JP2945723B2 - Aromatic polyamide resin composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to an aromatic polyamide resin composition, and more particularly to an aromatic polyamide resin composition having a high heat deformation temperature and excellent heat resistance.

Technical Background of the Invention Conventionally, various aromatic polyamide compositions have been proposed, and for example, JP-A-59-155,426 discloses
The next iteration component: And the molar ratio of each unit of A: B: C is about 60:20:20 to about 90:
A 5: 5 crystalline polyamide copolymer is described.

Further, the publication discloses that about 10 to about 60% of glass fiber, glass bead, mineral fiber, graphite fiber or a mixture thereof is blended with the above-mentioned polyamide copolyamer, and the resulting injection-molded composition is about 24%.
Polyamide copolymers having a heat deflection temperature from 0 ° C to about 305 ° C are described.

As described above, in the prior art, the filler such as glass fiber is generally used in an amount of about 10 to 60% by weight in the resin. That is, in the prior art, by using such a large amount of the filler, the properties such as the heat resistance inherent in the filler are directly utilized to improve the properties such as the heat resistance of the resin. I was doing it.

That is, in the prior art, no attempt has been made to improve the properties of the aromatic polyamide itself by changing the crystallinity of the aromatic polyamide. However, it has relied exclusively on the properties such as heat resistance of the fillers which are blended in a large amount into this polyamide.

Therefore, for example, when excellent smoothness of the resin surface is required together with an excellent heat distortion temperature, or in the case of precision molding or the like in which the above resin is used by blending a filler in a small amount, excellent heat denaturation is achieved. In order to obtain characteristics such as temperature, it still had to rely on the heat resistance of the resin itself.

By the way, JP-A-61-188,462 discloses that substantially
Polymerized by using 1,4-diaminobutane and adipic acid as monomers, a polyamide (nylon 46) resin having a molecular weight of at least 4,000 to 95 to 99,999% by weight, and having an average particle size of 5 μm or less and a decomposition temperature of 200 ° C. or more A polytetramethylene adipamide composition comprising 0.001 to 5% by weight of fine particles having an active site on the surface is described.

However, the technique described in JP-A-61-188,462 relates to an aliphatic polyamide,
There is no suggestion as to how to improve the physical properties such as the heat distortion temperature of the aromatic polyamide.

Object of the invention The present invention is to solve the problems associated with the prior art as described above, by mixing a specific amount of specific fine particles to an aromatic polyamide having a specific component unit, In particular, an object of the present invention is to provide an aromatic polyamide resin composition having excellent heat resistance such as heat distortion temperature.

SUMMARY OF THE INVENTION The aromatic polyamide resin composition according to the present invention comprises: [A] (a) a dicarboxylic acid component unit of 30 to 90 mol% of a terephthalic acid component unit and 10 to 70 mol% of an aliphatic dicarboxylic acid component unit; Or terephthalic acid component unit; 30 to 90 mol%, aromatic dicarboxylic acid component unit other than terephthalic acid component unit;
~ 30 mol%, and aliphatic dicarboxylic acid component unit; 10 ~ 7
(B) an aromatic polyamide in which the diamine component unit is an aliphatic alkylenediamine component unit and / or an alicyclic alkylenediamine component unit, and [B] talc, clay, kaolin, white carbon,
Wollastonite, potassium titanate, higher fatty acid metal salt,
It comprises at least one filler selected from organic metal phosphinates, graphite, carbon black, molybdenum disulfide, metal naphthenates, metal halides, organic phosphonic acid derivatives, and / or a high melting polymer powder. The fine particles [B] are contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the total of the polyamide [A] and the fine particles [B]. In addition to being excellent in heat resistance such as heat deformation temperature, it is also excellent in high temperature rigidity and the like.

DETAILED DESCRIPTION OF THE INVENTION As described below, the aromatic polyamide resin composition according to the present invention comprises an aromatic polyamide [A] and fine particles [B]. This will be specifically described.

