JPH07126516A - Aromatic polyamide resin composition - Google Patents

Abstract

PURPOSE:To obtain a n aromatic polyamide resin composition which gives a molding excellent in rigidity at high temperature and having high weld strength. CONSTITUTION:The resin composition consists of a polyphenylene ether and an aromatic polyamide which consists of repeating units comprising dicarboxylic acid constituent units composed of 50-100mol% terephthalic acid and 0-50mol% of other aromatic dicarboxylic acid and/or 0-50mol% 4-20C aliphatic dicarboxylic acid and diamine constituent units composed of an aliphatic diamine and/or an alicyclic diamine and which has a content of terminal amino groups of at least 0.1mmol/g and an intrinsic viscosity measured in concentrated sulfuric acid at 30 deg.C of 0.5-0.9dl/g.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an aromatic polyamide resin composition capable of obtaining a molded article having excellent rigidity especially at high temperature and improved weld strength.

[0002]

BACKGROUND OF THE INVENTION Conventionally, an aliphatic polyamide (nylon) such as nylon 6, nylon 66 or nylon 610 has been used as an engineering plastic.

Although such an aliphatic polyamide has good moldability, it has a low glass transition temperature (for example, the glass transition temperature of nylon 66 is usually around 60 ° C.), and the aliphatic polyamide is used at a high temperature. It is not always suitable as an engineering plastic.

As the polyamide, in addition to the above aliphatic polyamide, an aromatic polyamide whose dicarboxylic acid component is mainly an aromatic dicarboxylic acid is known. Aromatic polyamides are superior to aliphatic polyamides such as nylon 6 and nylon 66 in terms of heat resistance, chemical resistance, and water resistance, but their molding temperature is high, so when injection molding is used, injection molding The temperature drop rate (cooling rate) of the molded melt is significantly higher than that of ordinary polyamides, which causes a problem that the crystal growth rate becomes slow and the crystallinity of the resulting molded product becomes low. . When the degree of crystallinity of the molded body is low as described above, there arises a problem that the heat resistance of the molded body is insufficient.

In order to solve such problems, it has been considered to add polyphenylene ether to the above heat-resistant polyamide. However, the composition comprising the heat-resistant polyamide and polyphenylene ether as described above, that the fluidity of the polyphenylene ether is low, and the polyphenylene ether is difficult to uniformly disperse in the heat-resistant polyamide, the dispersion state is coarse. Therefore, when a resin is simultaneously injected from a gate of a mold having a plurality of gates to manufacture an injection-molded article, the strength of the weld, which is a portion where the composition injected from each gate is joined, becomes low. There is a problem.

When manufacturing a large molded product such as a mechanical structural part of an automobile by injection molding, it is usual to provide a plurality of gates on the mold, and in this case, a weld is not formed on the molded product. Inevitable. Therefore, in order to manufacture an injection molded body such as an automobile mechanism structural part using a composition composed of heat-resistant polyamide and polyphenylene ether, such improvement in weld strength is indispensable.

The present inventor has earnestly studied a method for improving the weld strength of a composition comprising a heat-resistant polyamide and polyphenylene ether, and as a result, found that an aromatic polyamide having a specific range of molecular weight and a specific amount of terminal amino groups was selected. It was found that the use thereof is effective in improving the weld strength, and the present invention has been completed.

[0008]

An object of the present invention is to improve the high temperature rigidity and weld strength of an aromatic polyamide.

[0009]

SUMMARY OF THE INVENTION The aromatic polyamide resin composition of the present invention comprises (a) a terephthalic acid component unit of 50 to 100 mol%.
And an aromatic dicarboxylic acid component unit other than terephthalic acid 0
To 50 mol% and / or 0 to 50 mol% of aliphatic dicarboxylic acid component units having 4 to 20 carbon atoms, and aliphatic diamine component units, and / or
Or a repeating unit consisting of a diamine component unit consisting of an alicyclic diamine component unit, and having a terminal amino group content (terminal amino group content in 1 g of aromatic polyamide, the same as in the present invention) is 0.1 mmol / g or more. And has an intrinsic viscosity of 0.0 measured in concentrated sulfuric acid at 30 ° C.
It is characterized by comprising an aromatic polyamide of 3 to 0.9 dl / g and (b) polyphenylene ether.

