JP2002105311A - Flame retardant polyamide composition and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retardant polyamide composition excellent in flame retardance and further mechanical characteristics such as toughness, good in fluidity and suitably usable for applications to electrical and electronic parts and the electrical and electronic parts formed by using the flame retardant polyamide composition, excellent in flame retardance and heat resistance and excellent even in mechanical characteristics. SOLUTION: This flame retardant polyamide composition is characterized as comprising (A) 20-80 pts.wt. of an aromatic polyamide, (B) 5-50 pts.wt. of an inorganic reinforcing material, (C) 5-40 pts.wt. of a polybrominated styrene and (D) 0.1-10 pts.wt. of a compound containing antimony and/or a compound oxide containing zinc [with the proviso that the sum of the components (A), (B), (C) and (D) is 100 pts.wt.].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyamide composition and an electric / electronic component formed from the polyamide composition. More specifically, the present invention is suitable for producing electrical and electronic components such as thin-walled connectors at a narrow pitch, and is a flame-retardant polyamide composition excellent in thin-walled fluidity, and formed from the polyamide composition. Electrical and electronic parts with excellent heat resistance.

[0002]

The present invention relates to a flame-retardant polyamide composition having excellent mechanical properties such as fluidity and toughness and excellent reflow heat resistance and a connector formed from the flame-retardant polyamide composition. Such electrical and electronic components. More specifically, the present invention relates to a flame-retardant polyamide composition and a flame-retardant polyamide composition particularly suitable for forming electric / electronic parts such as fine-pitch connectors having a thin wall and a short distance between connector terminals. Electrical and electronic components such as connectors having excellent heat resistance.

[0003]

BACKGROUND OF THE INVENTION Conventionally, soldering of connectors on a printed circuit board has been performed by a dipping (immersion) method. However, in recent years, reflow (surface mounting) soldering has been developed as a method for performing high-density mounting. In this method, creamy solder is applied on the printed wiring board using printing technology, and this creamy solder is applied
This is a method in which a component such as a connector is placed, and then the cream-like solder is heated and melted by infrared and / or hot air heating, and the mounted component such as a connector is surface-mounted with molten solder. When such a reflow soldering method is adopted, the surface mount component is exposed to a high temperature of 230 to 240 ° C. in a reflow furnace by infrared rays or hot air, so that the connector material for the surface mount needs to have high heat resistance.

Conventionally, as a material for forming an electronic component, a polyamide which can be heated and melted and molded into a predetermined shape has been used. Generally, polyamides include 6 nylon,
Nylon 66 is widely used, and such aliphatic polyamides have good moldability, but have sufficient heat resistance as a raw material for producing surface mount components exposed to high temperatures as described above. Has no property. Against this background, the demand for polyamides with high heat resistance has increased,
46 nylon was developed. This is 6 nylon, 66
Although it has higher heat resistance than nylon, it has a drawback of high water absorption. For this reason, dimensions of an electric / electronic component formed using the 46 nylon resin composition may change due to water absorption, and if the molded product absorbs water, blisters (blisters) are generated by heating during reflow. There was such a problem. On the other hand, an aromatic polyamide derived from an aromatic dicarboxylic acid such as terephthalic acid and an aliphatic alkylenediamine (see JP-A-59-53536) has been developed. This is 66 nylon, 46
Compared to aliphatic polyamides such as nylon, they have not only excellent heat resistance, mechanical strength and rigidity, but also low water absorption.

A polyamide resin is inherently self-extinguishing, but a flame retardant must be added to a surface mount component requiring high flame retardancy such as V-0 specified in UL94. Generally, a method of adding a flame retardant such as a halogen compound to polyamide is known. For example, a composition in which halogenated polystyrene is added to polyamide (see JP-A-51-47034), for example, A composition to which brominated polystyrene obtained by brominating polystyrene, such as Pyrocheck 68PB manufactured by Ferro, is added (see JP-A-3-66755), which has better heat stability than brominated polystyrene and Compositions to which polybrominated styrene obtained by polymerizing styrene is added (JP-A-5-320503, WO 98/14
No. 510) or a composition obtained by adding a condensation product of a brominated phenol to a polyamide (Japanese Patent Application Laid-Open No.
-2100).

[0006] In recent years, the surface mount parts such as connectors have been made thinner and narrower in pitch. Therefore, resins used for this purpose are required to have not only high heat resistance and high toughness but also high fluidity. became. This is because high fluidity is required to form a connector having a fine shape. Therefore, the appearance of a flame-retardant polyamide composition having excellent flame retardancy, good toughness, and high fluidity has been desired for use in surface mount components such as connectors.