Aromatic Polyamide [A] The aromatic polyamide [A] used in the present invention is composed of a dicarboxylic acid component unit (a) and an alkylenediamine component unit (b). a) is composed of an aromatic dicarboxylic acid component unit having a terephthalic acid component unit as a main component unit and an aliphatic dicarboxylic acid component unit.

That is, in the present invention, as the dicarboxylic acid component unit, in addition to the aromatic dicarboxylic acid component unit as described above, an aliphatic dicarboxylic acid component unit is included, and specific fine particles as described below are included. Since it is contained in a predetermined amount, the resulting aromatic polyamide resin composition,
In particular, it is excellent not only in heat resistance such as heat distortion temperature but also in high-temperature rigidity.

The aromatic polyamide [A] preferably has an intrinsic viscosity [η] measured in concentrated sulfuric acid at a temperature of 30 ° C., usually in the range of 0.5 to 3.0 dl / g, preferably 0.8 to 1.5 dl / g.

The aromatic dicarboxylic acid component unit constituting the dicarboxylic acid component unit (a) as described above may contain other aromatic dicarboxylic acid component units in addition to the terephthalic acid component unit as the main component unit. Good.

Specific examples of such other aromatic dicarboxylic acid component units include component units derived from isophthalic acid, phthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid, and the like. Acid unit or naphthalene dicarboxylic acid unit is preferable, and isophthalic acid unit is particularly preferable.

In the above dicarboxylic acid component unit (a), the terephthalic acid component unit which is a main component unit constituting the aromatic dicarboxylic acid component unit is usually 90 to 30 mol%, preferably 90 to 30 mol%.
In an amount of 60 mol%, the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is usually in an amount of 30 to 0 mol%, preferably 20 to 0 mol%, and the aliphatic dicarboxylic acid component unit is in an amount of 70 to 0 mol%. It is contained in an amount of 10 mol%, preferably 40 to 10 mol%. When the aromatic polyamide [A] containing the terephthalic acid component unit in an amount within the above range is used, the obtained aromatic polyamide resin composition has a high crystallization rate, and fine particles [B] described later such as talc or the like. ],
Further, the crystallization speed is improved, and as a result, heat resistance such as heat deformation temperature is remarkably improved.

If an aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is used in an amount of 30 to 0 mol% or less, the crystallization rate does not decrease.

When the aliphatic dicarboxylic acid component unit is used in an amount within the range of 10 to 70 mol%, the crystallinity can be kept high and the amorphous state is less likely.

The aromatic polyamide [A] used in the present invention is composed of the dicarboxylic acid component unit (a) and the aliphatic alkylenediamine component unit and / or the alicyclic alkylenediamine component unit (b). .

Among the aliphatic alkylenediamine component units,
A linear or branched chain alkylenediamine component unit having 4 to 25 carbon atoms is preferable, and a linear or branched chain alkylenediamine component unit having 6 to 18 carbon atoms is more preferable. Is desirable.

Specific examples of such an aliphatic diamine component unit include, for example, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, and 1,10- A component unit derived from a linear alkylenediamine such as diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane; and 1,4-diamino-1,1-dimethylbutane, 1,4-diamino -1-Ethylbutane, 1,4-diamino-1,2-dimethylbutane, 1,4-diamino-1,3-dimethylbutane, 1,4-diamino-1,4-dimethylbutane, 1,4-diamino- 2,3-dimethylbutane, 1,2-diamino-1-butylethane, 1,6-diamino-2,5-dimethylhexane, 1,6-diamino-2,4-dimethylhexane, 1,6-diamino-3 , 3-dimethylhexane, 1,6-diamino-2,2-dimethylhexane 1,6-diamino-2,2,4-trimethylhexane, 1,6-diamino-2,4,4-trimethylhexane, 1,7-diamino-2,3-dimethylheptane, 1,7-diamino-2 1,4-dimethylheptane, 1,7-diamino-2,5-dimethylheptane, 1,7-diamino-2,2-dimethylheptane, 1,8-diamino-1,3-dimethyloctane, 1,8-diamino -1,4-dimethyloctane, 1,8-diamino-2,4-dimethyloctane, 1,8-diamino-3,4-dimethyloctane, 1,8-diamino-4,5-dimethyloctane, 1,8 -Diamino-2,2-dimethyloctane, 1,8-diamino-3,3-dimethyloctane, 1,8-diamino-4,4-dimethyloctane, 1,6-diamino-2,4-diethylohexane, Examples of component units derived from a branched chain alkylenediamine such as 1,9-diamino-5-methylnonane it can.