The injection-molded article obtained from the aromatic polyamide resin composition of the present invention containing the specific aromatic polyamide and polyphenylene ether as described above is excellent in high temperature rigidity and weld strength.

Furthermore, by adding a fibrous filler to this composition, the heat resistance and mechanical properties of the molded product are improved.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Next, the aromatic polyamide resin composition of the present invention will be specifically described. The aromatic polyamide resin composition of the present invention comprises the following specific aromatic polyamide and polyphenylene ether.

The aromatic polyamide constituting the composition of the present invention is composed of a repeating unit composed of a specific dicarboxylic acid component unit [A] and a specific aliphatic diamine component unit [B].

The specific dicarboxylic acid component unit [A] constituting the polyamide has a terephthalic acid component unit (a) as an essential component unit. The repeating unit having such a terephthalic acid component unit (a) can be represented by the following formula [I].

[0015]

[Chemical 1]

However, in the above formula [I], R ¹ is
It represents a divalent carbon-hydrogen group corresponding to a diamine component described later.

The repeating units constituting the aromatic polyamide do not have to be all the constituent units represented by the above formula [I], and other dicarboxylic acid may be used in place of the above terephthalic acid constituent unit (a). It may have a component unit.

The carboxylic acid component unit other than the terephthalic acid component includes an aromatic dicarboxylic acid component unit (b) other than terephthalic acid and an aliphatic dicarboxylic acid component unit.
There is (c).

Examples of the aromatic dicarboxylic acid component unit (b) other than terephthalic acid include an isophthalic acid component unit, a 2-methylterephthalic acid component unit, a naphthalenedicarboxylic acid component unit and a biphenyldicarboxylic acid unit. When the aromatic polyamide used in the present invention has an aromatic dicarboxylic acid component unit other than terephthalic acid, an isophthalic acid component unit is particularly preferable as such a component unit.

Among the aromatic dicarboxylic acid component units (b) other than terephthalic acid, the repeating unit having an isophthalic acid component unit particularly preferred in the present invention can be represented by the following formula [II].

[0021]

[Chemical 2]

However, in the above formula [II], R ¹ has the same meaning as R ¹ in the above formula [I].

Further, the aliphatic dicarboxylic acid component unit is
It is usually derived from an aliphatic dicarboxylic acid having an alkylene group having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms.
Examples of the aliphatic dicarboxylic acid used for deriving such an aliphatic dicarboxylic acid component unit (c) include succinic acid, adipic acid, azelaic acid and sebacic acid.

When the polyamide has an aliphatic dicarboxylic acid component unit, an adipic acid component unit is particularly preferable as such a component unit.

A repeating unit having a repeating unit containing an aliphatic dicarboxylic acid component unit (c) as another dicarboxylic acid component unit constituting the dicarboxylic acid component unit [A] is
It can be expressed by the following formula [III].

[0026]

[Chemical 3]

[0027] However, in the above formula [III], R ¹ is the same meaning as R ¹ in the above 1, n is 4 to 20,
Preferably, it represents an integer of 6 to 12.

The aromatic polyamide constituting the composition of the present invention is composed of a dicarboxylic acid component unit [A] and a diamine component unit [B].

The diamine component unit [B] includes an aliphatic diamine component unit and an alicyclic diamine component unit.

The aliphatic diamine component unit is a component unit usually derived from an aliphatic alkylenediamine having 4 to 18 carbon atoms, preferably 6 to 18 carbon atoms.

Specific examples of such aliphatic alkylenediamines include 1,4-diaminobutane, 1,6-diaminohexane, trimethyl-1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Mention may be made of diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane.

Particularly in the present invention, the diamine component unit is preferably a component unit derived from a linear aliphatic alkylenediamine, and such linear aliphatic alkylenediamine includes 1,6-diaminohexane and 1,8 -Diaminooctane, 1,10-diaminodecane, 1,12-diaminododecane, and mixtures thereof are preferred. Furthermore, among these, 1,6-diaminohexane is particularly preferable.

The alicyclic diamine component unit is usually a component unit derived from an alicyclic diamine having 3 to 18 carbon atoms, preferably 6 to 18 carbon atoms.