The present inventor has conducted intensive studies in view of such circumstances, and as a result, a polyamide composition containing a specific aromatic polyamide and a polybrominated styrene having a specific bromine content and MFR has been found to be flame-retardant. The present inventors have found that they have excellent properties, good fluidity, and high toughness, and are suitable for use in electric and electronic parts, and have completed the present invention.

[0008]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant polyamide composition having excellent flame retardancy, good flowability and high toughness. Another object of the present invention is to provide an electric / electronic component having excellent flame retardancy and heat resistance formed using the above flame retardant polyamide composition.

[0009]

SUMMARY OF THE INVENTION The flame retardant polyamide composition of the present invention comprises:
(A) M measured at a load of 2.16 kg and a melting point of + 10 ° C.
FR is in the range of 40 to 300 g / 10 min and melting point is 2
Aromatic polyamide exceeding 90 ° C .: 20 to 80 parts by weight, (B) inorganic reinforcing material: 5 to 50 parts by weight, (C) bromine content is 44 to 61% by weight, load 3.8 kg, 230 ° C.
Polybrominated styrene having an MFR of 70 to 300 g / 10 min as measured in (5): 5 to 40 parts by weight, (D) a compound containing antimony, and / or a composite oxide containing zinc:
0.1 to 10 parts by weight (provided that (A), (B),
(The total of the components (C) and (D) is 100 parts by weight).

[0010] In the flame-retardant polyamide composition of the present invention, the viscosity number of a polyamide extracted from the composition using concentrated sulfuric acid is preferably in the range of 60 to 110 ml / g. Further, a flame-retardant electric / electronic component of the present invention is characterized by being formed from the flame-retardant polyamide composition of the present invention.

[0011]

DETAILED DESCRIPTION OF THE INVENTION The present invention will be specifically described below. <Flame-retardant polyamide composition> The flame-retardant polyamide composition of the present invention has (A) a MFR measured at a load of 2.16 kg and a melting point of + 10 ° C in the range of 40 to 300 g / 10 minutes, and a melting point of Aromatic polyamide exceeding 290 ° C .: 20 to
80 parts by weight, (B) an inorganic reinforcing material: 5 to 50 parts by weight, and (C) a bromine content of 44 to 61% by weight and a load of 3.8 k.
g, MFR measured at 230 ° C. is 70 to 300 g / 1.
0 minute polybrominated styrene: 5 to 40 parts by weight, (D)
Compound containing antimony and / or composite oxide containing zinc: 0.1 to 10 parts by weight (provided that (A),
(The total of the components (B), (C), and (D) is 100 parts by weight).

Hereinafter, each component constituting the flame-retardant polyamide composition of the present invention will be described. (A) Aromatic polyamide The aromatic polyamide (A) constituting the flame-retardant polyamide composition of the present invention has an MFR measured at a load of 2.16 kg and a melting point of + 10 ° C within a range of 40 to 300 g / 10 minutes. It is an aromatic polyamide having a melting point exceeding 290 ° C.

(A) The aromatic polyamide is formed of a repeating unit derived from (i) a dicarboxylic acid and (ii) a diamine. The (A) (i) dicarboxylic acid forming the aromatic polyamide used in the present invention contains an aromatic dicarboxylic acid as an essential component, and preferably contains (ia) terephthalic acid as the aromatic dicarboxylic acid. I have.

The (i) dicarboxylic acid may be (ib) an aromatic dicarboxylic acid other than terephthalic acid, or (ic)
It may contain an aliphatic dicarboxylic acid. (Ib) Examples of aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and combinations thereof.

(Ic) The aliphatic dicarboxylic acid specifically includes an aliphatic dicarboxylic acid having an alkylene group having 4 to 20, preferably 6 to 12 carbon atoms, such as succinic acid, adipic acid and azelaic acid. Acids, sebacic acid, and combinations thereof. Of these, adipic acid is preferred. As the (A) dicarboxylic acid component unit constituting the aromatic polyamide (A) used in the present invention, a dicarboxylic acid component unit derived from terephthalic acid is 30 to 100 mol%, preferably 50 mol%.
And (ib) an aromatic dicarboxylic acid other than the terephthalic acid component unit and / or (ic) 4 to 20, preferably 6 to 12 carbon atoms. 0 to 70 mol%, preferably 0 to 50 mol% of the structural unit derived from the aliphatic dicarboxylic acid
In the amount.