Among such linear or branched chain alkylenediamine component units, straight-chain alkylenediamine component units are preferred, and in particular, 1,6-diaminohexane, 1,8-diaminooctane, Component units derived from one or more compounds of linear alkylenediamines such as 10-diaminodecane and 1,12-diaminododecane are preferred, and 1,10-diaminodecane is more preferred.
Diaminodecane component units are preferred.

The alicyclic diamine component unit usually has 6 to 6 carbon atoms.
It is a component unit derived from a diamine of about 25 and containing at least one alicyclic hydrocarbon ring.

Specific examples of such alicyclic diamine component units include, for example, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis ( Aminomethyl) cyclohexane, isophoronediamine, piperazine, 2,5-dimethylpiperazine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, 4,4'-diamino-3,3'-dimethyldicyclohexylpropane 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diamino-3,3'-dimethyl-5,5'-dimethyldicyclohexylmethane 4,4'-diamino-3,3 '-Dimethyl-5,5'-dimethyldicyclohexylpropane,α-α'-bis (4-aminocyclohexyl) -p-
Diisopropylbenzene, α-α'-bis (4-aminocyclohexyl) -m-
Diisopropylbenzene, α-α'-bis (4-aminocyclohexyl) -1,4
-Cyclohexane, α-α'-bis (4-aminocyclohexyl) -1,3
-Component units derived from an alicyclic diamine such as cyclohexane.

Among these alicyclic diamine component units, bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, and 4,4'-diamino-3,3'-dimethyldicyclohexylmethane are preferred, and bis (4
-Aminocyclohexyl) methane, 1,3-bis (aminocyclohexyl) methane, 1,3-bis (aminomethyl)
Component units derived from alicyclic diamines such as cyclohexane are preferred.

In the dicarboxylic acid component unit (a), as described above, the terephthalic acid component unit is present in an amount of 30 to 90 mol%, and the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is 0 to 30 mol% and Aliphatic dicarboxylic acid component unit is 10 to
Depending on the type of the alkylenediamine component unit (b), the terephthalic acid component unit, the component unit other than the terephthalic acid component unit, and the aliphatic dicarboxylic acid, depending on the type of the alkylene diamine component unit (b) It is desirable to change the ratio to the component units.

For example, the diamine component unit (b) constituting the aromatic polyamide [A] is composed of a linear aliphatic alkylenediamine component unit of the aliphatic alkylenediamine component unit, and the linear aliphatic alkylenediamine component unit is In the case of a linear aliphatic alkylenediamine having a relatively short alkylene group having about 6 to 7 carbon atoms, a terephthalic acid component unit is contained in the dicarboxylic acid component unit (a).
The aromatic dicarboxylic acid component unit other than the terephthalic acid component unit is contained in an amount of 15 to 40 mol%,
Further, the aliphatic dicarboxylic acid component unit is contained in an amount of 10 to 30 mol%, and the sum of the aromatic dicarboxylic acid component unit other than the terephthalic acid component unit and the aliphatic dicarboxylic acid component unit is 20 to 40 mol%. It is preferable to use the aromatic polyamide [A] contained in such an amount because the aromatic polyamide resin composition obtained not only has excellent heat resistance such as heat distortion temperature but also has excellent high-temperature rigidity.

