JP2002309083A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition excellent in flame retarding property, heat resistance and property showing a beautiful surface. SOLUTION: This polyamide resin composition is obtained by blending (A) 100 pts.wt. polyamide containing of (a) a dicarboxylic acid unit containing 60-100 mol% terephthalic acid unit and (b) diamine unit containing 1,9-nonane diamine unit or 1,9-nonane diamine unit and 2-methyl-1,8-octane diamine unit and also having (100:0)-(20:80) molar ratio of the 1,9-nonane diaminie unit to the 2-methyl-1,8-octane diamine unit, and having 0.4-3 dl/g intrinsic viscosity, (B) 10-200 pt.wt. organic halogen compound and (C) 0.1-10 pt.wt. α-olefin polymer having 0.2-100 g/10 min MFR value measured at 230 deg.C and not having a functional group capable of reacting with the (A) polyamide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a polyamide composition and a molded article comprising the same. The polyamide composition of the present invention provides flame-retardant, heat-resistant, and molded products excellent in surface aesthetics, such as connectors, switches, relays, electric and electronic components such as printed wiring boards, reflectors such as lamp reflectors, It can be suitably used for applications requiring flame retardancy, such as machine parts, decorative parts, films, sheets, and fibers.

[0002]

2. Description of the Related Art Aliphatic polyamides represented by nylon 6 and nylon 66 have excellent properties such as heat resistance, chemical resistance, rigidity, abrasion resistance, and moldability, and thus are widely used as engineering plastics. Has been used for In the electric and electronic fields, since high flame retardancy based on the UL-94 standard is required, many flame retarding methods using various flame retardants have been proposed and put to practical use. However, these aliphatic polyamides have large water absorption,
There have been problems such as dimensional changes of molded articles and deterioration of physical properties.
Furthermore, in recent years, for electric and electronic parts that require flame retardancy, a method called a surface mount method (SMT) has rapidly spread in order to achieve high-density mounting of parts and efficiency of a soldering process. As a result, conventional polyamides cannot cope with heat resistance.

On the other hand, recently, semi-aromatic polyamides called 6T-based polyamides whose main component is a polyamide composed of 1,6-hexanediamine and terephthalic acid have entered the field of electric and electronic parts requiring flame retardancy. JP-A-3-239755, JP-A-4-96970 and the like propose flame-retarding techniques for semi-aromatic polyamides such as 6T-based polyamides. However, polyamide composed of terephthalic acid and 1,6-hexanediamine is 370 ° C., which is higher than the decomposition temperature of the polymer.
Since there is a melting point in the vicinity, melt polymerization and melt molding are difficult and are not practical. Therefore, a dicarboxylic acid component such as adipic acid or isophthalic acid or an aliphatic polyamide such as nylon 6 is actually used in an amount of 30 to 40 mol%.
At present, it is used in a composition whose melting point is lowered to a practically usable temperature range, that is, about 280 to 320 ° C. by copolymerization. Although copolymerization of such a large amount of the third component (or the fourth component in some cases) is certainly effective in lowering the melting point of the polymer, it is accompanied by a decrease in the crystallization speed and the ultimate crystallinity. As a result, not only physical properties such as rigidity at high temperatures, chemical resistance and dimensional stability are reduced, but also productivity is reduced due to extension of the molding cycle. Also, fluctuations in physical properties such as dimensional stability due to water absorption have been improved to some extent compared to conventional aliphatic polyamides by the introduction of aromatic groups, but have reached the level of substantial problem solving. Absent.

[0004] To solve these problems,
Japanese Unexamined Patent Publication (Kokai) No. 7-228775 proposes a flame retardant composition of a semi-aromatic polyamide containing a polyamide composed of 9-nonanediamine and terephthalic acid as a main component. If the dispersed particle size in the continuous phase is large, the surface of a molded product formed by injection molding or the like may be peeled and the surface may be roughened, and the colored surface of the colored product may be whitened. In recent years, in the electric and electronic fields, connectors, which are internal components, have become narrower and have more pins due to miniaturization and higher functionality of products, and injection molding conditions are severe, and the surface of molded products is more easily whitened.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a flame-retardant polyamide composition which gives a molded article having excellent flame retardancy, heat resistance and surface aesthetics.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by adding a specific amount of a specific α-olefin polymer to a specific semi-aromatic polyamide, The inventors have found that a flame-retardant polyamide composition having excellent surface beauty of a molded article can be obtained, and have completed the present invention.