The diamine component unit (A) which forms the aromatic polyamide (A) together with the dicarboxylic acid component has 4 to 20 carbon atoms, preferably 6 to 1 carbon atom.
Examples thereof include an alkylenediamine having 2 linear alkylene groups and / or an alkylenediamine having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms having a side chain alkyl group, and an alicyclic diamine. Among them, the alkylenediamine component unit includes a linear alkylenediamine having 4 to 18, preferably 6 to 12 carbon atoms and / or an alkylenediamine having 4 to 18, preferably 6 to 12 carbon atoms having a side chain alkyl group. Component units are exemplified.

Specific examples of the linear alkylenediamine having 4 to 18 carbon atoms include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, , 9-Diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2-methyl-1,5-diaminopentane, 2-methyl-1,8-diaminooctane and these Combinations and the like. Among these, 1,6-diaminohexane, 1,9-diaminononane, and 1,10-diaminodecane are preferable, and in particular,
1,6-diaminohexane is preferred.

Further, as an example of the alicyclic diamine, cyclohexanediamine can be mentioned. Examples of the repeating unit composed of a terephthalic acid component unit and an aliphatic diamine include a repeating unit represented by the following formula [I].

[0019]

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However, in the above formula, n is 4 to 20, preferably 6 to 12. In addition to the repeating unit represented by the above formula [I], a preferred repeating unit capable of forming the polyamide of the present invention includes a repeating unit represented by the following formula [II].

[0021]

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However, in the above formula [II], n is 4 to 20, preferably 6 to 12, independently of the above formula [I]. Further, a suitable repeating unit capable of forming the polyamide of the present invention together with the repeating unit represented by the above formula [I] includes a repeating unit represented by the following formula [III].

[0023]

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However, in the above formula [III], R ¹ and R
² is each independently a cyclic group represented by the following formula or a divalent hydrocarbon group having 4 to 20, preferably 6 to 12 carbon atoms. In R ¹ and R ² , it is desirable that at least one of R ¹ and R ² , preferably a component unit composed of a dicarboxylic acid, is a group having the following cyclic structure. In the above (III), R ¹ and R ² may each be a group having the following cyclic structure, but usually a dicarboxylic acid component unit is a group having a cyclic structure, and usually a diamine component. The unit may be a divalent hydrocarbon group having 4 to 20, preferably 6 to 12 carbon atoms. In this case, the diamine component unit may be a diamine in which the divalent hydrocarbon group having 4 to 20, preferably 6 to 12 carbon atoms has an alicyclic structure such as cyclohexanediamine. Furthermore, both have 4 to 18 carbon atoms, preferably 6 to 12 carbon atoms.
May be a divalent hydrocarbon group. Note that a hydrogen atom bonded to a carbon atom forming a cyclic structure of a group having a divalent cyclic structure as shown below is an alkyl group such as a methyl group or an ethyl group, another monovalent group, or a halogen atom. A monovalent atom such as an atom may be at least partially substituted.

[0025]

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[0026]

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[0027]

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[0028]

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Here, R ⁴ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and q is an integer of 1 to 4.
As described above, the aromatic polyamide (A) used in the present invention has a repeating unit derived from a dicarboxylic acid containing terephthalic acid and a diamine as described above. (A) The amount of the terephthalic acid component unit in the dicarboxylic acid component unit constituting the aromatic polyamide is in the range of 30 to 100 mol%, preferably 50 to 100 mol%. The aromatic dicarboxylic acid unit other than terephthalic acid and / or the aliphatic dicarboxylic acid unit in the dicarboxylic acid component unit constituting the above is contained in an amount of 0 to 70 mol%, preferably 0 to 50 mol%. ing.

Preferably, when the constitutional unit derived from dicarboxylic acid is 100 mol%, the constitutional unit (a) derived from terephthalic acid is used in an amount of 30 to 100 mol%, preferably 40 to 80 mol%. %, More preferably 50%
In an amount of from 0 to 70 mol%, and a structural unit (b) derived from an aromatic dicarboxylic acid other than terephthalic acid.
It is contained in an amount of 50 mol%, preferably 0 to 40 mol%, more preferably 0 to 20 mol%, and contains the structural unit (c) derived from an aliphatic dicarboxylic acid in an amount of 0 to 70 mol%, preferably Is 20 to 60 mol%, more preferably 30
Desirably, it is contained at 〜50 mol%.

The aromatic polyamide (A) used in the present invention must have an MFR measured under conditions of a load of 2.16 kg and a melting point of + 10 ° C. within a range of 40 to 300 g / 10 minutes. Yes, and this MFR is 50-2
It is preferably in the range of 50 g / 10 minutes, and particularly preferably in the range of 60 to 200 g / 10 minutes.