The aromatic polyamide [A] as described above can be produced by various conventionally known methods.

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 homogeneous solution, a method in which a halide of an aromatic dicarboxylic acid and adipic acid dissolved in a polar solvent and a non-polar solvent are used. Aromatic polyamide [A] can be produced by an interfacial method of condensing the dissolved aliphatic alkylenediamine at the interface. Further, the aromatic polyamide [A] as described above can also be produced by a melt polymerization method or a solid phase polymerization method.

Fine Particles [B] Examples of the fine particles [B] used in the present invention include talc, clay, kaolin, white carbon, wollastonite, potassium titanate, metal salts of higher fatty acids, metal salts of organic phosphinates, graphite, and carbon black. , Molybdenum disulfide, metal salts of naphthenic acids, metal halides,
Examples include at least one (inorganic) filler selected from organic phosphonic acid derivatives and / or a high melting point polymer powder.

 As the high melting point polymer powder, aromatic polyamide
Polymer powder having a higher melting point than that of [A] is used.
Specific examples of such polymer powders include wholly aromatic liquid crystals.
Polyester powder (e.g., Econol ),Thermosetting
Polymer powder and the like.

In the present invention, the wholly aromatic liquid crystal polyester is preferably the first to third polyesters described below.

That is, the first polyester [A] the following formula ^{[I] -CO-Ar 1 -O-} ... [I] ( wherein, Ar ¹ is p- phenylene group at least a 60
Aromatic oxycarboxylic acid residue represented by mol% is a divalent aromatic hydrocarbon group occupying), [B] the following formula ^{[II] -O-Ar 2 -O-} ... [II] ( wherein, Ar ² is at least one divalent aromatic group selected from the group consisting of p-phenylene, 4,4′-diphenylene and naphthalene), [C] an aromatic diol residue represented by the following formula [III] In represented by 4,4'-dihydroxydiphenyl ether residues, and [D] below equation ^{[IV] -CO-Ar 3 -CO-} ... [IV] ( wherein Ar ³ is p- phenylene group at least a 60 mol% And (E) a divalent aromatic group occupying the following), and [E] the residues of the above [A], [B], [C] and [D]. [A] residue is 30 to 80 mol% based on the total number of moles of
[B] residue is 1 to 20 mol%, and [C] residue is 1 to 32 mol%.
And [D] residues account for 10-35% by mole, and [B]
The sum of the number of moles of the residue and the [C] residue is a wholly aromatic polyester substantially equal to the number of moles of the [D] residue.

Further, the second polyester is [F] a group represented by the following formula [V]; (Here, a hydrogen atom present in the aromatic ring has 1 to 1 carbon atoms.
A group represented by the following formula [VI], which may be substituted with an atom or group selected from the group consisting of four alkyl groups, a C1 to C4 alkoxy group and a halogen atom); (Here, a hydrogen atom present in the aromatic ring has 1 to 1 carbon atoms.
Which may be substituted with an atom or group selected from the group consisting of four alkyl groups, an alkoxy group having 1 to 4 carbon atoms, and a halogen atom). About 10 to
A melt-processable wholly aromatic polyester containing 90 mol% and about 10 to 90 mol% of a group represented by the formula [VI], and capable of forming a thermocompatible molten phase at a temperature of about 350 ° C. or less. It is.