That is, the present invention relates to a dicarboxylic acid unit (a) containing 60 to 100 mol% of a terephthalic acid unit.
And 1,9-nonanediamine unit or 60 to 100 mol% of 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit, and
Nonanediamine unit: diamine unit (b) having a molar ratio of 2-methyl-1,8-octanediamine unit of 100: 0 to 20:80, and an intrinsic viscosity of 0.4 to 3.
Based on 100 parts by weight of the polyamide (A) of 0 dl / g, the organic halogen compound (B) has an MFR value of 10 to 200 parts by weight and an MFR value measured at 230 ° C. of 0.2 to 100 g / 1.
The present invention relates to a polyamide composition containing 0 to 10 minutes and 0.1 to 10% by weight of an α-olefin polymer (C) having no functional group capable of reacting with the polyamide (A), and a molded article comprising the same.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The dicarboxylic acid unit (a) constituting the polyamide (A) used in the present invention has a terephthalic acid unit of 60-1.
The terephthalic acid unit content is preferably in the range of 75 to 100 mol%, and is preferably 90 mol%.
More preferably, it is in the range of １００100 mol%. When the content of the terephthalic acid unit is less than 60 mol%, the heat resistance of the obtained polyamide composition decreases.

The above dicarboxylic acid unit (a) may contain a dicarboxylic acid unit other than terephthalic acid unit as long as it is 40 mol% or less, and the other dicarboxylic acid unit includes malonic acid, Dimethylmalonic acid, succinic acid,
Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid; 1,3
Alicyclic dicarboxylic acids such as -cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid;
1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, diphenic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid,
Diphenylsulfone-4,4'-dicarboxylic acid, 4,
Examples include units derived from an aromatic dicarboxylic acid such as 4'-biphenyldicarboxylic acid, and one or more of these units can be used. Of these, units derived from aromatic dicarboxylic acids are preferred. As the content of these other dicarboxylic acid units,
It is preferably at most 25 mol%, more preferably at most 10 mol%. Further, a unit derived from a polycarboxylic acid such as trimellitic acid, trimesic acid and pyromellitic acid may be contained within a range in which melt molding is possible.

The diamine unit (b) constituting the polyamide (A) used in the present invention comprises 1,9-nonanediamine unit or 60 units of 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit. ~ 100 mol%
contains. That is, when the diamine unit (b) contains a 1,9-nonanediamine unit and a 2-methyl-1,8-octanediamine unit, the total content of both units is 60.
To 100 mol%, and when not containing 2-methyl-1,8-octanediamine unit, the content of 1,9-nonanediamine unit is 60 to 100 mol%. The content is preferably in the range of 75 to 100 mol%,
More preferably, it is in the range of 90 to 100 mol%. 1,9-
When the content of the nonanediamine unit or the content of the 1,9-nonanediamine unit and the 2-methyl-1,8-octanediamine unit is within the above range, the heat resistance of the obtained polyamide is increased.

1,9 in the above diamine unit (b)
The molar ratio of -nonanediamine unit: 2-methyl-1,8-octanediamine unit is in the range of 100: 0 to 80:20, preferably in the range of 100: 0 to 60:40, and : 0 to 80:20. When the molar ratio of 1,9-nonanediamine unit: 2-methyl-1,8-octanediamine unit is within the above range, the heat resistance of the obtained polyamide is increased.

The above diamine unit (b) is 40 mol%
If it is the following, it may contain other diamine units other than 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and as the other diamine units, ethylenediamine, propylenediamine, 1,4 -Butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl Aliphatic diamines such as -1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine and 5-methyl-1,9-nonanediamine; fats such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine Cyclic diamine; p-phenylenediamine, m-phenylenediamine, xylene diamine , 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,
Examples include units derived from an aromatic diamine such as 4′-diaminodiphenyl ether, and one or more of these units can be used. The content of these other diamine units is preferably 25 mol% or less, more preferably 10 mol% or less.

