JP3423395B2 - Aromatic polyamide composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD OF THE INVENTION The present invention relates to an aromatic polyamide composition, and more specifically, to a molded article having excellent physical and chemical characteristics such as heat resistance, mechanical characteristics, water resistance and chemical resistance, and particularly excellent heat resistance. It relates to an aromatic polyamide composition which can be obtained.

[0002]

BACKGROUND OF THE INVENTION Generally, polycaprolactam (6-
Nylon), polyhexamethylene adipamide (6,6-nylon), polyhexamethylene azelite (6,9-nylon), polyhexamethylene sebasamide (6,10-nylon), polyhexamethylene dodecanoamide Aliphatic polyamides such as (6,12-nylon) and polylauric lactam (12-nylon) have higher strength, rigidity, heat resistance and abrasion resistance than thermoplastic resins such as polyolefins. It has excellent properties and is widely used as an engineering plastic for various molding applications.

However, the above-mentioned aliphatic polyamides have a melting point, a glass transition point, and
Mechanical properties such as heat resistance such as heat deformation temperature, rigidity, tensile strength, bending strength, limit PV value, wear resistance and physical properties such as water resistance, boiling water resistance, salt water resistance, saturated water absorption, chemical resistance, etc. Its chemical properties were not sufficient and its use was limited.

Examples of engineering plastics excellent in heat resistance, mechanical properties and physical / chemical properties include polytetrafluoroethylene (trade name: Teflon), polyparaphenylene terephthalamide (trade name: Kevlar), Examples thereof include polyimide (trade name: Kapton) made of a condensate of 4,4′-diaminophenyl ether and pyromellitic anhydride, polyphenylene sulfide, polyacetal and the like. Among these engineering plastics, polytetrafluoroethylene,
Polyparaphenylene terephthalamide and the above polyamide resin are materials excellent in heat resistance, mechanical properties and physical and chemical properties, but have a problem that melt molding cannot be performed. In addition, polyphenylene sulfide, polyacetal, etc. have melting points, glass transition points,
There is a problem in that mechanical properties such as heat resistance such as heat distortion temperature, impact strength, and wear resistance are poor.

On the other hand, as a polyamide composition having improved moldability and heat resistance, for example, molding polyamide resins disclosed in JP-A-61-188,457 and JP-A-61-188,458 have been developed. There is. The former is a polyamide composition in which 4,6-nylon contains glass fiber and a lubricant, and the latter is 4,6-nylon containing a lubricant such as bisamides, metal salts, polyethylene glycol, and aliphatic carboxylic acid. These polyamide compositions are contained, and these polyamide compositions have high rigidity and high heat distortion temperature in a high temperature atmosphere, and have excellent fluidity during melting and good moldability.

However, with the recent remarkable diversification of uses of engineering plastics, heat resistance,
In the situation where engineering plastics with high performance in terms of mechanical properties and physicochemical properties are sought, none of the above-mentioned materials has been confirmed to be satisfactory, and further, heat resistance and mechanical properties There is still room for improvement in terms of physical and chemical properties, particularly heat resistance.

In view of these points, the applicant of the present invention has determined that an aromatic dicarboxylic acid component unit (a) containing a terephthalic acid component unit as a main component unit and an aliphatic diamine component unit (b). A heat-resistant polyamide composed is proposed. Although this heat-resistant polyamide is extremely excellent in heat resistance, since the molding temperature is high, the temperature drop rate (cooling rate) of the injection-molded melt during molding by injection molding etc. It is remarkably large in comparison, and thus there is a problem that the crystal growth rate is slow and the crystallinity of the obtained compact is low. If the crystallinity of the obtained molded body becomes low, there arises a problem that the heat resistance of the molded body becomes insufficient.

In order to solve such a problem, it is considered to add talc, which is usually used as a nucleating agent, to the above heat-resistant polyamide, but talc is not sufficient for promoting the crystallization rate. Therefore, the appearance of a more excellent nucleating agent for heat-resistant polyamide has been strongly desired.

The inventors of the present invention searched for a nucleating agent for heat-resistant polyamide as described above, and found that a specific liquid crystal polymer had an excellent effect of promoting crystallization rate, and completed the present invention. I arrived.