Particularly, in the present invention, the MFR measured at the melting point of the aromatic polyamide (A) + 10 ° C. is from 40 to 300.
g / 10 min, preferably in the range of 50 to 250 g / 10 min, with a specific (A) aromatic polyamide and a load of 3.8
kg, MFR measured at 230 ° C. is 70 to 300 g / 1.
Obtaining a flame-retardant polyamide composition having very good fluidity, high heat resistance, and excellent mechanical properties by combining with a specific (C) polybrominated styrene described later in the range of 0 minutes. Can be.

The aromatic polyamide (A) as described above is
It has a high melting point, usually above 290 ° C. Among the aromatic polyamides having such a melting point, an aromatic polyamide having a melting point of 295 to 330C, preferably 300 to 320C has particularly excellent heat resistance. Further, the glass transition temperature in the amorphous part of the aromatic polyamide (A) is usually 80 ° C. or higher.

Further, since such an aromatic polyamide has a specific structure as described above, it exhibits a low water absorbency. The aromatic polyamide (A) used in the present invention is excellent in heat resistance, and the processing temperature during compounding and molding is usually 280 to 380 ° C, preferably 300 to 350 ° C.

In the flame-retardant polyamide composition of the present invention, the aromatic polyamide as described above comprises a composition, MFR,
An aromatic diamine having a melting point within the above range can be used alone, or a plurality of aromatic polyamides having different properties can be used in combination. When a plurality of aromatic polyamides are used, the kind and amount of the aromatic polyamide to be used can be adjusted so that the properties of the whole blended aromatic polyamide fall within the above range.

In the flame-retardant polyamide composition of the present invention, the aromatic polyamide (A) as described above comprises (A) an aromatic polyamide and (B) an inorganic polyamide constituting the flame-retardant polyamide composition of the present invention. The total amount of the reinforcing material, the compound containing (C) polybrominated styrene and (D) antimony and / or the composite oxide containing zinc is usually 20 to 80.
% By weight, preferably from 25 to 70% by weight.

(B) Inorganic Reinforcement The flame-retardant polyamide composition of the present invention contains (B) an inorganic reinforcement. In the present invention, various inorganic fillers having a shape such as fibrous, powdery, granular, plate-like, needle-like, cloth-like, and mat-like can be used as the inorganic reinforcing material. More specifically, as the inorganic reinforcing material, glass fiber (glass fiber), potassium titanate fiber, metal-coated glass fiber, ceramic fiber, wollastonite, carbon fiber, metal carbide fiber, metal cured fiber, asbestos fiber, Examples include inorganic fibers such as boron fibers. Glass fiber is particularly preferred as such a fibrous filler. By using glass fibers, the moldability of the composition is improved, and the tensile strength, bending strength, mechanical properties such as flexural modulus, and thermal deformation temperature of the molded article formed from the thermoplastic resin composition are improved. The heat resistance is improved. The average length of such glass fibers is usually
It is in the range of 0.1 to 20 mm, preferably 0.3 to 6 mm, and the aspect ratio is usually in the range of 10 to 2000, preferably 30 to 600. It is preferable to use glass fibers having an average length and an aspect ratio within such ranges. When such a glass fiber is used as the (B) inorganic filler in the flame-retardant polyamide composition of the present invention, the total amount of the components (A), (B), (C) and (D) is 100 parts by weight. On the other hand, it is usually added in an amount of 5 to 50% by weight, preferably 10 to 40% by weight.

An inorganic reinforcing material other than the fibrous inorganic reinforcing material used as the above-mentioned inorganic reinforcing material, that is, a powdery material,
Examples of various inorganic reinforcing materials having a granular, plate-like, needle-like, cloth-like, mat-like, etc. shape include silica, silica alumina, alumina, calcium carbonate, titanium dioxide, talc, wollastonite, diatomaceous earth, Examples include powdery or plate-like inorganic compounds such as clay, kaolin, spherical glass, mica, gypsum, red iron oxide, magnesium oxide and zinc oxide, and acicular inorganic compounds such as potassium titanate.

These inorganic reinforcing materials may be used alone or in combination of two or more. Further, these inorganic reinforcing materials can be used after being treated with a silane coupling agent or a titanium coupling agent. For example, the surface may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, or 2-glycidoxypropyltriethoxysilane. In addition, when such an inorganic reinforcing material is a granular material, its average particle size is usually 0.1 to 200 μm,
Preferably, it is in the range of 1 to 100 μm.