The polyamide (A) used in the present invention comprises:
It is preferable that 10% or more of the terminal groups of the molecular chain are blocked by a terminal blocking agent. The ratio of the terminal group of the molecular chain blocked by the terminal blocking agent (terminal blocking ratio)
It is more preferably at least 40%, and even more preferably at least 70%. When a polyamide having a terminal blocking rate of 10% or more is used, physical properties such as melt moldability and surface aesthetics become more excellent.

The terminal capping rate of the polyamide (A) is determined by measuring the number of carboxyl group terminals, amino group terminals and the number of terminal groups capped by the terminal capping agent in the polyamide, respectively, and the following formula (1) Can be obtained by The number of each terminal group is preferably determined from the integrated value of the characteristic signal corresponding to each terminal group by ¹ H-NMR from the viewpoint of accuracy and simplicity.

End-capping rate (%) = [(XY) / X] × 100 (1) wherein X is the total number of molecular chain terminal groups (this is usually equal to twice the number of polyamide molecules) ) And Y represents the total number of carboxyl group terminals and amino group terminals. ]

The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or the carboxyl group at the polyamide terminal, but it is not limited in terms of reactivity and stability of the blocked terminal. Thus, monocarboxylic acids or monoamines are preferred, and monocarboxylic acids are more preferred from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, and monoalcohols can also be used.

The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid,
Valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid,
Aliphatic monocarboxylic acids such as pivalic acid and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid And aromatic monocarboxylic acids; and arbitrary mixtures thereof. Of these,
Acetic acid, from the viewpoint of reactivity,
Preferred are propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, and benzoic acid.

The monoamine used as the terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. Examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine,
Aliphatic monoamines such as octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine;
Aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; arbitrary mixtures thereof; Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred from the viewpoints of reactivity, high boiling point, stability of a sealed terminal, and price.

The polyamide (A) used in the present invention comprises:
It can be produced using any method known as a method for producing a crystalline polyamide. For example, it can be produced by a solution polymerization method or an interfacial polymerization method using acid chloride and diamine as raw materials, a melt polymerization method using dicarboxylic acid and diamine as raw materials, a solid-phase polymerization method, a melt extruder polymerization method, or the like.

The polyamide (A) is prepared, for example, by first adding a diamine, a dicarboxylic acid, a catalyst and, if necessary, an end-capping agent all at once to produce a nylon salt.
Polymerization by heating at a temperature of ~ 250 ° C and 30 ° C in concentrated sulfuric acid
Can be produced by making a prepolymer having an intrinsic viscosity [η] of 0.1 to 0.6 dl / g, and further performing solid phase polymerization or polymerization using a melt extruder. The intrinsic viscosity [η] of the prepolymer is 0.1 to 0.6 d.
When the amount is within the range of 1 / g, a polyamide which has a small difference in the molar balance between carboxyl groups and amino groups and a small decrease in the polymerization rate in the post-polymerization stage, has a small molecular weight distribution, and is excellent in various physical properties and moldability is obtained. Can be When the final stage of the polymerization is carried out by solid-phase polymerization, it is preferably carried out under reduced pressure or under the flow of an inert gas.
Within the range of 280 ° C., the polymerization rate is high, the productivity is excellent, and the coloring and gelation can be effectively suppressed. The polymerization temperature in the case where the final stage of the polymerization is carried out by a melt extruder is preferably 370 ° C. or lower. When the polymerization is carried out under such conditions, the polyamide is hardly decomposed and the polyamide is not deteriorated.

In producing the polyamide (A), in addition to the terminal blocking agent, for example, phosphoric acid,
Phosphorous acid, hypophosphorous acid, their salts or esters can be added. Examples of the above salts or esters include phosphoric acid, phosphorous acid or hypophosphorous acid and metals such as potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony. Salt; phosphoric acid, ammonium salt of phosphorous acid or hypophosphorous acid; ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester of phosphoric acid, phosphorous acid or hypophosphorous acid , Stearyl ester, phenyl ester and the like.

The polyamide (A) used in the present invention comprises:
The intrinsic viscosity [η] measured at 30 ° C. in concentrated sulfuric acid is 0.4 to
3.0 dl / g, preferably 0.5 to 2.0 dl / g, and more preferably 0.6 to 1.8 dl / g. When the one having the intrinsic viscosity [η] within the above range is used, a molded article excellent in mechanical properties, heat resistance and the like can be obtained.