In addition to crystalline polyamide such as nylon,
By blending a polyester formed from 6-hydroxy-2-naphthalene acid and p-hydroxybenzoic acid, the viscosity of the crystalline polyamide is lowered,
Polymer, 1985, Vol. 26, pp. 1325 to 1330, the crystalline polyamide used in this document has a low melting point of 170 to 220 ° C, and in this document, crystalline polyamide is blended with polyester. There is no recognition that this promotes crystallization of the polyamide. The heat-resistant polyamide used in the present invention has a melting point of 300 to 330 ° C.

[0011]

SUMMARY OF THE INVENTION The present invention is intended to solve the problems associated with the prior art as described above, and has a specific heat resistance having a remarkably high melting point as compared with ordinary polyamides such as nylon. It is possible to obtain a molded product composed of a polyamide and a specific liquid crystal polymer, which has a high crystallization rate and therefore does not deform due to warpage or shrinkage during molding, has excellent heat resistance rigidity, and has excellent mechanical strength. The object is to provide such an aromatic polyamide composition.

[0012]

SUMMARY OF THE INVENTION The aromatic polyamide composition according to the present invention comprises a structural unit derived from [A] (i) dicarboxylic acid and (ii) diamine, and (i) a structural unit derived from dicarboxylic acid. Is a constitutional unit derived from terephthalic acid in an amount of 30 to 100 mol% (
However, 30 to 90 mol% is excluded. ) , The structural unit derived from an aromatic dicarboxylic acid other than terephthalic acid and / or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms is 0 to 70 mol% (however, 10 to 70 mol% is excluded).
Ku. ), And the structural unit derived from (ii) diamine has 4 carbon atoms.
To 18 linear alkylenediamines and / or aromatic polyamides composed of structural units derived from alkylenediamines having 4 to 18 carbon atoms having a side chain alkyl group; 100 parts by weight, and [B] below (c) The liquid crystal polymer shown is 0.001 part by weight or more and less than 1 part by weight, preferably 0.01 part by weight or more and less than 1 part by weight.

[0013]

[0014]

[0015]

[0016]

[0017]

(C): Liquid crystal polymer obtained by condensing the following compounds (h), (i) and (j):

[0019]

[Chemical 6]

(In the formulas (7), (8) and (9), R ¹ , R ⁵ and R ⁶ are a hydrogen atom, a benzoyl group or a lower alkanoyl group, and R ² , R ³ and R ⁴ are A hydrogen atom, a phenyl group, a benzyl group or a lower alkyl group, represented by the formula
The carbonyl groups of the dicarbonyl compound represented by (8) are in the meta position or the para position, the oxy groups of the dioxy compound represented by the formula (9) are in the meta position or the para position, and X is -O- , -CO -, - S- or -SO ₂ -
, M is 0 or 1, n is 0 or 1, the molar ratio of (i) :( j) is 15:10 to 10:15, and the molar ratio of (h) :( i) is The ratio is 1: 100 to 100: 1. ).

[0021]

DETAILED DESCRIPTION OF THE INVENTION The aromatic polyamide composition according to the present invention is formed from a specific [A] aromatic polyamide and a specific [B] liquid crystal polymer.

First, each component forming the aromatic polyamide composition according to the present invention will be described below. [A] Aromatic Polyamide The [A] aromatic polyamide used in the present invention comprises a structural unit derived from (i) a dicarboxylic acid containing terephthalic acid as an essential component and (ii) a diamine.

The aromatic polyamide [A] is formed.
(i) Dicarboxylic acid contains (ia) terephthalic acid as an essential component, but may contain (ib) aromatic dicarboxylic acid and / or (ic) aliphatic dicarboxylic acid other than terephthalic acid .

Examples of the aromatic dicarboxylic acid other than terephthalic acid (ib) include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid, and combinations thereof.

Of these, isophthalic acid is preferred. Specific examples of the (ic) aliphatic dicarboxylic acid include aliphatic dicarboxylic acids having an alkylene group having 2 to 20 carbon atoms, preferably 4 to 12 carbon atoms, and examples thereof include succinic acid, adipic acid, azelaic acid and sebacine. Acids, and combinations thereof.

Of these, adipic acid and sebacic acid are preferred. Further, as described above, (i) a diamine that forms an aromatic polyamide together with a dicarboxylic acid is a diamine having 4 to 18 carbon atoms having a linear alkylenediamine having 4 to 18 carbon atoms and / or a side chain alkyl group. It consists of alkylenediamine.