Specific examples of such alicyclic diamines include cyclohexylenediamine, bis (aminomethyl) cyclohexane, and bis (4-aminocyclohexyl).
Mention may be made of methane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 1,3-bis (aminocyclohexyl) methane and 1,3-bis (aminomethyl) cyclohexane.

Such diamine components may be used alone or in combination.

The content of the terephthalic acid component unit (a) in the total dicarboxylic acid component (100 mol%) of the aromatic polyamide used in the present invention is 50 to 100 mol%, preferably 60 to 100 mol%. The content of the aromatic dicarboxylic acid component unit (b) other than terephthalic acid is 0 to 50 mol%, preferably 0 to 40 mol%, and the content of the aliphatic dicarboxylic acid component unit (c) is 0. ˜50 mol%, preferably 0-40 mol%.

In the aromatic polyamide, the terephthalic acid component unit, which is the main component unit, and a component unit derived from a divalent aromatic carboxylic acid other than terephthalic acid, which is represented by an isophthalic acid component unit. And in addition to the repeating unit having an aliphatic dicarboxylic acid component unit described above, even if it contains a small amount of a repeating unit having a polybasic carboxylic acid component unit of tribasic or more such as trimellitic acid or pyromellitic acid Good. The content of the repeating unit containing the component unit derived from such a polycarboxylic acid in the aromatic polyamide used in the present invention is usually 0 to 5 mol%.

The aromatic polyamide (a) used in the present invention further has a terminal amino group content of 0.1 mmol / g or more in 1 g of the aromatic polyamide, and 3
Intrinsic viscosity [η] measured in 0 ° C concentrated sulfuric acid is 0.03 to 0.9
It is necessary to be dl / g.

When the terminal amino group content of the aromatic polyamide (a) is less than 0.1 mmol / g polymer, the polyphenylene ether in the resin composition of the present invention comprising the aromatic polyamide and the polyphenylene ether is poorly dispersed. Become. Therefore, the injection molded articles obtained from this composition do not improve to the extent that weld strength is required. Even if the content of the terminal amino groups of the aromatic polyamide (a) is 0.1 mmol / g or more, the intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C is 0.9d.
If it exceeds 1 / g, the fluidity of the resin composition comprising this aromatic polyamide and polyphenylene ether will be reduced. Therefore, the injection molded articles obtained from this composition do not improve to the extent that weld strength is required.

Further, the terminal amino group content is 0.1 to 0.2.
By using an aromatic polyamide having an intrinsic viscosity [η] of 0.7 to 0.9 dl / g measured in concentrated sulfuric acid at 30 ° C., an injection-molded article having a higher weld strength can be obtained. Obtainable.

The aromatic polyamide (a) as described above is
It can be manufactured according to various methods for manufacturing a polyamide.

For example, a solution method in which an aromatic dicarboxylic acid and adipic acid are converted into a halide and polycondensed with an aliphatic alkylenediamine in a uniform solution, a halide of an aromatic dicarboxylic acid and adipic acid dissolved in a polar solvent, and a nonpolar The aromatic polyamide (a) can be produced by an interfacial method in which an aliphatic alkylenediamine dissolved in a solvent is condensed at the interface. The aromatic polyamide as described above can also be produced by a melt polymerization method or a solid phase polymerization method.

In order to adjust the terminal amino group content of the aromatic polyamide as described above, for example, in the polycondensation, the compounding mole number of the aliphatic alkylenediamine is set to the aromatic dicarboxylic acid and the adipic acid. The amount of each of the ingredients is adjusted so that the total amount is more than the total number of moles. In particular, in the present invention, [aliphatic alkylenediamine /
(The total number of moles of aromatic dicarboxylic acid and adipic acid blended)] is 1.08 to 1.15, preferably 1.0.
By adjusting the charging amount so as to be 9 to 1.12, it is possible to obtain an aromatic polyamide capable of producing a molded product having high weld strength.

The intrinsic viscosity of this aromatic polyamide can be adjusted, for example, by mixing a molecular weight modifier in the reaction system and reacting the dicarboxylic acid with the diamine. As the molecular weight modifier used here,
Monocarboxylic acids and monoamines (eg primary or secondary amines) can be used.

Examples of monocarboxylic acids used here include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, aromatic monocarboxylic acids and alicyclic monocarboxylic acids. The aromatic monocarboxylic acid and the alicyclic monocarboxylic acid may have a substituent in the cyclic structure portion.