The polyamide composition of the present invention contains an organic halogen compound (B) as a component other than the above-mentioned polyamide (A). The organic halogen compound (B) is a component that imparts flame retardancy to the polyamide composition, and includes, for example, brominated polystyrene, polybrominated styrene, brominated polyphenylene ether, brominated bisphenol type epoxy copolymer, brominated Styrene-maleic anhydride copolymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromobiphenyl,
Brominated polycarbonate, perchlorochloropentadecane, brominated cross-linked aromatic polymer and the like can be mentioned, and one or more of these can be used. Among these, polybrominated styrene, brominated polystyrene, and brominated polyphenylene ether are preferred from the viewpoint of heat resistance. The halogen atom content of the organic halogen compound (B) is preferably in the range of 15 to 87% by weight, and more preferably in the range of 50 to 80% by weight. The compounding amount of the organic halogen compound (B) is 10
0 to 100 parts by weight, preferably 20 to 100 parts by weight, more preferably 30 to 8 parts by weight with respect to 0 parts by weight.
More preferably, the amount is within the range of 0 parts by weight. If the amount of the organic halide (B) is less than 10 parts by weight, flame retardancy cannot be imparted, and if it exceeds 200 parts by weight, the mechanical and thermal properties deteriorate.

The polyamide composition of the present invention comprises, together with the polyamide (A) and the organic halogen compound (B),
Α having an MFR value of 0.2 to 100 g / 10 minutes measured at 0 ° C. and having no functional group capable of reacting with polyamide.
-Contains an olefin polymer (C). Thereby, when the polyamide composition of the present invention is molded by a molding method such as injection molding, the bleed-out phenomenon of the organic halogen compound can be suppressed, and the surface roughness of the molded product and the whitening of the colored product can be prevented.

When the MFR value of the α-olefin polymer (C) measured at 230 ° C. is less than 0.2 g / 10 minutes, the effect of suppressing whitening is small. Cause. The above MFR value is preferably in the range of 1 to 70 g / 10 minutes.

As the α-olefin polymer (C), ethylene-octene copolymer, styrene-ethylene propylene-styrene (SEPS), polypropylene (P
P), polyethylene (PE) and the like, and from the viewpoint of surface aesthetics, ethylene-octene copolymer (engage) and SEPS are preferable. One or more of these α-olefin copolymers can be used, and they do not have a functional group capable of reacting with the polyamide (A) such as an acid anhydride group or an epoxy group.

The amount of the α-olefin polymer (C) is
0.1 to 10 with respect to 100 parts by weight of the polyamide (A)
It is within the range of parts by weight, preferably within the range of 0.1 to 5 parts by weight. When the blending amount of the α-olefin polymer (C) is 0.1
If it is less than 10 parts by weight, the effect of suppressing whitening is small, and if it exceeds 10 parts by weight, mechanical properties, heat resistance and flame retardancy are reduced.

The polyamide composition of the present invention may optionally contain a flame retardant aid (D). Flame retardant aid (D)
Metal salts of stannic acid such as zinc stannate, zinc hydroxy stannate, magnesium stannate, cobalt stannate, sodium stannate and potassium stannate; metal salts of boric acid such as zinc borate, calcium borate and magnesium borate; Antimony trioxide, antimony pentoxide, sodium antimonate, sodium oxide, tin oxide, zinc oxide, iron oxide, magnesium hydroxide,
Examples include calcium hydroxide, kaolin clay, and calcium carbonate. These flame retardant aids may be treated with a silane coupler, a titanium coupler or the like in order to improve the dispersibility in the polyamide.
More than one species can be used. Among these, a mixture of antimony pentoxide and sodium oxide, zinc stannate, and zinc borate are preferred. As the compounding amount of the flame retardant auxiliary (D),
The amount is preferably in the range of 1 to 50 parts by weight, more preferably 1 to 30 parts by weight, based on 100 parts by weight of the polyamide (A). The metal salts of stannic acid and boric acid are
It can be used in a form containing water of crystallization, but about 40
Firing at a temperature of 0 ° C. or higher to remove water of crystallization is preferable because there is no danger of the polyamide being hydrolyzed due to volatilization of the water of crystal during melt molding. These compounds are usually powdery solids, and as an average particle size,
From the viewpoint of obtaining a molded article having better appearance, the thickness is preferably 100 μm or less, more preferably 30 μm or less, and still more preferably 10 μm or less.