Specific examples of such (ii-a) straight chain alkylenediamine having 4 to 18 carbon atoms include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10
-Diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, and combinations thereof.

Of these, 1,6-diaminohexane, 1,
8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane are preferable, and 1,6-diaminohexane is particularly preferable.

Specific examples of the alkylenediamine having a side chain alkyl group (ii-b) include 1-butyl-1,2-diamino-ethane, 1,1-dimethyl-1,4-diamino-butane, 1-
Ethyl-1,4-diamino-butane, 1,2-dimethyl-1,4-diamino-butane, 1,3-dimethyl-1,4-diamino-butane, 1,4
-Dimethyl-1,4-diamino-butane, 2,3-dimethyl-1,4-diamino-butane, 2-methyl-1,5-diaminopentane, 2,5-
Dimethyl-1,6-diamino-hexane, 2,4-dimethyl-1,6-
Diamino-hexane, 3,3-dimethyl-1,6-diamino-hexane, 2,2-dimethyl-1,6-diamino-hexane, 2,2,4-trimethyl-1,6-diamino-hexane, 2, 4,4-trimethyl-
1,6-diamino-hexane, 2,4-diethyl-1,6-diamino-
Hexane, 2,3-dimethyl-1,7-diamino-heptane, 2,4-
Dimethyl-1,7-diamino-heptane, 2,5-dimethyl-1,7-
Diamino-heptane, 2,2-dimethyl-1,7-diamino-heptane, 2-methyl-4-ethyl-1,7-diamino-heptane, 2-
Ethyl-4-methyl-1,7-diamino-heptane, 2,2,5,5-tetramethyl-1,7-diamino-heptane, 3-isopropyl-
1,7-diamino-heptane, 3-isooctyl-1,7-diamino
-Heptane, 1,3-dimethyl-1,8-diamino-octane, 1,4
-Dimethyl-1,8-diamino-octane, 2,4-dimethyl-1,8-
Diamino-octane, 3,4-dimethyl-1,8-diamino-octane, 4,5-dimethyl-1,8-diamino-octane, 2,2-dimethyl-1,8-diamino-octane, 3,3- Dimethyl-1,8-diamino-octane, 4,4-dimethyl-1,8-diamino-octane, 3,3,5-trimethyl-1,8-diamino-octane, 2,4-diethyl-1,8- Diamino-octane, 5-methyl-1,9-diamino-nonane, and combinations thereof and the like.

Of these, the number of carbon atoms in the main chain is 4
Alkylenediamines having 10 to 10 and 1 to 2 side chain alkyl groups having 1 to 2 carbon atoms are preferable, and especially 2-
Methyl-1,5-diaminopentane is preferred.

Unless otherwise specified, the number of carbon atoms of the alkylenediamine having a side chain alkyl group (ii-b) means the number of carbon atoms of the main chain alkylene group and the number of carbon atoms of the side chain alkyl group. And the total.

In the aromatic polyamide [A] derived from (i) dicarboxylic acid and (ii) diamine as described above, specifically, when (i) dicarboxylic acid is terephthalic acid,
The structural unit (a) derived from (ia) terephthalic acid and (ii) diamine is represented by the following formula [Ia].

[0033]

[Chemical 7]

In the formula, R ¹ is a group derived from the above diamine (ii) and is an alkylene group having 4 to 18 carbon atoms which may have a side chain alkyl group. Also (ib)
Structural units derived from isophthalic acid as an aromatic dicarboxylic acid other than terephthalic acid, and (ii) diamine (b)
Is represented by the following formula [Ib].

[0035]

[Chemical 8]

[0036] In the formula, R ¹ is the same as R ¹ in the above formula [Ia]. The structural unit (c) derived from (ic) an aliphatic dicarboxylic acid and (ii) a diamine is represented by the following formula [Ic].

[0037]

[Chemical 9]

In the formula, n is usually 2 to 20, preferably 4 to 1.
Is 2, R ¹ is the same as R ¹ in the above formula [Ia]. Furthermore, when (ii) diamine is (ii-a) linear alkylenediamine, for example, (ii-a) a structural unit derived from 1,6-hexadiamine as a linear alkylenediamine and (i) dicarboxylic acid. Is represented by the following formula [II-a].