In the present invention, glass fiber is preferably used among the above-mentioned inorganic reinforcing materials. In the flame-retardant polyamide composition of the present invention, the inorganic reinforcing material (B) as described above comprises (A) an aromatic polyamide, (B) an inorganic reinforcing material, which constitutes the flame-retardant polyamide composition of the present invention; Usually 5 to 50% by weight, preferably 1% by weight, based on the total amount of the compound containing (C) polybrominated styrene and (D) antimony and / or the composite oxide containing zinc.
It is desirably contained in an amount of 0 to 45% by weight.

(C) Polybrominated Styrene The flame-retardant polyamide composition of the present invention contains (C) polybrominated styrene. In the present invention, the (C) polybrominated styrene is brominated styrene or brominated α-polystyrene.
It may be produced by polymerizing methylstyrene, or may be polystyrene or brominated polystyrene produced by brominating poly-α-methylstyrene, including both of them.

Examples of the polybrominated styrene (C) include, for example, polydibromostyrene,
Polytribromostyrene, polypentabromostyrene,
And polytribromo α-methylstyrene.
In particular, in the present invention, it is preferable to use a brominated styrene or a polybrominated styrene produced by polymerizing a brominated α-methylstyrene in the stage of a monomer. Polybrominated styrene obtained by brominating at least a part of hydrogen atoms forming an aromatic ring of styrene or α-methylstyrene as a raw material monomer and then polymerizing the brominated atoms has an aromatic ring. It is present in the polymer by replacing a hydrogen atom bonded to a carbon atom to be formed, and a hydrogen atom forming an alkyl chain constituting a main skeleton of the polymer is not substantially substituted by a bromine atom.

On the other hand, brominated polystyrene obtained by polymerizing polystyrene or the like using styrene or α-methylstyrene as a raw material and then brominating is mainly composed of hydrogen bonded to a carbon atom forming an aromatic ring. Some of the atoms are replaced with bromine atoms, but some of the hydrogen atoms that form the alkyl chain that forms the main skeleton of the polymer are also replaced with bromine atoms, and the alkyl chain that forms the main skeleton of the polymer. Are different from each other in whether or not they are substituted with a hydrogen atom forming

However, both are generally represented by the following [IV] when represented by the formula.

[0045]

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Here, m is an integer of 1 to 5. That is,
Brominated polystyrene is brominated after polymerizing styrene represented by the following formula [V] as a raw material.

[0047]

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On the other hand, polybrominated styrene is obtained by polymerizing brominated styrene represented by the following formula [VI].

[0049]

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Among these (C) polybrominated styrenes, in the present invention, it is preferable to use a polybrominated styrene obtained by preliminarily brominating a monomer and then polymerizing the same. The polybrominated styrene (C) used in the present invention has a bromine content of 44 to 61% by weight, preferably 54 to 61% by weight, an orifice inner diameter of 2.095 mm, and a load of 3.8 k.
g, MFR measured at 230 ° C. is desirably 70 to 300, preferably 70 to 200, more preferably 80 to 150. Or, the weight average molecular weight (Mw)
It is desirable to be 2,000 to 100,000, preferably 5,000 to 80,000, and more preferably 8,000 to 60,000.

When the flame-retardant polyamide composition of the present invention contains such a polybrominated styrene (C), it is particularly excellent in flame retardancy and also excellent in flowability.
In the flame-retardant polyamide composition of the present invention, the above-mentioned (C) polybrominated styrene comprises (A) an aromatic polyamide constituting the flame-retardant polyamide composition of the present invention, and (B)
Inorganic reinforcing material, (C) polybrominated styrene and (D)
It is desirable that the content is usually 5 to 50% by weight, preferably 10 to 45% by weight, based on the total amount of the compound containing antimony and / or the composite oxide containing zinc.

(D) Compound containing antimony / containing zinc
Examples of compounds containing antimony used no composite oxide in the present invention as the component (D), antimony trioxide, antimony pentoxide, antimony tetraoxide, antimony sodium and the like. Similarly, examples of the composite oxide containing zinc used as the component (D) include the following formula 2ZnO · 3
_{B 2 O 3, 4ZnO · B} 2 O 3 · H 2 O, 2ZnO · 3B 2 O
Zinc borate represented by ₃ · 3.5H ₂ O, formula ZnSn
Examples include calcium zinc molybdate, basic zinc molybdate, a compound of high efficiency zinc molybdate and magnesium silicate, zinc phosphate and the like, such as zinc stannate represented by O ₃ and ZnSn (OH) ₆ .

Such an antimony-containing compound and a zinc-containing composite oxide can be used alone, or a plurality of antimony-containing compounds or a plurality of zinc-containing composite oxides can be used in combination. . Furthermore, a compound containing antimony and a composite oxide containing zinc can be used in combination. Further, a compound containing antimony and a composite oxide containing zinc can be used in combination. Of these, sodium antimonate,
2ZnO · 3B ₂ O _3, and combinations thereof are preferably used.

