JPH09279019A - Semi-aromatic polyamide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semi-aromatic polyamide composition from which a highly accurate and heat resistant molding can be produced with little stain on a mold and little clogging in mold vent. SOLUTION: This semi-aromatic polyamide composition comprises [I] 99-30-wt.% semi-aromatic polyamide having 40-90mol% repeated unit comprising terephthalic acid and a 4-12Caliphatic diamine (A), 0-50mol% repeated unit comprising isophthalic acid and a 4-12C aliphatic diamine (B), 0-60mol% repeated unit comprising a 4-12C aliphatic dicarboxylic acid and a 4-12 C aliphatic diamine (C), and 0-50mol% repeated unit comprising a 6-12C lactam or aminocarboxylic acid (D) and contg. not more than 0.25wt.% low mol. wt. boiling water soluble component(MO component), and [II] 1-70wt.% modified elastic polymer.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a semi-aromatic polyamide composition formed by polycondensation of a dicarboxylic acid consisting of an aromatic dicarboxylic acid and a diamine. More specifically, the present invention is a semi-aromatic compound which has excellent mechanical strength such as heat resistance, impact resistance, and bending strength, and which can efficiently produce a molded product with less mold fouling during the production of the molded product. It relates to a polyamide composition.

[0002]

BACKGROUND OF THE INVENTION Various proposals have hitherto been made regarding a method for producing a semi-aromatic polyamide. For example, the applicant of the present invention has already disclosed in Japanese Patent Application Laid-Open No. 4-50230 that a terephthalic acid component unit of 50 to 90 is used. Aromatic dicarboxylic acid component unit (a) consisting of 0 to 40 mol% of an aromatic dicarboxylic acid other than terephthalic acid or a linear aliphatic component unit having 6 to 18 carbon atoms, and an alkylenediamine component unit (b) And a semiaromatic polyamide resin having an intrinsic viscosity in the range of 0.5 to 3.0 dl / g as measured in concentrated sulfuric acid at 30 ° C. It is also known that a composition comprising such a semi-aromatic polyamide resin and a modified elastic polymer is excellent in heat resistance and impact resistance.

Such a polyamide resin composition is remarkably excellent in heat resistance, mechanical properties and chemical / physical properties, but on the other hand, since it has a high melting point, it does not have sufficient fluidity during injection molding and is molded. Defects are likely to occur. For this reason, the molding die is often molded at a high temperature of 100 ° C. or higher. In this way, when injection molding is repeated using a high temperature mold, white powder may be deposited in the mold and stains on the mold may occur. As a result of analysis of this powder, it was found that this powder was an unreacted monomer and a low-order oligomer component. This unreacted monomer or low-order oligomer component (hereinafter referred to as "MO component") may cause mold stains or spoil appearance as described above when molding fine parts such as electronic parts, especially connectors. There is a problem in that the dimensional accuracy does not appear. Further, since the vent hole of the mold is clogged, it is necessary to stop the molding and clean the mold.

Therefore, it is excellent in mechanical strength such as impact resistance and bending strength, and also excellent in chemical and physical characteristics such as excellent heat resistance. Moreover, it is hard to cause mold stains during molding, and the vent of the mold is clogged. Therefore, it has been desired to develop a semi-aromatic polyamide composition capable of producing a precision molded article having excellent appearance and excellent appearance.

[0005]

An object of the present invention is to provide a semi-aromatic polyamide composition capable of producing a molded product which is less likely to be contaminated by a mold during molding and which is excellent in mechanical strength such as impact resistance and bending strength and heat resistance. The purpose is to provide things.

[0006]

SUMMARY OF THE INVENTION The semi-aromatic polyamide composition of the present invention comprises a repeating unit derived from [I] (A) terephthalic acid and an aliphatic diamine having 4 to 12 carbon atoms, (B) isophthalic acid and carbon number. A repeating unit derived from an aliphatic diamine having 4 to 12 carbon atoms, (C) a repeating unit derived from an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic diamine having 4 to 12 carbon atoms, and (D ) A semi-aromatic polyamide having a repeating unit derived from a lactam having 6 to 20 carbon atoms or an aminocarboxylic acid: 99 to 30% by weight and [II] a modified elastic polymer: 1 to 70% by weight, The semi-aromatic polyamide has the repeating unit (A) of 40 to
90 mol%, repeating unit (B) 0 to 50 mol%, repeating unit (C) 0 to 60 mol%, repeating unit (D) 0
A low molecular weight boiling water soluble component (extracted and measured) measured by immersing in a semi-aromatic polyamide in an amount of 50 mol% and contained in the semi-aromatic polyamide for 24 hours in boiling water at 100 ° C. It is characterized in that the content of (MO component) is 0.25% by weight or less.