[0039]

[Chemical 10]

In the formula [II-a], R ² is a divalent hydrocarbon group such as p-phenylene group, m-phenylene group or alkylene group derived from the above (i) dicarboxylic acid. When (ii) diamine is (ii-b) an alkylenediamine having a side chain alkyl group, for example, (ii-b) 2-methyl-1,5-diaminopentane as an alkylenediamine having a side chain alkyl group, The structural unit derived from (i) dicarboxylic acid is represented by the following formula [II-b].

[0041]

[Chemical 11]

In the formula [II-b], R ² is R in the above formula [II-a].
Same as ² . The aromatic polyamide [A] used in the present invention is composed of structural units derived from (i) dicarboxylic acid and (ii) diamine as described above. When the amount is 100 mol%, the structural unit (a) derived from terephthalic acid is 30
~ 100 mol% (excluding 30 to 90 mol%)
Preferably 45 to 100 mol% (however, 45 to 90 mol%
Excluding le%. ) More preferably 70-100 mol%
(However, 70 to 90 mol% is excluded.) . Further, the structural unit (b) derived from an aromatic dicarboxylic acid other than terephthalic acid and / or the structural unit (c) derived from an aliphatic dicarboxylic acid is 0 to 70 mol% (
However, 10 to 70 mol% is excluded. ) Preferably 0-55
Mol% (however, 10-55 mol% is excluded.) More preferably 0-30 mol% (however, 10-30 mol% is
except. ) Content.

A polyamide having a content of the structural unit (c) derived from an aliphatic dicarboxylic acid exceeding 70 mol% has a high water absorption rate, and a molded article obtained from such a polyamide has a large dimensional change due to water absorption. Sometimes.

The aromatic polyamide [A] used in the present invention comprises a structural unit derived from a tribasic or higher polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid.
It may be contained in a small amount, usually 5 mol% or less.

Further, the aromatic polyamide [A] used in the present invention includes an aromatic polyamide containing a structural unit (a) derived from terephthalic acid as a dicarboxylic acid as a main structural unit, and a dicarboxylic acid. The mixture may be a mixture with an aromatic polyamide having the structural unit (b) derived from isophthalic acid as the main structural unit.

The aromatic polyamide [A] used in the present invention has an intrinsic viscosity [η] measured in concentrated sulfuric acid at 30 ° C. of 0.5 to 3.0 dl / g, preferably 0.5 to 3.0 dl / g.
2.8 dl / g Especially preferably, it is desirable that it is 0.6-2.5 dl / g.

The aromatic polyamide [A] having a specific structure as described above is excellent in moldability and heat resistance, and has a low water absorption. Further, the glass transition temperature (T
g) is higher than the glass transition temperature of the conventionally used aliphatic polyamide and is usually 80 ° C. or higher, preferably 9
It is 0 to 150 ° C. Since the amorphous part has a high glass transition temperature, a molded article formed by including the aromatic polyamide [A] is unlikely to be in a molten state even when exposed to a high temperature, and its dimensions change. Hateful.

The aromatic polyamide [A] used in the present invention can be produced by polycondensing the above-mentioned (i) dicarboxylic acid and (ii) diamine.
Specifically, first, the amount of terephthalic acid (i-
dicarboxylic acid (i) containing a) as an essential component and diamine
(ii) and, in an aqueous medium, in the presence of a catalyst such as sodium hypophosphite, to produce a polyamide precursor by heating under pressure, then by melt-kneading this polyamide precursor may be produced it can. When producing the polyamide precursor, a molecular weight modifier such as benzoic acid may be added.

[B] Liquid Crystal Polymer In the present invention, the following liquid crystal polymer (C) is used as the liquid crystal polymer.

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

Liquid Crystal Polymer (C) The liquid crystal polymer (C) used in the present invention is the following compound
It is obtained by condensing (h), (i) and (j).