When the component (D) is used in combination with the polybrominated styrene (C), the flame retardancy is improved.
In the flame-retardant polyamide composition of the present invention, the component (D) as described above contains (A) an aromatic polyamide, (B) an inorganic reinforcing material, (C) polybrominated styrene, and (D) antimony. The amount is usually 0.1 to 10% by weight, preferably 1 to 8% by weight, based on the total amount of the compound and / or zinc-containing composite oxide.

Other Ingredients The flame-retardant polyamide composition of the present invention may further comprise, in addition to the above-mentioned components, a heat stabilizer, a weather stabilizer, a plasticizer, Thickener, antistatic agent, release agent, pigment, dye, inorganic or organic filler, nucleating agent, fiber reinforcing agent, carbon black, talc, clay,
A compounding agent such as an inorganic compound such as mica may be contained.

Particularly, the flame-retardant polyamide composition of the present invention comprises:
By containing a fiber reinforcing agent among the above, heat resistance, flame retardancy, rigidity, tensile strength, bending strength and impact strength are further improved. Further, the flame-retardant polyamide composition of the present invention may contain another polymer as long as the object of the present invention is not impaired. Examples of such another polymer include polyethylene, polypropylene, and poly (propylene). 4-methyl-1-
Pentene, ethylene / 1-butene copolymer, propylene
Examples include ethylene copolymer, propylene / 1-butene copolymer, polyolefin such as polyolefin elastomer, polystyrene, polyamide, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, fluororesin, and silicone resin.

Further, the flame-retardant polyamide composition of the present invention comprises:
A brominated flame retardant other than the above (C) polybrominated styrene may be contained. Examples of such brominated flame retardants include the following bromine compounds. Hexabromobenzene, pentabromoethylbenzene, hexabromobiphenyl, decabromodiphenyl, hexabromodiphenyloxide, octabromodiphenyloxide, decabromodiphenyloxide, tetrabromobisphenol A and tetrabromobisphenol A-bis (hydroxyethyl ether), tetrabromo Tetrabromobisphenol A derivatives such as bisphenol A-bis (2,3-dibromopropyl ether), tetrabromobisphenol A-bis (bromoethyl ether), and tetrabromobisphenol A-bis (allyl ether);
Tetrabromobisphenol S and tetrabromobisphenol S derivatives such as tetrabromobisphenol S-bis (hydroxyethyl ether) and tetrabromobisphenol S-bis (2,3-dibromopropyl ether), tetrabromophthalic anhydride, tetrabromophthalimide, ethylene Tetrabromophthalic anhydride derivatives such as bistetrabromophthalimide; ethylenebis (5,6-
Dibromonorbornane-2,3-dicarboximide), tris- (2,3-dibromopropyl-1) -isocyanurate, Diels-Alder adduct of hexabromocyclopentadiene, tribromophenyl glycidyl ether, tribromophenyl acrylate, ethylene Bistribromophenyl ether, ethylenebispentabromophenyl,
Ethylene bispentabromophenyl ether, tetradecabromodiphenoxybenzene, brominated polyphenylene oxide, brominated epoxy resin, brominated polycarbonate, polypentabromobenzyl acrylate, octabromonaphthalene, pentabromocyclohexane, hexabromocyclododecane, bis (tri Bromophenyl)
Fumaramide, N-methylhexabromodiphenylamine and the like.

Composition The flame-retardant polyamide composition of the present invention contains the above components (A), (B), (C), and (D), and if necessary, other components. And the viscosity number measured for the polyamide extracted with concentrated sulfuric acid is 60-
110 ml / g, preferably 70 to 105 ml / g.
g is desirable.

In the present invention, the viscosity number is determined according to ISO 307-1984.
It is a value measured in accordance with (E), and specifically, a polyamide is extracted from the flame retardant polyamide composition of the present invention using 96% concentrated sulfuric acid, and the polyamide is contained at a concentration of 0.005 g / ml. A concentrated sulfuric acid solution of the polyamide to be prepared is prepared. This is a value obtained by measuring the viscosity of the solution obtained at 25 ° C. using a Ubbelode type viscometer described in ISO 3105.

The flame retardant polyamide composition of the present invention desirably has a flame retardancy evaluated according to UL94 standard of V-0. Here, the evaluation of the flame retardancy according to the UL94 standard is performed as follows. The upper end of the test piece is locked to the test device with a clamp, and the test piece is set vertically. After a predetermined flame is applied to the lower end of the test piece for 10 seconds, the flame is released and the first burning time of the test piece is measured.