Further, the third polyester is represented by the following formula [H]: An oxybenzoyl compound represented by the formula: [I] the following formula [VIII] An aromatic dicarbonyl compound represented by the formula: and [J] the following formula [IX] An aromatic dioxy compound represented by the formula: (In the above formulas [VII], [VIII] and [IX], X is -O
—, —CO—, —S— or —SO ₂ —, m is 0 or 1, n is 0 or 1, and the molar ratio of [I]: [J] is from 15:10 to 10: And the molar ratio of [H]: [I] is from 1: 100 to 100: 1, and R ⁴ , R ⁵ and R ⁶ are each independently a group consisting of a hydrogen atom, a benzoyl group and a lower alkanoyl group. Represents a selected atom or group,
R ² , R ³ and R ⁴ each represent an atom or a group independently selected from the group consisting of a hydrogen atom, a phenyl group, a benzyl group and a lower alkyl group, and the carbonyl groups of the dicarbonyl compound are meta or para to each other. And the oxy groups of the dioxy compound are meta or para to each other).

Details of an example of a wholly aromatic polyester having liquid crystallinity and a preferred embodiment thereof used in the present invention are described in Japanese Patent Application No. 62-46925.

That is, in the present invention, among the above-mentioned first polyesters, particularly preferred wholly aromatic polyesters include: [A-1] the following formula [I-1] A p-oxybenzoic acid residue represented by the following formula: [B-1] [C] a hydroquinone residue represented by the following formula [III]: A 4,4'-dihydroxydiphenyl ether residue represented by the following formula: [D-1] The following formula [IV-1] And [E] the above [A-1], [B-1], [C] and [D
[A-1] is 40 based on the total number of moles of the residue of [-1].
~ 70 mol%, [B-1] is 3 ~ 16 mol%, [C] is 3 ~
24 mol% and [D-1] account for 15 to 30 mol%, and the sum of the number of moles of the [B-1] residue and the [C] residue is [D-1]
Polyester substantially equal to the number of moles of residue.

Further, instead of part of the hydroquinone residue of the above formula [II-1], preferably 40 mol% of the hydroquinone residue, the following formula [II-2] A wholly aromatic polyester containing an aromatic diol residue represented by is also a particularly preferred polymer.

The wholly aromatic polyester used in the present invention preferably has a melt viscosity of 10 ² to 10 ⁷ poise, preferably measured at a temperature 30 ° C. higher than the melting point of the wholly aromatic polyester and a shear rate of 100 sec ^−1. Represents ² × 10 ² to 10 ⁶ poise, particularly preferably 5 × 10 ² to 10 ⁵ poise.

When it is difficult to measure the melting point of the wholly aromatic polyester, the same melt viscosity range as described above can be defined using the softening point as an index instead of the above melting point.

The above wholly aromatic polyesters used in the present invention are all substantially linear, and any of the aforementioned residues may be located at the terminal of the polymer chain. In addition, the carboxyl group terminal is esterified with a monohydric lower alcohol such as methanol, ethanol and isopropanol or a monovalent aromatic hydroxy compound such as phenol and cresol, and the hydroxyl group terminal by a conventional method. For example, it may be esterified with a monovalent carboxylic acid such as acetic acid, propionic acid or benzoic acid.

The glass transition temperature (Tg) of the first wholly aromatic polyester used in the present invention is usually determined by a differential scanning calorimeter (DS).
Melting point (Tm) measured by DSC, not detected in C)
Is usually in the range of 250 to 450 ° C, preferably 250 to 380 ° C.

These measuring methods are described in Japanese Patent Application No. 62-56925.

In the present invention, similarly to the above-described wholly aromatic polyester, a wholly aromatic polyester having the following liquid crystallinity can be used.

That is, a wholly aromatic polyester is represented by [F] a group represented by the following formula [V], (Here, a hydrogen atom present in the aromatic ring has 1 to 1 carbon atoms.
A group represented by the following formula [VI], which may be substituted with an atom or group selected from the group consisting of four alkyl groups, an alkoxy group having 1 to 4 carbon atoms and a halogen atom); (Here, a hydrogen atom present in the aromatic ring has 1 to 1 carbon atoms.
Which may be substituted with an atom or group selected from the group consisting of four alkyl groups, an alkoxy group having 1 to 4 carbon atoms and a halogen atom), and the polyester represented by the formula [V] About 10 to 90 mol% of the repeating unit represented by the formula (VI) and about 10 to 90 mol% of the repeating unit represented by the formula [VI]
It is a melt-processable wholly aromatic polyester which contains a mole% and can form a thermochromic melt phase at a temperature of about 350 ° C. or less.

