω-laurolactam, tetramethylenediamine, hexamerenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylene Diamine, 2,2,4- / 2,4
4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5 , 5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, etc. Aliphatic, alicyclic, aromatic diamines, and adipic, spearic, azelaic, sebacic, dodecandioic, terephthalic, isophthalic, 2-chloroterephthalic, 2-methylterephthalic, 5-methyl Aliphatic, alicyclic and aromatic dicarboxylic acids such as sophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, nylon derived from these raw materials is used. The homopolymers or copolymers can each be used alone or in a mixture.

In the present invention, a particularly useful nylon resin is a nylon resin having a melting point of 200 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (nylon 6) and polyhexamethylene. Adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polyhexamethylene adipamide / polyhexamethylene Terephthalamide copolymer (nylon 66 /
6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66/6
I), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6) and mixtures or copolymers thereof Is mentioned.

Particularly preferred are nylon 6, nylon 66, nylon 610, nylon 6/66.
Examples thereof include copolymers, nylon 6/12 copolymers, and the like.
It is practically suitable to use the mixture as a mixture depending on the required properties such as heat resistance, toughness, and surface properties.

The degree of polymerization of these nylon resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 1% concentrated sulfuric acid solution is in the range of 1.5 to 5.0, particularly 2.0 to 4.0. Those in the range of 0 are preferred.

In the present invention, examples of the (B) brominated flame retardant include polydibromostyrene, polytribromostyrene, polypentabromostyrene, decabromodiphenyl, tetrabromodiphenyl, hexabromodiphenylether, octabromodiphenylether, and polydibromo. Known difficulties such as phenylene oxide, decabromodiphenyl ether, tetrabromodiphenyl sulfide, hexabromodiphenylsulfone, ethylenebispentabromodiphenyl, polybromobenzyl polyacrylate, ethylenebistetrabromophthalimide, bispentabromophenoxyethane, and hexabromocyclododecane The use of a flame retardant is possible.

The amount of the brominated flame retardant in the present invention is as follows:
It is usually 5 to 50 parts by weight, preferably 10 to 40 parts by weight, and more preferably 10 to 30 parts by weight, based on 100 parts by weight of the nylon resin. If the amount is less than 5 parts by weight, the flame-retardant effect is not sufficient, and if it exceeds 50 parts by weight, the tracking resistance and mechanical properties are undesirably reduced.

In the present invention, (C) an antimony compound is further blended. This usually acts as a flame retardant aid, specifically, antimony oxides such as antimony trioxide and antimony pentoxide, antimony phosphate, sodium antimonate, potassium antimonyl tartrate, Sb
(OCH ₂ CH ₃ ) ₃ , Sb (OCH (CH ₃ ) CH ₂ CH ₃ ) ₃ and triphenylstibine. Preferred examples of these include antimony oxide which exhibits a flame retardant effect by a synergistic effect when used in combination with an organic bromine compound. Among them, the antimony oxide group, particularly antimony trioxide, is preferably used. The median average particle size of antimony oxide used in the present invention is not particularly limited, but is preferably 2 μm or less, more preferably 1.5 μm or less. When the particles of antimony oxide are large, the amount of antimony oxide added increases to maintain the same flammability, and as a result, the tracking resistance tends to decrease.

The amount of the antimony compound in the present invention is usually 2 to 15 parts by weight based on 100 parts by weight of the nylon resin.
Parts by weight, preferably 5 to 10 parts by weight. If the amount is less than 2 parts by weight, the flame-retardant effect is not sufficient, and if it exceeds 15 parts by weight, the tracking resistance and mechanical properties deteriorate, which is not preferable.