Examples of aliphatic monocarboxylic acids are acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid. Can be mentioned. Further, examples of the aromatic monocarboxylic acid can include benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid and phenylacetic acid, and examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid. Can be mentioned.

As the monoamine, aliphatic, alicyclic and aromatic primary amines and secondary amines can be used. Here, examples of the first and second aliphatic monoamines include methylamine, ethylamine, propylamine, butylamine, hexylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine. . Further, examples of the first and second aromatic monoamines include aniline, toluidine, diphenylamine and naphthylamine, and further examples of the first and second alicyclic monoamines include cyclohexylamine and dicyclohexylamine. Can be mentioned.

Such a molecular weight modifier is used in the reaction of the above-mentioned aromatic dicarboxylic acid and diamine. This molecular weight modifier is used for the dicarboxylic acid component 1 in the reaction system.
Normally, 0.0001 to 0.05 mol, preferably
Used in an amount of 0.0005 to 0.02 mol. By using the molecular weight modifier in such an amount, at least a part thereof is incorporated into the polyamide, and thereby the molecular weight of the aromatic polyamide, that is, the intrinsic viscosity is adjusted within the range defined by the present invention.

Further, the intrinsic viscosity of the aromatic polyamide can be adjusted within the above range by adjusting the reaction time, the reaction temperature and the like.

The aromatic polyamide used in the present invention includes an aromatic polyamide having a repeating unit represented by the above formula [I] as a main repeating unit, the above formula [II] and / or the above formula [III]. ] It may be a mixture of an aromatic polyamide having a repeating unit represented by the following as a main repeating unit. In this case, the content of the aromatic polyamide containing the repeating unit represented by the formula [I] as a main repeating unit is usually 50% by weight or more, preferably 60% by weight or more.

The aromatic polyamide constituting the composition of the present invention has a melting point higher than that of the conventionally used aliphatic polyamide. That is, the melting point of the aromatic polyamide used in the present invention is usually 280 ° C or higher, preferably 290 to 340 ° C. Furthermore, the glass transition temperature in the amorphous part of the aromatic polyamide used in the present invention is usually 70 ° C. or higher.

Further, since this aromatic polyamide has a glass transition temperature of 70 ° C. or higher in the amorphous portion, cracks and the like will not occur even when the molded product formed from the composition of the present invention is exposed to high temperatures. Hard to occur.

This aromatic polyamide has excellent chemical resistance and low water absorption as compared with conventional aliphatic polyamides.
The composition of the present invention containing this aromatic polyamide and polyphenylene ether exhibits extremely low water absorption.

The polyphenylene ether constituting the aromatic polyamide resin composition of the present invention is a polyphenylene ether having a structure represented by the formula [IV], and in the present invention, the polyphenylene ether is an unmodified polyphenylene ether as described above. Not only the ether but also a modified polyphenylene ether containing a polar group as described later is included.

[0055]

[Chemical 4]

However, in the above formula [IV], R ² , R ³ ,
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom,
It is an alkyl group, an alkoxy group, a cyano group, a nitro group, an amino group, a phenoxy group or a sulfone group, and n is a positive integer indicating the degree of polymerization.

In the above formula [IV], n is 20 to 100.
0 is preferred.

Examples of the polyphenylene ether represented by the formula [IV] are poly-1,4-phenylene ether, poly-2,6-dimethyl-1,4-phenylene ether and poly-2,6. -Diethyl-1,4-phenylene ether, poly-2,6-
Dipropyl-1,4-phenylene ether, poly-2-methyl-6
-Isopropyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2,6-dichloromethyl-1,4-phenylene ether, poly-2,6-diphenyl
-1,4-phenylene ether, poly-2,6-dinitrile-1,4-
Examples thereof include phenylene ether, poly-2,6-dichloro-1,4-phenylene ether, poly-2,5-dimethyl-1,4-phenylene ether and the like. These may be used alone or in admixture of two or more.

About these polyphenylene ethers, 3
The intrinsic viscosity [η] measured in chloroform at 0 ° C is usually 0.01 to 5 dl / g, preferably 0.1 to 3 dl / g.
Is.