The polyamide composition of the present invention may further contain, if necessary, a filler (E) having a fibrous, powdery, cloth-like or the like form.

Examples of the fibrous filler include polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber, diaminodiphenyl ether and terephthalic acid or isophthalic acid. Organic fibrous fillers such as wholly aromatic polyamide fibers such as fibers obtained from condensates, and wholly aromatic liquid crystal polyester fibers; and inorganic fibrous fillers such as glass fibers, carbon fibers, and boron fibers. Can be When such a fibrous filler is blended, not only the mechanical strength of the obtained molded article is improved, but also the dimensional stability, low water absorption and the like are further improved. The average length of the fibrous filler is preferably in the range of 0.05 to 50 mm,
From the viewpoint of further improving the moldability of the polyamide composition and further improving the sliding properties, heat resistance, and mechanical properties of the obtained molded product, it is more preferably within the range of 1 to 10 mm. These fibrous fillers may be subjected to secondary processing such as cloth.

Examples of the powdery filler include silica, silica alumina, alumina, titanium oxide, zinc oxide, boron nitride, talc, mica, potassium titanate, and the like.
Calcium silicate, magnesium sulfate, aluminum borate, asbestos, glass beads, carbon black,
Examples include graphite, molybdenum disulfide, and polytetrafluoroethylene. The average particle size of these powdery fillers is preferably in the range of 0.1 to 200 μm, and more preferably in the range of 1 to 100 μm. When these powdery fillers are blended, the dimensional stability, mechanical properties, heat resistance properties, chemical physical properties, sliding properties, and the like of the obtained molded product are further improved.

The above fillers (E) can be used alone or in combination of two or more. The content of these fillers (E) is preferably from 1 to 300 parts by weight, preferably from 10 to 1 part by weight, per 100 parts by weight of the polyamide (A).
The amount is more preferably 80 parts by weight, and even more preferably 50 to 150 parts by weight. When the compounding amount of the filler is within the above range, a polyamide composition excellent in both moldability and mechanical properties can be obtained. Furthermore, the surface of these fillers, for the purpose of enhancing dispersibility in polyamide,
It is preferable that the surface has been treated with a silane coupling agent, a titanium coupling agent, or another high-molecular or low-molecular surface treating agent.

The polyamide composition of the present invention may further comprise, if necessary, an acid catcher such as hydrotalcite; an anti-drip agent such as Teflon (registered trademark), Aerosil, Zonoheide, Mossheide, and Ionomer; polyphenylene sulfide, polyester, and fat. Other polymers such as aromatic polyamides, polyphenylene oxides, and liquid crystal polymers; coloring agents; ultraviolet absorbers; light stabilizers; antioxidants such as hindered phenol, thio, phosphorus, and amines; antistatic agents; A nucleating agent; a plasticizer; a release agent;

The polyamide composition of the present invention comprises the above-mentioned polyamide (A), organic halogen compound (B), α-olefin copolymer (C) and, if necessary, a flame retardant auxiliary (D) and a filler ( E), it can be produced by blending components such as the various additives described above. As a compounding method, for example, using a vertical or horizontal mixer usually used for resin mixing, after mixing the above components at a predetermined ratio, a single screw extruder, a twin screw extruder, a kneader, A method of melt-kneading using a Banbury mixer or the like can be used.

The polyamide composition of the present invention is injection-molded,
Extrusion molding, press molding, blow molding, calendar molding,
By molding by a molding method generally used for thermoplastic resin compositions such as cast molding, molded articles having various shapes can be produced. For example,
The polyamide composition of the present invention is melted in a cylinder of an injection molding machine in which the cylinder temperature is adjusted to a range from the melting point of the polyamide to 350 ° C. or less, and is introduced (injected) into a mold having a predetermined shape. Thus, a molded product having a predetermined shape can be manufactured. Further, the polyamide composition is melted in an extruder in which the cylinder temperature is adjusted within the above range,
By spinning from a die nozzle, a fibrous molded article can be manufactured. Further, the polyamide composition is melted in an extruder in which the cylinder temperature is adjusted within the above range, and extruded from a T-die, whereby a film or sheet-like molded product can be manufactured. Further, the molded article produced by such a method may be used in a form in which a coating layer made of a paint, a metal, another kind of polymer or the like is formed on the surface.