[0071]

[Chemical 17]

(In the formulas (7), (8) and (9), R ¹ , R ⁵ and R ⁶ are a hydrogen atom, a benzoyl group or a lower alkanoyl group, and R ² , R ³ and R ⁴ are A hydrogen atom, a phenyl group, a benzyl group or a lower alkyl group, represented by the formula
The carbonyl groups of the dicarbonyl compound represented by (8) are in the meta position or the para position, the oxy groups of the dioxy compound represented by the formula (9) are in the meta position or the para position, and X is -O- , -CO -, - S- or -SO ₂ -
, M is 0 or 1, n is 0 or 1, the molar ratio of (i) :( j) is 15:10 to 10:15, and the molar ratio of (h) :( i) is The ratio is 1: 100 to 100: 1. The liquid crystal polymer (C) obtained by condensing the compounds (h), (i) and (j) as described above usually has a glass transition temperature (Tg) detected by a differential scanning calorimeter (DSC). No, DSC
Melting point (Tm) measured by
C., preferably 250 to 350.degree.

As the liquid crystal polymer (c), a wholly aromatic polyester is specifically used, and the wholly aromatic polyester is described in detail, for example, in Japanese Examined Patent Publication No. 47-47870.

Among such liquid crystal polymers (C), particularly polyester compounds (C) composed of the following constitutional units
-1), (C-2), and (C-3) are preferably used.

[0075]

[Chemical 18]

Further, in the present invention, in addition to the above-mentioned liquid crystal polymer, liquid crystal wholly aromatic polyesters shown in the following Table 1 can be used as the liquid crystal polymer.

[0077]

[Table 1]

Among the compounds shown in Table 1 above, the wholly aromatic polyester shown by symbol 4 is preferably used. The liquid crystal polymer [B] used in the present invention as described above preferably has an intrinsic viscosity [η] of 0.1 to 5 dl / g measured at 60 ° C. in pentafluorophenol.

In the present invention, as the liquid crystal polymer [B], among the above, the liquid crystal polymer represented by (C-3) is particularly preferably used. Aromatic Polyamide Composition The aromatic polyamide composition according to the present invention comprises 0.001 part by weight or more of the liquid crystal polymer [B] with respect to 100 parts by weight of the aromatic polyamide [A] as described above. It is contained in an amount of less than 1 part by weight, preferably 0.01 or more and less than 1 part by weight, more preferably 0.1 or more and less than 1 part by weight.

Thus, the aromatic polyamide composition according to the present invention formed from the aromatic polyamide [A] and a specific amount of the liquid crystal polymer [B] with respect to the aromatic polyamide [A] has a crystallization rate. It has excellent heat resistance, especially heat resistance, and mechanical strength.

When the amount of the liquid crystal polymer [B] is less than 0.001 part by weight based on 100 parts by weight of the polyamide [A], the liquid crystal polymer exhibits a sufficient nucleating agent effect on the polyamide. In some cases, the heat resistance, especially the heat resistance of the aromatic polyamide composition may not be sufficiently improved.

In the present invention, the crystallization rate of the aromatic polyamide composition is such that the composition is once heated at 350 ° C. for 5 minutes to melt the polyamide, and then immersed in a bath at 120 ° C. for rapid cooling. It is determined by measuring its crystallinity by an X-ray measuring method.

The aromatic polyamide composition according to the present invention is
It is composed of the aromatic polyamide [A] and the liquid crystal polymer [B] as described above, and together with these [A] and [B],
A crystal nucleating agent [C] other than the liquid crystal polymer [B] may be contained if necessary.

Examples of the [C] crystal nucleating agent include powdery, granular, plate-like, and fibrous inorganic or organic compounds, and specifically, silica, alumina, silica-alumina, talc, diatomaceous earth. Powdery, plate-like inorganic compounds such as clay, kaolin, quartz, glass, mica, graphite, molybdenum disulfide, gypsum, red iron oxide, titanium dioxide, zinc oxide, aluminum, copper, stainless steel, glass fiber, carbon fiber, boron Fibers, ceramic fibers, asbestos fibers, fibrous inorganic compounds such as stainless steel fibers, polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenyleneisophthalamide, polymetaphenyleneisophthalamide, diaminodiphenyl ether Condensate with terephthalic acid (isophthalic acid), A wholly aromatic polyamide such as a condensate of la (meth) aminobenzoic acid, a wholly aromatic polyamideimide such as a condensate of diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride, a wholly aromatic polyimide, poly Examples thereof include heterocycle-containing compounds such as benzimidazole and polyimidazophenanthroline, and powdery, plate-like, and fibrous organic compounds such as polytetrafluoroethylene.