The softening temperature (TMA) of the above polyphenylene ether measured by a thermo mechanical analyzer is usually 100 ° C. or higher, preferably 1
It is 50 to 250 ° C., and the glass transition temperature (Tg) is usually 100 ° C. or higher, preferably 150 to 250 ° C.

In the present invention, the unmodified polyphenylene ether as described above can be used as the polyphenylene ether, and the modified polyphenylene ether containing a polar group can be used as the polyphenylene ether. Examples of the polar group introduced into the polyphenylene ether include a carboxyl group, a carboxylic acid anhydride group and an epoxy group.

The polyphenylene ether having such a polar group introduced (modified polyphenylene ether containing a polar group) is, for example, (a) a vinyl monomer having the polar group in the molecule as described above is grafted onto the polyphenylene ether. Polymerized, or (b) polycarboxylic acid or its acid anhydride acid chloride, epichlorohydrin,
It can be synthesized by reacting a diglycidyl ester of isocyanuric acid monochloride with a terminal hydroxyl group of polyphenylene ether in the presence of a base catalyst.

As the carboxyl group-containing vinyl monomer used for introducing a carboxyl group into polyphenylene ether, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, bicyclo [2] , 2,1] Hept-2-ene-5,6-
Unsaturated carboxylic acids such as dicarboxylic acids are used. Of these, fumaric acid is particularly preferably used.

Further, to introduce a carboxylic acid anhydride into polyphenylene ether, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo [2,2,1] hept-2-ene-5, 6-dicarboxylic acid anhydride or the like is used. Of these, maleic anhydride is particularly preferably used.

As the vinyl monomer having an epoxy group in the molecule used for introducing an epoxy group into polyphenylene ether, glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconic acid ester, diglycidyl butene dicarboxylic acid ester, Butenedicarboxylic acid monoglycidyl ester, 2-methylallyl glycidyl ether, vinyl glycidyl ether-3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, vinylcyclohexene monoxide, p-glycidyl styrene, etc. Among these, glycidyl methacrylate is preferably used.

The acid chloride of the polycarboxylic acid used for introducing the polar group is a compound in which a part or all of the carboxyl groups of the polycarboxylic acid are acid chloride groups, and examples thereof include terephthaloyl chloride and chloride. Isophthaloyl, phthaloyl chloride, oxalyl chloride, succinyl chloride, malonyl chloride, trimellitic acid chloride, trimellitic anhydride chloride and the like are used. Of these,
Trimellitic anhydride chloride is preferably used. When using an acid chloride of a polycarboxylic acid, it is desirable to add a chlorine acceptor, for example, a metal oxide.

The aromatic polyamide resin composition of the present invention comprises
It contains the aromatic polyamide (a) as described above and a polyphenylene ether (or a polar group-containing modified polyphenylene ether) (b). The aromatic polyamide resin composition of the present invention contains the aromatic polyamide (a) and the polyphenylene ether (b) in an amount of usually 1:99 to 99:
1, preferably in a weight ratio of 20:80 to 80:20.

The aromatic polyamide resin composition of the present invention is
As described above, a compatibilizer may be contained in order to satisfactorily mix the aromatic polyamide (a) and the polyphenylene ether (b). The compatibilizing agent used here is not particularly limited, and a usual compatibilizing agent used when mixing resins can be used. Particularly in the present invention, polycarboxylic acid or its derivative is highly effective as a compatibilizing agent. Examples of the polycarboxylic acid preferably used as the compatibilizing agent in the present invention include citric acid and malic acid. These compatibilizers can be used alone or in combination. Such a compatibilizer is usually used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the resin component forming the composition of the present invention.

This compatibilizing agent can be used by adding and mixing it in the polyamide (a) and / or the polyphenylene ether (b), or by previously mixing the compatibilizing agent in the polyphenylene ether (b). The polyphenylene ether (b) may be reacted with at least a part of the compatibilizing agent, and then the polyphenylene ether (b) and the polyamide (a) may be kneaded. In particular, the use of such a compatibilizer is highly useful when using unmodified polyphenylene ether.

The aromatic polyamide resin composition of the present invention is
In addition to the aromatic polyamide (a) as described above and the polyphenylene ether (including the polar group-containing modified polyphenylene ether) (b), it may further contain another polar group-containing polymer (c). .