The glass transition temperature (Tg) of the second wholly aromatic polyester used in the present invention is usually determined by a differential scanning calorimeter (DS).
Melting point (Tm) measured by DSC, not detected in C)
Is usually in the range of 250 to 450 ° C, preferably 250 to 380 ° C.

This wholly aromatic polyester is disclosed in
This is described in detail in JP-A-79691.

Particularly preferred compounds among the second wholly aromatic polyesters are described below.

The third wholly aromatic polyester used in the present invention is represented by the following formula [H]: An oxobenzoyl compound represented by the following formula: [I] the following formula [VIII] An aromatic dicarbonyl compound represented by the formula: and [J] the following formula [IX] Is a wholly aromatic polyester compound obtained by condensing an aromatic dioxy compound represented by the formula:

However, in the above formulas [VII], [VIII] and [IX],
X is -O -, - CO -, - an S- or -SO _2, m is 0 or 1, [I]: the molar ratio of [J] is to no 15:10 10:15, [ The molar ratio of H]: [I] is from 1: 100 to 100: 1, wherein R ⁴ , R ⁵ and R ⁶ are each independently selected from the group consisting of hydrogen, benzoyl and lower alkanoyl, or R ² , R ³ and R ⁴ are each an atom or group independently selected from the group consisting of a hydrogen atom, a phenyl group, a benzyl group and a lower alkyl group, and the carbonyl groups of the dicarbonyl compound are It is in the meta or para position, and the oxy groups of the dioxy compound are in the meta or para position to each other.

The glass transition temperature (Tg) of the third wholly aromatic polyester used in the present invention is usually determined by a differential scanning calorimeter (DS).
Melting point (Tm) measured by DSC, not detected in C)
Is usually in the range of 250 to 450 ° C, preferably 250 to 380 ° C.

This wholly aromatic polyester is described in
It is described in detail in JP-A-47-47870.

Particularly preferred compounds among the third wholly aromatic polyesters are described below.

Further, in the present invention, besides the compound represented by the above formula, a liquid crystalline wholly aromatic polyester represented by the formula shown in Table 1 can also be used.

In addition, among the compounds described in Table 1 above, particularly preferred compounds are the wholly aromatic polyesters represented by the symbol 4 when indicated by the symbols given in Table 1.

In the present invention, among these fine particles, talc and high melting point polymer powder are preferably used. When talc and the high melting point polymer powder are blended with the aromatic polyamide [A], not only the heat resistance such as the heat distortion temperature of the obtained composition is remarkably improved, but also the high temperature rigidity tends to be improved. .

These particles may be used alone or in combination of two or more.

In the present invention, the fine particles [B] are based on 100 parts by weight in total of the polyamide [A] and the fine particles [B].
It is used in an amount of 0.1 to 10 parts by weight, preferably 1 to 5 parts by weight.

In the present invention, the aromatic polyamide [A] containing the adipic acid component unit is blended with the fine particles [B] in the amount described above. The composition is particularly excellent in heat resistance such as heat distortion temperature.

Moreover, in the aromatic polyamide containing the adipic acid component unit, an aromatic polyamide resin having excellent properties such as heat distortion temperature can be obtained by blending a small amount of fine particles [B] with the aromatic polyamide. A composition is obtained.

As described above, in the aromatic polyamide containing the adipic acid component unit, the fine particles [B] are presumed to have a function of a nucleating agent.

As described above, the aromatic polyamide resin composition containing a small amount of fine particles and having excellent properties such as heat deformation temperature is used for electrical parts such as connectors, coil bobbins, housings, and automobile parts used in the electric and electronic fields. It is particularly preferably used for such purposes.