Two or more of these compounds may be used in combination, or these compounds may be treated with a silane coupling agent or a titanium coupling agent before use. Among the above crystal nucleating agents [C], the powdery crystal nucleating agent has an average particle size of 0.1 to 200 μm, preferably 1
It is desirable that the thickness is 100 μm. It is preferable that the aromatic polyamide composition contains the powdery crystal nucleating agent having such an average particle diameter because the abrasion resistance of the aromatic polyamide composition is remarkably improved.

As the powdery crystal nucleating agent [C], powdery silica, alumina, silica-alumina, titanium dioxide, graphite, molybdenum disulfide, polytetrafluoroethylene, etc. are preferably used among the above, and particularly powdery. Graphite, molybdenum disulfide, polytetrafluoroethylene and the like are preferably used.

From the aromatic polyamide composition containing such a powdery crystal nucleating agent, a molded article having improved wear resistance such as dynamic friction coefficient, taper wear, and limit PV value is formed, which is preferable.

Among the above crystal nucleating agents, the organic fibers include wholly aromatic polyamide fibers such as polyparaphenylene terephthalamide fibers, polymetaphenylene terephthalamide fibers, polyparaphenylene resophthalamide fibers, and polymetaphenylene. Renisophthalamide fibers, fibers obtained from a condensate of diaminodiphenyl ether and terephthalic acid (or isophthalic acid), etc. are preferably used, and as the inorganic fibers, glass fibers, carbon fibers,
Boron fiber or the like is preferably used.

These organic or inorganic fibrous crystal nucleating agents have an average fiber length of 0.1 to 20 mm, preferably 1 to 1
It is preferably 0 mm. When the fibrous crystal nucleating agent having such an average length is contained, the aromatic polyamide composition has improved moldability, and the molded body has heat resistance such as heat distortion temperature, tensile strength, and bending strength. It is preferable because mechanical properties such as are improved. Specifically, a molded article of an aromatic polyamide composition containing organic fibers has improved mechanical properties such as tensile strength and Izod impact strength, heat resistance such as heat distortion temperature, and the like. The molded article of the composition has tensile strength, bending strength,
Mechanical properties such as flexural modulus, heat resistance such as heat deformation temperature, and physical and chemical properties such as water resistance are improved, which is preferable.

The aromatic polyamide composition according to the present invention is
The crystal nucleating agent [C] as described above is usually added to 0.001 to 1 part by weight, preferably 0.01 to 1 part by weight, and particularly preferably 0.1 to 100 parts by weight of the aromatic polyamide [A].
It may be contained in an amount of 1 to 1 part by weight.

Further, the aromatic polyamide composition according to the present invention contains other thermoplastic resin, an organic or inorganic filler, an antioxidant, an infrared absorber, a photoprotective agent, a heat stabilizer, a phosphorous acid, if necessary. It may contain a salt stabilizer, a peroxide decomposer, a basic auxiliary agent, a nucleating agent, a plasticizer, a lubricant, an antistatic agent, a flame retardant, a pigment, a dye and the like.

As other thermoplastic resins, aromatic polyamides other than the aromatic polyamide [A] used in the present invention, aliphatic polyamides, (meth) acrylic resins, polyolefin resins, polyolefin elastomers, polyphenylene oxide, polyphenylene sulfone. , Polyester, polystyrene, ABS resin, polycarbonate and the like. The aromatic polyamide composition according to the present invention contains the above-mentioned other thermoplastic resin together with the aromatic polyamide [A], so that the aromatic polyamide [A] is obtained.
And other thermoplastic resins can be formed into a polymer alloy.

As the above-mentioned filler, the same organic and inorganic compounds as the above-mentioned [C] crystal nucleating agent can be used, but the shape thereof is not limited to the above-mentioned powder form, granular form and fibrous form. It may be in the form of a strand, a cloth, a mat or the like without any use, and may be a secondary processed product of these compounds.

The aromatic polyamide composition according to the present invention is
Such a filler may be contained in an amount of usually 200 parts by weight or less, preferably 100 parts by weight, particularly preferably 0.5 to 50 parts by weight, based on 100 parts by weight of the aromatic polyamide [A]. Especially when the filler is fibrous, it is usually 5 to 100 parts by weight of the aromatic polyamide [A].
It may be contained in an amount of 180 parts by weight or less, preferably 5 to 100 parts by weight, particularly preferably 5 to 150 parts by weight.