Specific examples of such a polymer (c) include maleic anhydride graft-modified polyethylene, acrylic acid graft-modified ethylene-propylene copolymer, maleic anhydride graft-modified hydrogenated styrene-butadiene-styrene. Block copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, styrene-maleic anhydride copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, etc. are used. be able to.

When the aromatic polyamide resin composition of the present invention contains the above-mentioned polymer (c), the total amount of the above-mentioned aromatic polyamide (a) and polyphenylene ether (b) is 100 parts by weight. It is preferable to use the polymer (c) in an amount of 5 to 50 parts by weight.

The impact resistance of the resin composition can be increased by incorporating the polymer (c) into the aromatic polyamide resin composition.

Further, in addition to the components (a) and (b), and optionally the component (c), the resin composition of the present invention may be added within a range not impairing the properties of the composition. Heat resistance stabilizer, flame retardant, weather resistance stabilizer, antistatic agent,
Slip agent, anti-blocking agent, anti-fog agent, lubricant,
Dyes, pigments, natural oils, synthetic oils, waxes and the like can be added, and the mixing ratio is an appropriate amount.

Further, it is preferable to add a fibrous filler to the aromatic polyamide resin composition of the present invention.

The fibrous filler used here includes organic fibers and inorganic fibers, and any of them can be used in the present invention. In particular, the fibrous filler made of inorganic fibers is used. Is preferred. Further, suitable examples of such inorganic fibers include glass fibers and boron fibers. As such a fibrous filler, glass fiber is particularly preferable. By using glass fiber, mechanical properties such as tensile strength, flexural strength, flexural modulus of elasticity, and heat resistance properties such as heat distortion temperature of the molded product formed from the aromatic polyamide resin composition of the present invention are improved. When glass fibers are used as the fibrous filler, the average length of the glass fibers used is usually 0.1 to 20 mm, preferably 0.3 to 6 mm,
The aspect ratio is usually 10 to 2000, preferably 3
Those in the range of 0 to 600 are preferably used. By compounding such a glass fiber, a moldability of the composition of the present invention is improved, and a molded product having particularly good heat resistance such as heat deformation temperature, tensile strength, mechanical properties such as bending strength is obtained. be able to.

When the fibrous filler is blended with the composition of the present invention, the fibrous filler is usually 0.5 based on 100 parts by weight of the total weight of the aromatic polyamide and the polyphenylene ether in the composition. To 200 parts by weight, preferably 5 to 180 parts by weight, more preferably 5-1.
It is compounded in an amount within the range of 50 parts by weight.

In the aromatic polyamide resin composition of the present invention, in addition to the above-mentioned inorganic fibrous filler, in the present invention, shapes such as powder, granules, plates, needles, cloths and mats are used. Various fillers having a can be used.
Examples of such fillers include powdery or plate-like inorganic compounds such as silica, silica-alumina, alumina, titanium dioxide, diatomaceous earth, clay, kaolin, glass, mica, gypsum, red iron oxide, and zinc oxide, and polypara. Phenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, condensate of diaminodiphenyl ether and terephthalic acid (and / or isophthalic acid), condensate of para (meth) aminobenzoic acid, etc. Wholly aromatic polyamides, wholly aromatic polyamideimides such as condensation products of diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride, wholly aromatic polyesters, wholly aromatic polyimides, polybenzimidazole, polyimidazov Heterocyclic ring-containing compounds such as Nantororin powdery formed from polytetrafluoroethylene, plate, fabricated articles, such as fibrous or cloth-like material, and the like.

Two or more kinds of these fillers can be mixed and used. Further, these fillers may be treated with a silane coupling agent or a titanium coupling agent before use. The average particle size of such powdery filler is usually in the range of 0.1 to 200 μm, preferably 1 to 100 μm.

Such a powdery filler is generally used in an amount of 200 parts by weight or less, preferably 100 parts by weight of the total amount of the aromatic polyamide and polyphenylene sulfide, that is, generally 100 parts by weight of the resin component in the composition. It is used in amounts of up to 100 parts by weight, particularly preferably in amounts of 0.5 to 50 parts by weight.

A heat resistant resin may be added to the resin composition of the present invention within a range that does not impair the characteristics of the composition of the present invention. Examples of such heat resistant resins include PPS (polyphenylene sulfide), PES (polyether sulfone), PEI (polyetherimide) and LCP (liquid crystal polymer), and modified products of these resins. Can be mentioned. The content of such a heat resistant resin is usually less than 50% by weight, preferably 0 to 40% by weight.