The magnesium hydroxide (D) used in the present invention includes magnesium hydroxide of relatively high purity containing 80% by weight or more of an inorganic substance represented by the chemical formula Mg (OH) _2. Strength,
From the viewpoint of melt viscosity, preferably, the inorganic substance represented by Mg (OH) ₂ is 80% by weight or more, the CaO content is 5% by weight or less, the chlorine content is 1% by weight or less, more preferably 9% by weight of Mg (OH) ₂ .
Containing 5% by weight or more and having a CaO content of 0.1% by weight or less,
High purity magnesium hydroxide having a chlorine content of 0.1% by weight or less is suitable. The shape of the magnesium hydroxide used in the present invention may be any of a particle shape, a flake shape, and a fibrous shape, but the particle shape and the flake shape are most preferable from the viewpoint of dispersibility and the like. The specific surface area is 15 m ² / g or less,
It is preferably 0 m ² / g or less, and if it exceeds 15 m ² / g, it is not preferable because it affects the dispersibility of magnesium hydroxide or adversely affects the effect of improving the tracking resistance and the mechanical strength. In the case of particles and flakes, the average particle size is 0.3 to 10 μm, preferably 0.3 to 2 μm
Are suitable for the balance between the effect of improving the tracking resistance, the mechanical strength, and the melt viscosity. When a fibrous material is used, it is suitable that the average fiber diameter is 0.1 to 2 μm and the aspect ratio is 20 to 60, preferably the average fiber diameter is 0.3 to 2 μm and the aspect ratio is 30 to 50 μm.
This magnesium hydroxide is converted into a long-chain fatty acid or a long-chain aliphatic alcohol such as stearic acid, oleic acid, montanic acid, stearyl alcohol, a vinylsilane compound such as vinyltriethoxysilane or vinyltrichlorosilane, β-glycidoxypropyltrimethoxy. Silane, β
Epoxysilane compounds such as glycidoxypropyltriethoxysilane and aminosilane compounds such as γ-aminopropyltrimethoxysilane may be used.

The amount of magnesium hydroxide in the present invention is usually 20 to 100 parts by weight of the nylon resin.
It is 50 parts by weight, preferably 20 to 40 parts by weight. If the amount is less than 20 parts by weight, the effect of improving the tracking resistance is not sufficient, and if it exceeds 50 parts by weight, the mechanical properties deteriorate, which is not preferable.

The glass fiber (E) used in the present invention is:
It is possible to use a known glass fiber, but the number average aspect ratio of the glass fiber in the molded product after molding is 15%.
It is important to adjust to ~ 45, preferably 20-30. If the average aspect ratio of the glass fiber in the molded article is small, the mechanical properties tend to decrease, and if the average aspect ratio is large, the tracking resistance of the molded article tends to decrease. The glass fiber used in the present invention can exhibit its performance by being blended as it is, but can be treated with an appropriate surface treatment agent to enhance the affinity and adhesion to the resin. Examples of the surface treatment agent include a silane coupling agent, a zircoaluminate coupling agent, a titanate coupling agent, and the like. In particular, a silane coupling agent (particularly, aminosilane or epoxysilane) can be suitably used. The use of a material subjected to these surface treatments further improves the mechanical properties.

The amount of the glass fiber in the present invention is usually 10 to 100 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the nylon resin. If the amount is less than 10 parts by weight, the mechanical properties deteriorate, which is not preferable. If the amount exceeds 1000 parts by weight, the fluidity becomes insufficient and a good molded product cannot be obtained.

It is preferable that the nylon resin composition of the present invention further contains (F) a fluorine resin. The fluorine-based resin used in the present invention is a resin containing a fluorine atom in the resin. Specific examples thereof include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / perfluoroalkylvinyl ether copolymer, and tetrafluoroethylene. Ethylene / ethylene copolymer, tetrafluoroethylene / hexafluoropropylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer, chlorotrifluoroethylene / ethylene copolymer, tetrafluoro Examples thereof include an ethylene / vinylidene fluoride copolymer, a vinylidene fluoride / hexafluoropropylene copolymer, and a fluorinated ethylene / propylene copolymer. Further, a copolymer obtainable by polymerization using a monomer copolymerizable with the above-mentioned fluorine-based resin or an end-capping agent to the extent that the effects of the present invention are not impaired may be used.