If the fine particles [B] are blended in an amount of less than 0.1 part by weight with respect to 100 parts by weight of the total of the aromatic polyamide [A] and the fine particles [B], the crystallization speed is not much improved. Tend to lower the heat distortion temperature, high-temperature rigidity, etc.
Even if it is added in an amount exceeding the parts by weight, the heat distortion temperature and the like hardly change.

These fine particles [B] can take various shapes such as powder, granule, plate, and fiber.

For example, in the case of powdery fine particles, the size of the particles in the molding material is 5 μm or less in average particle diameter, preferably 3 μm.
The following maximum particle size is preferably 20 μm or less. If the fine particles are larger than the above values, the mechanical strength and the appearance are poor due to the foreign matter effect. The particle size can be measured using an image analyzer or the like.

Production The aromatic polyamide resin composition according to the present invention comprises the aromatic polyamide [A] in a molten state, for example, at 330 to 360 ° C.
It can be adjusted by a method such as mixing fine particles with the polyamide [A] while heating and maintaining the temperature. At this time, an extruder, a kneader, or the like can be used.

The aromatic polyamide resin composition according to the present invention as described above can be molded by a usual melt molding method, for example, a compression molding method, an injection molding method, or an extrusion molding method.

As described above, the aromatic polyamide resin composition according to the present invention contains the aromatic polyamide [A] and the fine particles [B] as essential components. In addition to these essential components, if necessary, Inorganic fillers other than the above, antioxidants, ultraviolet absorbers, light protectants, heat stabilizers, phosphite stabilizers, peroxide decomposers, basic auxiliaries, nucleating agents, plasticizers, lubricants,
It may contain an antistatic agent, a flame retardant, a pigment, a dye, and the like.

Among the fillers, as a fibrous inorganic filler,
Specifically, glass fiber, carbon fiber, boron fiber, or the like can be given. When such a fiber is used, tensile strength, bending strength, mechanical properties such as flexural modulus of a molded product obtained from the aromatic polyamide resin composition,
There is a tendency that heat resistance such as heat distortion temperature and physical and chemical properties such as water resistance are improved.

The average length of the fibrous inorganic filler as described above is usually in the range of 0.1 to 20 mm, preferably 1 to 10 mm. When the average length of the fibrous inorganic filler is in such a range, the moldability of the aromatic polyamide resin composition is improved, and the heat deformation temperature of a molded article obtained from the aromatic polyamide resin composition is improved. Heat resistance, tensile strength,
There is a tendency for mechanical properties such as bending strength to be improved.

Such a fibrous inorganic filler is generally used in an amount of 60 parts by weight or less, preferably 10 to 60 parts by weight, based on 100 parts by weight of the aromatic polyamide [A] and the fine particles [B] in total. It is desirable that the aromatic polyamide resin composition is contained in the aromatic polyamide resin composition of the present invention in an amount, more preferably in an amount of 10 to 50 parts by weight.

The aromatic polyamide resin composition according to the present invention is formed by a usual molding method, and in addition to particularly excellent heat resistance, a field where excellent surface smoothness is required, or a precision molding field, specifically, an automobile part, It is used for various purposes such as electrical components such as connectors, coil bobbins, and housings used in the electric and electronic fields.

Effect of the Invention Since the aromatic polyamide resin composition according to the present invention is such that the fine particles as described above are blended in the amount as described above in the aromatic polyamide containing the aliphatic dicarboxylic acid component unit, In particular, it is excellent in heat resistance such as heat deformation temperature.

[Examples] Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.