The kneading method for producing the aromatic polyamide resin composition of the present invention is not particularly limited. For example, the pelletized aromatic polyamide (a) and the polyphenylene ether (b) are further added, respectively, if desired. Cylinder temperature 30 after dry blending with other ingredients in advance.
A method of melt-kneading with an extruder heated to 0 to 360 ° C.,
A method in which the polyphenylene ether (b) and other optional components are added in a molten state in the preceding stage of the extruder, and the pelletized aromatic polyamide (a) is added from a hopper provided in the middle of the cylinder, and the mixture is further kneaded. A method in which the aromatic polyamide (a) is in a molten state before the extruder and the polyphenylene ether (b) and other components optionally added are added from a hopper provided in the middle of the cylinder and further kneaded You can As the kneading device, a kneader or the like can be used in addition to the extruder.

The aromatic polyamide resin composition of the present invention as described above can be molded by a usual melt molding method such as compression molding method, injection molding method or extrusion molding method.

Since the aromatic polyamide resin composition obtained as described above contains the aromatic polyamide (a) and the polyphenylene ether (b), the aromatic polyamide resin composition retains various characteristics of the aromatic polyamide and is more heat resistant. , Electrical characteristics,
It has excellent moldability, and since an aromatic polyamide having a specific degree of polymerization and a terminal amino group content is used as the aromatic polyamide, the weld strength of an injection-molded product of this resin composition is excellent.

The aromatic polyamide resin composition of the present invention comprises
Molded by a normal molding method, and widely used in fields where conventional surface smoothness and precision moldability are required, in addition to conventional applications of aromatic polyamide. You can

Examples of the uses of the resin composition of the present invention include automobile mechanism structural parts such as engine mount brackets and cylinder head covers; power tools, OA equipment, cameras, pumps and other housings, chassis, precision equipment parts. Automotive components such as instrumental panels, radiator grills, cluster grills, console boxes, garnishes, foil covers, column covers, fenders, bonnets, trunks; electronic components such as connectors, coil bobbins, switch cases; covers; bottles Sheet, cast film, biaxially stretched film,
Films such as multilayer films; foams such as extruded foams and injection foams can be mentioned.

[0087]

Since the aromatic polyamide resin composition of the present invention contains a specific aromatic polyamide and a polyphenylene ether resin, it is excellent in thermal characteristics such as heat distortion temperature and high temperature rigidity at the same time. The injection molded article obtained from this resin composition has excellent weld strength.

[0088]

The present invention will now be described in more detail with reference to the examples of the present invention, but the present invention should not be construed in a limited manner by these examples.

[0089]

[Production Example 1] 286.1 g of 1,6-diaminohexane (2.4
6 mol) and 205.6 g (1.24 mol) of terephthalic acid
And adipic acid 148.0 g (1.01 mol), and 3.43g benzoic acid (2.81 × 10 ^-2 mol) as a molecular weight modifier, a catalyst sodium hypophosphite 0.48g
(4.50 × 10 ⁻³ mol) and 62 ml of ion-exchanged water were charged into a reactor having a capacity of 1 liter, and after purging with nitrogen, 2
The reaction was carried out at 50 ° C. and 35 kg / cm ² for 1 hour. The molar ratio (charged amount) of terephthalic acid and adipic acid is 55:
45.

After 1 hour, the reaction product formed in the reactor was connected to the reactor and the pressure was adjusted to about 10%.
Kg / cm ^{2 It} was pulled out to the receiver set low and the intrinsic viscosity (30
560 g of polyamide precursor having [η] of 0.15 dl / g was obtained.

Then, the polyamide precursor is dried,
The obtained dried product was supplied to a twin-screw extruder and melt-polymerized at a cylinder temperature of 330 ° C. to obtain an aromatic polyamide. The physical properties of this aromatic polyamide are as follows.

Intrinsic viscosity [η] = 0.76 dl / g Terminal amino group content (titration value with paratoluenesulfonic acid in meta-cresol solution) = 0.183 mmol / g
Polymer Melting point = 312 ° C. Glass transition point = 80 ° C.