Immediately after burning (extinguishment) in the first burning test of the test piece, a flame was applied from the lower end for 10 seconds, the flame was released, and the second burning time of the test was measured. The maximum value among the ten data is M, and the total is T. Based on this result, the flame retardancy is evaluated based on the following criteria. V-0 equivalent: M is 10 seconds or less, T is 50 seconds or less, the test piece does not burn up to the clamp, the melt falls,
If you do not ignite the cotton laid below, it is equivalent to V-0.

V-1 equivalent: M is 30 seconds or less, T is 250
In less than a second, the prejudice does not burn up to the clamp, and the melt is equivalent to V-1 if it does not ignite the cotton below. V-2 equivalent: M is 30 seconds or less, T is 250 seconds or less, the test piece does not burn up to the clamp, the melt falls, and the lower cotton is ignited, equivalent to V-2. In the present invention, by mainly using polybrominated styrene as the flame retardant, the flame retardant forms fine particles in the aromatic polyamide and is very uniformly dispersed. For this reason, the flame-retardant polyamide composition of the present invention has good flame retardancy, is also excellent in flowability, shows good moldability, and has a fine electrical / electronic component, particularly like a connector. It is suitable as a flame-retardant resin for forming an electronic / electric component having a structure in which a fine terminal is inserted.

The flame-retardant polyamide composition of the present invention is excellent in moldability as described above, and a molded article obtained by molding the composition has low water absorption and low toughness. Since it has excellent mechanical properties, it is particularly suitable for electric and electronic parts. The flame-retardant polyamide composition of the present invention is a method of mixing the above components with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or the like, or after mixing, a single-screw extruder, a multi-screw extruder, a kneader, After melt-kneading with a Banbury mixer or the like, it can be produced by a method of granulating or pulverizing.

<Flame-Resistant Electric / Electronic Parts>
The electronic component can be manufactured by heating and melting the flame-retardant polyamide composition of the present invention obtained as described above, shaping it into a desired shape, and cooling. This shaping can be produced by a method of melt-molding the flame-retardant polyamide composition of the present invention in a mold capable of forming a desired shape.

By using the flame-retardant polyamide composition of the present invention, the flowability of the melt shown in the thin-wall flow length test is good, and electronic parts such as connectors having many thin-walled parts can be efficiently produced. can do. Moreover, electronic components such as connectors manufactured from the flame-retardant polyamide composition of the present invention have high toughness, and cracks occur when connectors are joined (for example, when inserting the terminals of a male connector into a female connector). Hard to do. Further, the electric / electronic component of the present invention has excellent heat resistance, and is less likely to be thermally deformed even in a reflow soldering process.

Such a flame-retardant electric / electronic component of the present invention has excellent flame retardancy and heat resistance, low water absorption, and excellent mechanical strength such as toughness.

[0067]

According to the present invention, there is provided a flame-retardant polyamide composition which is excellent in flame retardancy, excellent in mechanical properties such as toughness, has good fluidity, and can be suitably used for electric and electronic parts. Can be provided. Further, according to the present invention, formed using the flame-retardant polyamide composition as described above,
It is possible to provide an electric / electronic component having excellent flame retardancy and heat resistance and also excellent mechanical properties.

[0068]

EXAMPLES Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples. In Examples and Comparative Examples, measurement and evaluation of each property were performed by the following methods. <Melting point> An endothermic curve of DSC was determined for polyamide,
The temperature at the maximum peak position was defined as the melting point (Tm). The endothermic curve was determined by packing the sample in an aluminum pan and increasing the temperature at a rate of 10 ° C./min. <MFR> Measured according to ASTM D1238.

The pellets are dried under reduced pressure at 120 ° C. for 12 hours using a vacuum dryer. Next, the measurement was performed at an orifice inner diameter of 2.095 mm using an automatic extrusion type plastometer. In addition, the load and temperature conditions at the time of MFR measurement are as follows. (A) Aromatic polyamide Load: 2.16 kg, Measurement temperature: Melting point + 10 ° C (C) Polybrominated styrene Load: 3.8 kg, Measurement temperature: 230 ° C <Viscosity number> Based on ISO 307-1984 (E) Measured. The polyamide is extracted from the polyamide composition using 96% concentrated sulfuric acid to prepare a concentrated sulfuric acid solution of the polyamide having a concentration of 0.005 g / ml. It measured at 25 degreeC using the Ubbelohde type viscometer described in ISO3105. <Bending test (toughness)> Length 64m prepared by injection molding
Using a test piece having a width of 6 mm and a thickness of 0.8 mm, a bending test is performed at a span of 26 mm and a bending speed of 5 mm / min, and the bending strength, the bending elastic modulus, and the energy (toughness) required for breaking the test piece ), The amount of strain at the time of breaking was measured.