The aromatic polyamide composition according to the present invention is
It can be prepared by a conventionally known method of preparing a resin composition, for example, a method of blending a filler while maintaining the above components in a molten state. At this time, an extruder, a kneader or the like can be used.

The aromatic polyamide composition according to the present invention is
It can be molded by a usual molding method (melt molding method) such as a compression molding method, an injection molding method or an extrusion molding method.

The aromatic polyamide composition according to the present invention is
Used for various purposes such as engineering plastics.

[0098]

EFFECT OF THE INVENTION The aromatic polyamide composition of the present invention has a high crystallization rate and, therefore, a molded article having excellent heat resistance, particularly heat resistance and mechanical properties, without causing deformation due to warpage or shrinkage. Obtainable.

[0099]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

[0100]

[Production of aromatic polyamide PA-1] 1,6-diaminohexane 291 g (2.5 mol), dimethyl terephthalate 3
40 g (1.75 mol), dimethyl isophthalate 146
g (0.75 mol) and 600 ml of ion-exchanged water were charged into a 2 liter reactor, refluxed at 100 ° C. for 4 hours under N ₂ atmosphere, and then the distillate was distilled off at 140 ° C. over 4 hours. Then, the distillate was distilled off while the temperature was raised from 140 ° C to 350 ° C over 6 hours, and the intrinsic viscosity [η] was 0.7.
590 g of 0 dl / g (concentrated sulfuric acid, 30 ° C.) polyamide was obtained. Then, solid phase polymerization was carried out for 10 hours at 300 ° C. and 1 mmHg to obtain an intrinsic viscosity [η] of 1.5 dl / g (concentrated sulfuric acid, 30
℃) was obtained.

The aromatic polyamide obtained has a melting point of 33.
0 ° C, terephthalic acid constituent unit content is 71 mol%
Met.

[0102]

[Reference Examples 1 to 3] Aromatic polyamide PA-1 produced as described above and 100 parts by weight of this PA-1
The amount of liquid crystal polymer represented by the following structure shown in Table 2 was melt-mixed at 350 ° C. using a uniaxial extruder to obtain pellets of an aromatic polyamide composition. Table 2 shows the results of evaluations of the obtained aromatic polyamide composition as described below.

[0103]

[Chemical 19]

(I) The crystallization rate of the obtained aromatic polyamide composition was evaluated as follows. About 20 mg of a sample (aromatic polyamide composition) was added to D
Put in a SC liquid aluminum pan (diameter about 5 mm), 3
After being placed in a wood metal bath set at 50 ° C. and left for 5 minutes, it was quickly transferred to a separately prepared wood metal bath set at 120 ° C. and left for 20 seconds. Immediately after this, the crystallinity of the sample was measured at room temperature. The larger the crystallinity at this time, the faster the crystallization rate. (ii) Further, the crystallinity of the injection-molded product of the aromatic polyamide composition was measured.

That is, the pellets of the aromatic polyamide composition were injection molded at 350 ° C. to obtain a test piece having a thickness of 1.6 mm, and the crystallinity of this test piece was measured. The crystallinity was measured by the X-ray transmission method by the PSPC method. (iii) Measurement of Izod impact strength (IZ) It was measured according to ASTM D256 (with notch).

[0106]

[Comparative Examples 1 and 2] In Reference Example 1, the liquid crystal polymer is shown in Table 2.
A composition was obtained in the same manner as in Reference Example 1 except that the composition was used in the amount shown in.

The crystallinity and IZ impact strength of the obtained composition were measured in the same manner as in Reference Example 1. The results are shown in Table 2.

[0108]

[Table 2]

[0109]

[Production of aromatic polyamide PA-2] 13,6-diaminohexane 139.3 g (1.20 mol), 2-methyl-1,5-diaminopentane 139.3 g (1.20 mol), terephthalic acid 365. 5 g (2.2 mol) and 0.55 g (5.2 × 10 ⁻³ mol) of sodium hypophosphite as a catalyst
And 64 ml of ion-exchanged water were charged into a 1-liter reactor, and after purging with nitrogen, the temperature was 1 at 250 ° C. and 35 kg / cm ^2.
Reacted for hours. 1,6-diaminohexane and 2-methyl-1,5
-The molar ratio with diaminopentane is 50:50.