Further, this semi-aromatic polyamide composition is
[III] It is preferable to include a fibrous reinforcing material.

This semi-aromatic polyamide [I] contains terephthalic acid, and if necessary, isophthalic acid and 4 to 4 carbon atoms.
(A) terephthalic acid and 4 to 12 carbon atoms by bringing 12 aliphatic dicarboxylic acid, 4 to 12 carbon aliphatic diamine, and optionally 6 to 12 carbon lactam or aminocarboxylic acid into contact with each other. 60 to 90 mol% of repeating units derived from 12 aliphatic diamines, 0 to 50 mol% of repeating units derived from (B) isophthalic acid and aliphatic diamines having 4 to 12 carbon atoms, (C ) 0 to 60 mol% of repeating units derived from an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic diamine having 4 to 12 carbon atoms, and (D) a lactam or aminocarboxylic acid having 6 to 12 carbon atoms A semi-aromatic polyamide containing an acid-derived repeating unit in an amount of 0 to 50 mol% is prepared, and then the obtained semi-aromatic polyamide and an aqueous medium are contained in the semi-aromatic polyamide. MO success Can content is prepared by contacting to be 0.25 wt% or less.

In the present specification, the MO component (low-molecular-weight water-soluble component) contained in the semi-aromatic polyamide is a linear or cyclic monomer or a low-order oligomer, and is boiled at -100 ° C. for 24 hours. It is a general term for what is extracted in water.

A semiaromatic polyamide in which the MO component (low-molecular-weight boiling water-soluble component) contained in the semiaromatic polyamide is adjusted to 0.25% by weight or less by contacting the semiaromatic polyamide with an aqueous medium, When a molded product is produced from a semi-aromatic polyamide composition comprising a modified elastic polymer, mold stains are less likely to occur, the molded product can be efficiently produced, and the resulting molded product has impact resistance, Excellent mechanical strength such as bending strength and heat resistance.

[0011]

DETAILED DESCRIPTION OF THE INVENTION Next, the semi-aromatic polyamide composition of the present invention will be specifically described.

Semi-aromatic polyamide Polyamide is generally a polymer compound in which repeating units derived from a dicarboxylic acid and a diamine or further repeating lactam ring-opening repeating units are bonded.

The dicarboxylic acid forming the semi-aromatic polyamide used in the present invention is an aromatic dicarboxylic acid,
There are alicyclic dicarboxylic acids and aliphatic dicarboxylic acids. Here, as the aromatic dicarboxylic acid, terephthalic acid and its functional derivatives (eg, salts, halides, esters, etc.), aromatic dicarboxylic acids other than terephthalic acid (eg, isophthalic acid, naphthalenedicarboxylic acid), and their functional compounds Derivatives can be mentioned.

Further, in the present invention, as the dicarboxylic acid,
In addition to the above-mentioned aromatic dicarboxylic acids, aliphatic dicarboxylic acids and alicyclic dicarboxylic acids can also be used. When an aliphatic dicarboxylic acid is used here, the aliphatic dicarboxylic acid is preferably a linear aliphatic dicarboxylic acid, and more preferably a linear aliphatic dicarboxylic acid having an alkylene group having 4 to 12 carbon atoms. Examples of such a linear aliphatic dicarboxylic acid include succinic acid (S
Mention may be made of A), adipic acid (AA), azelaic acid, sebacic acid and their functional derivatives. Of these aliphatic dicarboxylic acids, adipic acid and sebacic acid are preferred. Examples of the alicyclic dicarboxylic acid include tetracyclohexanedicarboxylic acid and its functional derivative.

Here, the functional derivative includes a functional derivative (eg, salt, halide, ester, etc.) capable of forming a repeating unit by reaction with a diamine,
Further, in the present invention, the dicarboxylic acid and diamine may have a substituent such as an alkyl group within the range that does not impair the properties of the obtained polyamide resin. Hereinafter, each component used in the present invention has the same meaning as described above.

The diamine constituting the repeating unit forming the semi-aromatic polyamide of the present invention together with the above dicarboxylic acid is an aliphatic diamine having 4 to 12 carbon atoms or a functional derivative thereof.

The aliphatic diamine may be a linear alkylenediamine or a branched chain alkylenediamine. Specific examples of such alkylenediamine include 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,
Linear alkylenediamines such as 8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 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, 1,5-diamino-2-methylpentene, 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-2,4-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-
Dimethyl octane, 1,8-diamino-4,5-dimethyl octane, 1,8-diamino-2,2-dimethyl octane, 1,8-diamino-3,3-dimethyl octane, 1,8-diamino-4, 4-dimethyloctane, 1,6-diamino-2,4-diethylhexane and
A chain-like branched alkylenediamine such as 1,9-diamino-5-methylnonane can be mentioned.