Example 1 [Synthesis of aromatic polyamide] 254 g (2.19 M) of 1,6-diaminohexane, 247 g (1.49 M) of terephthalic acid (TA), 94 g (0.64 M) of adipic acid (AA)
And sodium hypophosphite 0.45 g (4.25 × 10
^-3 M) and 148 ml of ion-exchanged water in a 1.0 reactor,
After the replacement with nitrogen, the reaction was carried out at 250 ° C. and 35 kg / cm ² for 1 hour.
After the completion of the reaction, the solution was withdrawn to a receiver at a pressure set at about 10 kg / cm ² lower than the reactor, and the intrinsic viscosity [η] was 0.10 dl / g (concentrated sulfuric acid,
545 g of polyamide (C).

Next, after drying the polyamide, it was melt-polymerized at a cylinder setting temperature of 330 ° C. using a twin-screw extruder to obtain an aromatic polyamide having an intrinsic viscosity [η] of 1.1 dl / g (concentrated sulfuric acid, 30 ° C.). .

The mole% of the terephthalic acid component unit in this aromatic polyamide was 71%, and the melting point was 335 ° C.

[Manufacture of polyamide resin composition] Twin screw extruder with vent [Ikegai Iron Works Co., Ltd., model number PCM-4
Using 5], 95 parts by weight of the above-mentioned aromatic polyamide and 5 parts by weight of talc were supplied from a vent portion and granulated at 340 ° C.

Test pieces were injection-molded from the pellets of the polyamide resin composition thus obtained using an injection molding machine (manufactured by Toshiba Machine Co., IS-50) under the following conditions.

[Injection molding conditions] Cylinder temperature (° C): 320/340/340/340 Injection pressure (kg / cm ² ): primary / secondary = 1000/800 Mold temperature (° C): 120 The above test piece was bent. Properties, heat resistance, etc. were evaluated according to the following methods.

 Table 2 shows the results.

[Evaluation method] Bending characteristics: Size 3.2 mm x 12.7 mm x 12 according to ASTM D790
Using a 7 mm test piece, a bending test is performed to determine bending strength and bending elastic modulus.

Heat resistance: The heat resistance is evaluated at the heat deformation temperature.

The heat distortion temperature is 18.6 kg / cm ³ according to ASTM-D-648.
The test piece having a size of 6.4 mm × 12.7 mm × 127 mm to which the bending stress is applied is heated at a rate of 2 ° C./min to a temperature at which the deflection reaches 0.254 mm.

Tensile strength and tensile elongation: according to ASTM D 638.

Izod impact strength (with and without notch): A
Compliant with STM D 256.

Examples 2 to 7, Comparative Examples 1 to 3 In Example 1, the molar ratio of dicarboxylic acid component units,
That is, the molar ratios of the terephthalic acid (TA): isophthalic acid (IA): adipic acid (AA) component units were changed as shown in Table 2, and the fine particles and ash content and various conditions were changed as shown in Table 2. Except for the above, it was the same as Example 1.

 The results are shown in Table 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification code FI C08L 67:03) (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 77/06 C08L 67/03 C08K 3 / 00-3/40 C08K 5/09 C08K 5/49

Claims (1)

(57) [Claims] 1. [A] (a) The dicarboxylic acid component unit is a terephthalic acid component unit; 30 to 90 mol% and an aliphatic dicarboxylic acid component unit; 10 to 70 mol%, or a terephthalic acid component unit; Mole%, aromatic dicarboxylic acid component unit other than terephthalic acid component unit;
30 mol%, and aliphatic dicarboxylic acid component unit; 10 to 70
(B) an aromatic polyamide in which the diamine component unit is an aliphatic alkylenediamine component unit and / or an alicyclic alkylenediamine component unit, and [B] talc, clay, kaolin, white carbon,
Wollastonite, potassium titanate, higher fatty acid metal salt,
It comprises at least one filler selected from organic metal phosphinates, graphite, carbon black, molybdenum disulfide, metal naphthenates, metal halides, organic phosphonic acid derivatives, and / or a high melting polymer powder. The fine particles [B] are contained in an amount of 0.1 to 10 parts by weight based on 100 parts by weight in total of the polyamide [A] and the fine particles [B]. Aromatic polyamide resin composition.