[0093]

[Production Examples 2-5] Table 1 shows the amount of 1,6-diaminohexane charged.
An aromatic polyamide was obtained in the same manner as in Production Example 1 except that the amount was changed to that shown in. Table 1 also shows the physical properties of these aromatic polyamides.

[0094]

[Table 1]

[0095]

[Production Example 6] 100 parts by weight of 2,6-dimethyl-1,4-polyphenylene ether [intrinsic viscosity: IV = 0.5 dl / g (measured in chloroform at 30 ° C)], 1 part by weight of maleic anhydride and 2 parts by weight A solution of 0.05 part by weight of 5,5-dimethyl-2,5-di (t-butylperoxy) hexin-3 (Perhexin 25B manufactured by NOF CORPORATION) and 0.6 part by weight of acetone was added, After mixing, twin-screw extruder (PCM-made by Ikegai Tekko KK
45) was melt-kneaded under the following conditions to obtain maleic anhydride-modified polyphenylene ether.

Cylinder set temperature 350 ° C., screw rotation speed 250 rpm, feed speed 250 g / min.

[0097]

Example 1 and Comparative Examples 1 to 6 The aromatic polyamides obtained in Production Examples 1 to 5, the maleic anhydride-modified polyphenylene ether obtained in Production Example 6 and the heat-resistant stabilizer were mixed in the weight ratios shown in Table 2. After dry-blending, a twin-screw extruder (BT-30 manufactured by Plastic Engineering Laboratory Co., Ltd.) was melt-kneaded under the following conditions to obtain an aromatic polyamide resin composition.

Cylinder set temperature 320 ° C. Screw rotation speed 150 rpm Feed speed 100 g / min.

[0099]

[Table 2]

The pellets of the aromatic polyamide resin composition thus obtained were injected into an injection molding machine [TOSHIBA MACHINE, IS
-55 EPN] was used to injection-mold a test piece under the following conditions.

[Injection molding conditions] Cylinder temperature: 320
℃ Injection pressure: Primary / Secondary = 1000/800 kg / cm ² Mold temperature: 70 ° C.

The test pieces were evaluated for bending property, Izod impact strength, fluidity and weld strength according to the following methods.

[Evaluation Method] Bending Property: Bending elastic modulus was determined by performing a bending test using a test piece having a size of 3.2 mm × 12.7 mm × 127 mm according to ASTM D790.

Izod impact strength (notched): ASTM
Compliant with D256. Fluidity: The spiral flow value was evaluated.

Weld strength: ASTM with a weld at the center of the test piece using a mold with gates at two locations
D638 No. 1 test piece (thickness 3 mm) was prepared. For this test piece, chuck distance = 115 mm, pulling speed 5 mm
The tensile strength was measured under the condition of / min. For comparison, one of the two gates of the same mold was closed to prepare a weld-free test piece, and the tensile strength was measured under the same conditions.

[0106]

[Table 3]

[Brief description of drawings]

FIG. 1 is a view schematically showing a test piece used for measuring weld strength.

Claims (3)

[Claims] 1. (a) 50 to 10 terephthalic acid component units
0 mol% and 0 to 50 mol% of aromatic dicarboxylic acid component units other than terephthalic acid and / or 4 to 2 carbon atoms
A dicarboxylic acid component unit consisting of 0 to 50 mol% of an aliphatic dicarboxylic acid component unit of 0, and a repeating unit consisting of a diamine component unit consisting of an aliphatic diamine component unit and / or an alicyclic diamine component unit, Terminal amino group content is 0.1 mmol /
An aromatic polyamide resin composition comprising an aromatic polyamide having an intrinsic viscosity of at least g and having an intrinsic viscosity of 0.5 to 0.9 dl / g measured in concentrated sulfuric acid at 30 ° C., and (b) a polyphenylene ether. 2. The aromatic polyamide resin composition comprises an aromatic polyamide (a) and a polyphenylene ether (b).
The aromatic polyamide resin composition according to claim 1, wherein and are contained in a weight ratio of 1:99 to 99: 1. 3. The aromatic polyamide resin composition comprises an aromatic polyamide (a) and a polyphenylene ether (b).
The aromatic polyamide resin composition according to claim 1 or 2, which contains 0.5 to 200 parts by weight of the fibrous filler with respect to 100 parts by weight as the total amount.