The amount of the fluororesin is usually 0.01 to 100 parts by weight of the nylon resin from the viewpoint of mechanical properties and moldability.
To 5 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

When the nylon resin composition of the present invention further contains (G) a hindered phenol-based stabilizer, the tracking resistance is further improved. Such stabilizers include, for example, octadecyl-3- (3,5-di-t-
Butyl-4-hydroxyphenyl) propionate,
3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-
2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3
-T-butyl-6-methyl-4-hydroxyphenyl)
Propane, N, N} -hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), N, N} -trimethylenebis (3,5-di-t-
Butyl-4-hydroxy-hydrocinnamamide, triethylene glycol-bis [3- (3-tert-butyl-5-
Methyl-4-hydroxyphenyl) propionate],
1,6-hexanediol-bis [3- (3,5-di-
t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate].

The amount of the hindered phenol-based stabilizer is usually 0.01 to 100 parts by weight of the nylon resin.
3 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.1 to 1 part by weight.

Further, in order to improve strength and dimensional stability, a fibrous and / or non-fibrous filler other than glass fiber and magnesium hydroxide is used in the nylon resin composition of the present invention, if necessary. Can be Examples of such a fibrous and / or non-fibrous filler include carbon fiber, potassium whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber,
Fibrous fillers such as ceramic fiber, asbestos fiber, stone fiber, metal fiber, wollastenite, zeolite,
Metal compounds such as sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate, alumina, silicon oxide, zirconium oxide, titanium oxide, iron oxide, calcium carbonate, magnesium carbonate, Carbonates such as dolomite, calcium sulfate, sulfates such as barium sulfate, glass beads, ceramic beads, boron nitride, non-fibrous fillers such as silicon carbide and silica, which may be hollow, Two or more of these fillers can be used in combination. In addition, crystal nucleating agents such as polyetheretherketone, anti-coloring agents such as hypophosphite, phosphorus-based non-hindered phenol-based, sulfur-based antioxidants and heat stabilizers, lubricants, UV inhibitors, One or more conventional additives such as a coloring agent can be added.

The method for preparing the nylon resin composition of the present invention is not limited to a specific method, but specific and efficient examples are a mixture of raw materials using a single-screw or twin-screw extruder, a Banbury mixer, a kneader and a mixing roll. For example, a method of melt-kneading at a temperature of 220 to 330 ° C. depending on the melting point of the nylon resin used and supplied to a known melt-kneading machine can be used.

It is desirable to sufficiently control the kneading conditions. For example, when using a melt kneader,
It is desirable to control / D, presence / absence of venting, kneading temperature, residence time, addition position and amount of each component. In general, it is preferable to increase the L / D and the residence time of the melt kneader in order to increase the amount of the deposit on the filler.

The resin composition of the present invention thus obtained has excellent balance of surface appearance, dimensional stability, high-speed impact ductile fracture, rigidity and ductility of a molded product, and is excellent in injection molding and injection molding. It is particularly useful when a molded product is prepared and used by extrusion molding or blow molding.

The resin composition of the present invention is excellent in electrical properties such as tracking resistance, and is excellent in flame retardancy, mechanical properties, heat resistance and moldability. , Such as lighting equipment parts, sockets, coils, terminal blocks, plugs, switches, relay parts, and withstand voltage parts that require high flame retardancy and high tracking resistance.

[0029]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, the blending ratios shown in Examples and Comparative Examples are all parts by weight.

In the following examples, the material strength, flammability, and aspect ratio of the tracking-resistant fiber were determined by the following method.

[Material strength] Measured according to the following standard method. Tensile strength: ASTM D638 Flexural modulus: ASTM D790 Izod Impact strength: ASTM D256

[Flammability] After the composition was blended and extruded, the test pieces for flame retardancy evaluation obtained by injection molding were evaluated as follows.
Flame retardancy was evaluated according to the evaluation criteria defined in L94.

[Tracking resistance] The composition is blended,
After extrusion, a square plate molded product (80 ×
80 × 3tmm) using the International Electrotechnical Commission (IEC),
The comparative tracking index was measured according to the IEC112 method.

[Fiber Aspect Ratio] After the molded article was heated and incinerated, the length of 1,000 glass fibers was measured, and the number average fiber length was divided by the glass fiber diameter.