[0036]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited to these examples. In the examples, the average dispersed particle diameter of the organic halogen compound, the appearance of the molded product and the flammability were evaluated by the following methods.

Average dispersed particle diameter of organic halogen compound: The frozen fractured surface of the molded article was etched in chloroform at 80 ° C. for 1 hour, and observed by a scanning electron microscope. The particle diameter d and the number n of particles were determined, and the average particle diameter of the dispersed phase was calculated by the following equation. Average particle size = (Σd ⁴ · n) / (Σd ³ · n)

Appearance of molded product: Injection molded product of board-to-board connector (connector for joining substrates) [Number of cores: 64 cores, pitch: 0.5 mm, gate diameter: 0.1 mm
5 mmφ], and the appearance (surface condition) of the molded product is visually observed.
And those where only the vicinity of the gate was not smooth were evaluated as “Δ”, and those where the entire molded product was not smooth were evaluated as “x”.

Flammability: Performed according to the UL-94 standard shown below. The test piece is vertically fixed by clamping the upper end of the injection molded product having a thickness of 1 mm with a clamp, and a predetermined flame is applied to the lower end for 10 seconds and then separated, and the burning time (first time) of the test piece is measured. Immediately after the fire is extinguished, apply the flame to the lower end again and release.
The burning time (second time) of the test piece is measured. The same measurement is repeated for five pieces to obtain a total of ten data, five data of the first burning time and five data of the second burning time. The total of the ten data is T, and the maximum value of the ten data is M. If T is 50 seconds or less, M is 10 seconds or less, and it does not burn up to the clamp, if the melted flame falls and does not ignite the cotton 12 inches below, "V-0", T is 250 seconds or less, If M is 30 seconds or less and otherwise satisfy the same conditions as V-0, "V-1", T is 2
If the M does not burn up to the clamp in 50 seconds or less and M is 30 seconds or less, the flamed melt falls and ignites the cotton 12 inches below, resulting in "V-2".

In the following Examples and Comparative Examples, the following polyamides were used. PA9MT: terephthalic acid unit as dicarboxylic acid unit, 1,9-nonanediamine unit and 2-methyl-
1,8-octanediamine unit is replaced by diamine unit (1,9
-Intrinsic diamine unit: 2-methyl-1,8-octanediamine unit: 85:15), intrinsic viscosity [η]: 1.00 dl / g, melting point: 308 ° C, endcapping ratio: 9
0% (end capping agent: benzoic acid) polyamide.

<Examples 1 to 6> Polybrominated styrene (PBrS; “PBS-64” manufactured by Great Lakes Chemical) and brominated polystyrene (68PB; “Pyrocheck 68P” manufactured by Albemarle) were used for the above polyamide.
B "), zinc borate (" Firebreak 415 "manufactured by Borax), a mixture of sodium oxide and antimony pentoxide (" Sun Epoque NA-107 "manufactured by Nissan Chemical Industries, Ltd.)
0L "), zinc stannate (" FL "manufactured by DK Fine Co., Ltd.
AMTARD-S ”), ethylene-octene copolymer (“ Engage EG8200 ”manufactured by Dow Chemical, MFR
= 5g / 10min), SEPS (Kuraray “Septon 20”)
02 ", MFR = 70 g / 10 min), polypropylene (PP; Japan polyolefin" J106W ", MFR =
15g / 10 minutes), glass fiber (Nitto Boseki Co., Ltd. “C
S-3J-256S ") were premixed in the proportions shown in Table 1 below. This was supplied to a twin-screw extruder (“TEX44C” manufactured by Nippon Steel Works, Ltd.) and the cylinder temperature was set to 320.
The resulting mixture was melt-kneaded at a temperature of ° C., extruded, cooled and cut to obtain pellets of the polyamide composition. Table 1 shows the results of evaluation of the molded product obtained by injection molding of this pellet (cylinder temperature 330 ° C., mold temperature 150 ° C.) by the above method.