Molding machine: Sodick Plustech Co., Ltd., Tupar TR40S3A Cylinder temperature: NT / C1 / C2 / C3 = 320 ° C. /
320 ° C./310° C./300° C. Mold temperature: 120 ° C. Bending tester: AB5 manufactured by NTESCO <Thin wall flow length test> A bar flow mold having a width of 10 mm and a thickness of 0.5 mm was injected under the following conditions. The first 20 shots were discarded, and then the flow length (mm) of 10 shots was measured and averaged.

Injection molding machine: IS-55EPN manufactured by Toshiba Machine Co., Ltd. Injection pressure: 1000 kg / cm ² Injection speed: 99% Cylinder temperature: NT / C1 / C2 / C3 = 320 ° C. /
320 ° C./310° C./300° C. Mold temperature: 120 ° C. <Flame retardancy> The flame retardancy is evaluated according to UL94 regulations.

[0072]

Example 1 The following components were used as the components (A) to (D) in the amounts shown in Table 1. Further, based on 100 parts by weight of the total amount of the components (A) to (D), 1 part by weight of maleated SEBS (Tuftec M1913, manufactured by Asahi Kasei Corporation) as a drip inhibitor, and hydrotalcite (DHT-4, manufactured by Kyowa Chemical Co., Ltd.) as a halogen catcher.
C) in an amount of 0.3 part by weight, and a wax as a release agent (Hostermont NaV101 manufactured by Clariant Japan KK)
0.3 parts by weight, and talc as a crystal nucleating agent (High Filler # 100 Hakudo 95, manufactured by Matsumura Sangyo V Co., Ltd.) 0.7
Parts by weight were added and mixed, and the mixture was charged into a twin-screw vented extruder set at a temperature of 310 ° C., melt-kneaded and pelletized to obtain a pellet-shaped polyamide resin composition. (A) Aromatic polyamide Composition: dicarboxylic acid component: 55 mol% of terephthalic acid and 45 mol% of adipic acid, diamine component: 100 mol% of 1,6-diaminohexane Intrinsic viscosity [η]: 0.8 dl / g Melting point: 310 ° C MFR 150g / 10min (measured at 320 ° C) (B) Inorganic reinforcing material Glass fiber (Asahi Fiberglass CS03JAFT2)
A) (C) Polybrominated styrene a Bromine content: 60% by weight MFR: 100 g / 10 min (load: 3.8 kg, measuring temperature: 230 ° C.) (D) Compound oxidation containing antimony and / or composite oxidation containing zinc Sodium antimonate (NaSbO ₃ ) Next, properties of the obtained polyamide resin composition were evaluated. Table 1 shows the results.

[0073]

Comparative Examples 1 to 4 In the same manner as in Example 1, except that polybrominated styrenes b to d having the properties shown in Table 1 were used as the component (C), the polyamide resin composition was changed in the same manner as in Example 1. A product was produced, and properties of the obtained polyamide resin composition were evaluated. Table 1 shows the results.

[0074]

[Table 1]

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (reference) C09K 21/14 C09K 21/14 F term (reference) 4H028 AA06 AA08 AA11 AA43 AA44 AB04 BA06 4J002 BC112 CL001 DA016 DB016 DE076 DE127 DE136 DE146 DE236 DG056 DJ006 DJ016 DJ036 DJ046 DJ056 DK006 DL006 FA046 FB096 GQ00

Claims (3)

[Claims] (A) An aromatic polyamide having an MFR measured at a load of 2.16 kg and a melting point of + 10 ° C. in the range of 40 to 300 g / 10 min.
80 parts by weight, (B) an inorganic reinforcing material: 5 to 50 parts by weight, and (C) a bromine content of 44 to 61% by weight and a load of 3.8 k.
g, MFR measured at 230 ° C. is 70 to 300 g / 1.
0 minute polybrominated styrene: 5 to 40 parts by weight, (D)
Compound containing antimony and / or composite oxide containing zinc: 0.1 to 10 parts by weight (provided that (A),
(B), (C), and (D) wherein the total of the components is 100 parts by weight). 2. A polyamide extracted from said flame retardant polyamide composition with concentrated sulfuric acid has a viscosity number of 6 measured.
2. The flame-retardant polyamide composition according to claim 1, wherein the composition is in the range of 0 to 110 ml / g. 3. A flame-retardant electric / electronic component characterized by being formed from the flame-retardant polyamide composition according to claim 1.