Example 1 100 parts by weight of nylon 66 having a relative viscosity of 2.55, 15 parts by weight of ethylene bispentabromodiphenyl having a bromine content of 82% by weight as a brominated flame retardant, and an average particle diameter of 0.3 μm as an antimony compound 6 parts by weight of antimony trioxide, Mg (OH) ₂ content 9 as magnesium hydroxide
30 parts by weight of magnesium hydroxide having 8.8% by weight, 0.05% by weight of CaO and 0.04% by weight of chlorine, and 60 parts by weight of glass fiber having a fiber diameter of 10 μm and a fiber length of 3 mm were added and uniformly mixed with a stirrer. Thing, φ45m
The mixture was melt-kneaded with a m-diameter twin-screw extruder and pelletized. After vacuum drying the obtained pellets at 80 ° C., test pieces were molded by injection molding under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C., and evaluated.

Table 1 shows the type of nylon, Table 2 shows the type of brominated flame retardant, and Table 3 shows the evaluation results.

Example 2 Test pieces were obtained at the ratios shown in Table 3 and evaluated in the same manner as in Example 1 except that polydibromophenylene oxide having a bromine content of 60% by weight was used as the brominated flame retardant. .

Example 3 Test pieces were obtained at the ratios shown in Table 3 and evaluated in the same manner as in Example 1 except that the amount of glass fiber was changed to 40 parts by weight.

Example 4 Test pieces were obtained at the ratios shown in Table 3 and evaluated in the same manner as in Example 1 except that nylon 6 having a relative viscosity of 2.70 was used as the nylon resin.

Example 5 Test pieces were obtained at the ratios shown in Table 3 and evaluated in the same manner as in Example 1 except that TTAD from Toray Fine Chemical Co., Ltd. was added as a hindered phenol-based stabilizer.

Example 6 Test pieces were obtained at the ratios shown in Table 3 and evaluated in the same manner as in Example 1 except that polytetrafluoraethylene "Rublon" L5 manufactured by Daikin Industries, Ltd. was added as a fluororesin. . In each of the examples, the tracking resistance is improved without impairing the flame retardancy.

Comparative Examples 1 to 3 Nylon, brominated flame retardant, antimony trioxide, magnesium hydroxide and glass fiber used in Example 1 were tested in the same manner as in Example 1 in the proportions shown in Table 3. Was evaluated.

[0043]

[Table 1]

[Table 2]

[0044]

[Table 3]

[0045]

The reinforced nylon resin composition of the present invention comprises:
It is a nylon resin composition having high flame retardancy and tracking resistance.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // (C08L 77/00 27:12)

Claims (9)

[Claims] 1. A nylon resin composition comprising (A) a nylon resin, (B) a brominated flame retardant, (C) an antimony compound, (D) magnesium hydroxide, and (E) glass fiber. 2. (A) 5 to 50 parts by weight of a brominated flame retardant, (C) 2 to 15 parts by weight of an antimony compound, and (D) 20 to 50 parts by weight of nylon resin with respect to 100 parts by weight of a nylon resin. Parts by weight, and (E) glass fiber 10 to 10
2. The nylon resin composition according to claim 1, comprising 0 parts by weight. 3. The nylon resin composition according to claim 1, wherein the brominated flame retardant (B) has a bromine content of 60% by weight or more. (E) the glass fiber has an aspect ratio of 15 to
The nylon resin composition according to any one of claims 1 to 3, which is 45. 5. The nylon resin composition according to claim 1, further comprising (F) a fluorine resin. 6. The nylon resin composition according to claim 5, wherein 0.01 to 5 parts by weight of a fluorine resin is blended with respect to 100 parts by weight of the nylon. 7. The nylon resin composition according to claim 1, further comprising (G) a hindered phenol-based stabilizer. 8. The nylon resin composition according to claim 7, wherein 0.01 to 3 parts by weight of a hindered phenol stabilizer is blended with 100 parts by weight of nylon. 9. A molded article for electric equipment parts, comprising a molded article obtained by molding the nylon resin composition according to claim 1.