<Comparative Examples 1 and 2> Polyamide compositions were prepared in the same manner as in Examples 1 to 6, except that the α-olefin polymer was not used and other components were blended in the proportions shown in Table 1 below. A product pellet was obtained. Table 1 shows the results of evaluation of the molded product obtained by injection molding of this pellet (cylinder temperature 330 ° C., mold temperature 150 ° C.) by the above method.

Comparative Example 3 Pellets of a polyamide composition were prepared in the same manner as in Examples 1 to 6, except that an α-olefin polymer was used and other components were blended in the proportions shown in Table 1 below. I got Table 1 shows the results of evaluation of the molded product obtained by injection molding of this pellet (cylinder temperature 330 ° C., mold temperature 150 ° C.) by the above method. <Comparative Example 4> Except that Kuraray's “Septon 4055” (MFR = 0.01 g / 10 min) was used as an α-olefin polymer and other components were blended in the ratios shown in Table 1 below. Pellets of the polyamide composition were obtained in the same manner as in Examples 1 to 6. Table 1 shows the results of evaluation of the molded product obtained by injection molding of this pellet (cylinder temperature 330 ° C., mold temperature 150 ° C.) by the above method.

[0044]

[Table 1]

From the results shown in Table 1 above, the polyamide compositions of Examples 1 to 6 containing the α-olefin polymer in the proportions specified in the present invention are comparative examples 1 and 2 containing no α-olefin polymer. It can be seen that the surface composition is extremely excellent as compared with the polyamide composition of Example 1. Furthermore, α-
In the polyamide composition of Comparative Example 3 in which the blending amount of the olefin polymer exceeds the ratio specified in the present invention, the α-olefin polymer peeled off on the surface of the molded product, resulting in poor appearance and markedly reduced flame retardancy. Comparative Example 4 in which the MRF value of the α-olefin polymer was out of the range specified in the present invention.
In the polyamide composition, the appearance of the molded product is poor.

[0046]

According to the present invention, there is provided a polyamide composition which gives a molded article having excellent flame retardancy, heat resistance and surface aesthetics.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) C08K 5/02 C08K 5/02 // (C08L 77/06 C08L 23:00 23:00) F-term (reference ) 4F071 AA14 AA15 AA20 AA22 AA54 AB18 AB19 AC03 AE01 AE07 AF27 AF45 AF47 AH12 AH17 BA01 BB02 BB03 BB04 BB05 BB06 BC01 BC07 4J001 DA01 DB04 DC14 EB37 EC04 EC09 EE23E FA01 FB03 J03B01 J03B03 FC06 JA07B02

Claims (6)

[Claims] 1. A terephthalic acid unit having a content of 60 to 100 mol%
The contained dicarboxylic acid unit (a) and 1,9-nonanediamine unit, or 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit are 60 to 1
And containing 1,9-nonanediamine unit:
A polyamide (A) comprising a diamine unit (b) having a molar ratio of 2-methyl-1,8-octanediamine units of 100: 0 to 20:80 and having an intrinsic viscosity of 0.4 to 3.0 dl / g. A) a functional group capable of reacting with the polyamide (A) having an MFR value of 0.2 to 100 g / 10 min measured at 10 to 200 parts by weight and 230 ° C. based on 100 parts by weight; The polyamide composition which mix | blended 0.1-10 weight of (alpha) -olefin polymer (C) which does not have this. 2. The polyamide composition according to claim 1, wherein the organic halogen compound (B) is at least one compound selected from the group consisting of polybrominated styrene, brominated polystyrene, and brominated polyphenylene ether. 3. The α-olefin polymer (C) is at least one polymer selected from the group consisting of ethylene-octene copolymer, styrene-ethylene propylene-styrene (SEPS), polypropylene and polyethylene. Item 3. The polyamide composition according to Item 1 or 2. 4. The polyamide composition according to claim 1, further comprising 1 to 50 parts by weight of a flame retardant aid (D) based on 100 parts by weight of the polyamide (A). 5. The polyamide composition according to claim 1, further comprising 1 to 300 parts by weight of a filler (E) based on 100 parts by weight of the polyamide (A). 6. A molded article comprising the polyamide composition according to any one of claims 1 to 5.