After 1 hour, the reaction product formed in the reactor was connected to the reactor and the amount of the reaction product was about 10 kg / cm ^2.
By extracting into a receiver set to a low pressure, a polyamide precursor 561 having an intrinsic viscosity [η] of 0.15 dl / g
g was obtained.

The polyamide precursor was dried and then melt-polymerized at a cylinder temperature of 330 ° C. using a twin-screw extruder to obtain an aromatic polyamide. The diamine constitutional units of the obtained aromatic polyamide were 50 mol% of 1,6-diaminohexane constitutional units and 50 mol% of 2-methyl-1,5-diaminopentane constitutional units.

[0112]

In Example 4-6 Reference Example 1, the aromatic polyamide PA-1, except that instead of the aromatic polyamide PA-2 obtained as described above, aromatic polyamide in the same manner as in Reference Example 1 A composition was obtained.

With respect to the obtained aromatic polyamide composition, the crystallinity and IZ impact strength were measured in the same manner as in Reference Example 1. The results are shown in Table 3.

[0114]

Comparative Examples 3 to 4 In Example 5, the liquid crystal polymer is shown in Table 3.
A composition was obtained in the same manner as in Example 5, except that the amount was changed to that shown in.

With respect to the obtained composition, the crystallinity and IZ impact strength were measured in the same manner as in Example 5. The results are shown in Table 3.

[0116]

[Table 3]

Front page continuation (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 67/00-67/03 C08L 77/00-77/12

Claims (6)

(57) [Claims] 1. A constitutional unit derived from [A] (i) dicarboxylic acid and (ii) diamine, wherein the constitutional unit derived from (i) dicarboxylic acid is a constitutional unit derived from terephthalic acid. 30 to 100 mol% (for
However, 30 to 90 mol% is excluded. ) , The structural unit derived from an aromatic dicarboxylic acid other than terephthalic acid and / or an aliphatic dicarboxylic acid having 4 to 20 carbon atoms is 0 to 70 mol% (however, 10 to 70 mol% is excluded).
Ku. ), And the structural unit derived from (ii) diamine has 4 carbon atoms.
To 18 linear alkylenediamines and / or aromatic polyamides composed of structural units derived from alkylenediamines having 4 to 18 carbon atoms having a side chain alkyl group; 100 parts by weight, and [B] below (c) Aromatic polyamide composition characterized by comprising 0.001 part by weight or more and less than 1 part by weight of the liquid crystal polymer: (c): the following compounds (h), (i), (j) Liquid crystal polymer obtained by condensing); (In the formulas (7), (8) and (9), R ¹ , R ⁵ and R ⁶ are a hydrogen atom, a benzoyl group or a lower alkanoyl group;
² , R ³ and R ⁴ are a hydrogen atom, a phenyl group, a benzyl group or a lower alkyl group, and the carbonyl groups of the dicarbonyl compound represented by the formula (8) are in the meta position or the para position with each other; ), The oxy groups of the dioxy compound are in the meta position or the para position, and X is -O-, -CO-,-.
S- or -SO ₂ - and is, m is 0 or 1,
n is 0 or 1, the molar ratio of (i) :( j) is 15:10 to 10:15,
The molar ratio of (h) :( i) is 1: 100 to 100: 1. ). 2. The above [A] aromatic polyamide; [B] in an amount of 0.01 parts by weight or more and less than 1 part by weight with respect to 100 parts by weight .
The aromatic polyamide composition according to claim 1, comprising a liquid crystal polymer. 3. Forming the [A] aromatic polyamide.
(ii) In the diamine constitutional unit, the alkylenediamine having 4 to 18 carbon atoms and having a side chain alkyl group is 2-methyl-1,5-diaminopentane. Aromatic polyamide composition. 4. The above-mentioned [A] aromatic polyamide is formed.
(ii) In the diamine constitutional unit, a linear alkylenediamine having 4 to 18 carbon atoms is 1,6-
The aromatic polyamide composition according to claim 1 or 2, which is diaminohexane. 5. The liquid crystal polymer [B] has an intrinsic viscosity [η] measured in pentafluorophenol at 60 ° C. of 0.1 to 5 dl / g. The aromatic polyamide composition as described in 1. 6. A molded product comprising the aromatic polyamide composition according to claim 1.