Of these linear or branched chain alkylenediamines, linear alkylenediamines are preferred, with 1,6-diaminohexane (hexamethylenediamine: HMDA) and 1,8-diamino being particularly preferred. Linear alkylenediamines such as octane, 1,10-diaminodecane and 1,12-diaminododecane are preferred and these can be used alone or in combination. The diamine as described above may be a functional derivative such as a salt as long as it can react with the dicarboxylic acid to form a repeating unit.

In the semi-aromatic polyamide used in the present invention,
A repeating unit represented by the following formula [I] is formed from terephthalic acid (TA) and diamine.

[0020]

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In the above formula [I], R ¹ is a divalent hydrocarbon group derived from the diamine component used and represents an alkylene group having 4 to 12 carbon atoms. Further, in the present invention, when isophthalic acid (IA) is used together with terephthalic acid (TA), from this isophthalic acid and diamine,
A repeating unit represented by the following [II] is formed.

[0022]

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In the above formula [II], R ¹ is a divalent hydrocarbon group derived from the diamine component used and represents an alkylene group having 4 to 12 carbon atoms. Also, when an aliphatic dicarboxylic acid is used together with terephthalic acid, the following [III]
The repeating unit represented by is formed.

[0024]

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In the above formula [III], R ¹ is a divalent hydrocarbon group derived from the diamine component used and represents an alkylene group having 4 to 12 carbon atoms. Further, n usually represents a positive integer of 4 to 12.

Further, the semi-aromatic polyamide used in the present invention has, in addition to the repeating unit composed of the dicarboxylic acid and the diamine as described above, a repeating unit in which a lactam having 6 to 12 carbon atoms is opened. May be.

Specific examples of such lactams having 6 to 12 carbon atoms or aminocarboxylic acids include ε-caprolactam, ω-laurolactam, 11-aminoundecanoic acid and 12-aminododecanoic acid. it can.

A repeating unit having a structure represented by the following formula [IV] is formed from the lactam or aminocarboxylic acid as described above.

[0029]

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In the above formula [IV], n is an integer of 5-12. In the semi-aromatic polyamide used in the present invention, the amount of the repeating units represented by the above formulas [I] to [III] corresponds to the amount of the dicarboxylic acid used and is represented by the formula [IV]. The amount of repeating units corresponds to the amount of lactam or aminocarboxylic acid used.

In the semi-aromatic polyamide used in the present invention, the repeating unit (A) derived from terephthalic acid represented by the above formula [I] and an aliphatic diamine having 4 to 12 carbon atoms is 40 units. ~ 90 mol%, preferably 45 ~
A repeating unit (B) which is present in an amount of 65 mol%, particularly preferably 45 to 55 mol%, and is derived from an isophthalic acid represented by the formula [II] and an aliphatic diamine having 4 to 12 carbon atoms. Is 0 to 50 mol%, preferably 5 to 45 mol%,
Most preferably, it is present in an amount of 15 to 45 mol%,
The repeating unit (C) derived from an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic diamine having 4 to 12 carbon atoms represented by [I] is 0 to 60 mol%, preferably 10
To 55 mol%, particularly preferably 45 to 55 mol%, and the repeating unit (D) derived from the lactam or aminocarboxylic acid represented by the formula [IV] is 0 to 50 mol%, preferably Is 5 to 30 mol%, particularly preferably 10 to
It is preferably present in an amount of 20 mol%.

In order to produce such a semi-aromatic polyamide, when the total amount of dicarboxylic acids is 100 mol%,
Terephthalic acid is usually 40 to 100 mol%, preferably 40 to 90 mol%, more preferably 45 to 70 mol%.
The aromatic dicarboxylic acid other than terephthalic acid is usually used in the range of 0 to 50 mol%, preferably 5 to 40 mol%, more preferably 10 to 30 mol%. In addition, the linear aliphatic dicarboxylic acid is usually contained in an amount of 0 to 60 mol%, preferably 10
It can be used in the range of ˜55 mol%, particularly preferably 40 to 55 mol%.

The diamine is used so as to be almost equimolar to the above dicarboxylic acid.
0 mol% has 4 carbon atoms as an essential component in the present invention.
The -12 aliphatic diamine is generally used in an amount in the range of 50 to 100 mol%, preferably 80 to 100 mol%.

In the present invention, the repeating unit derived from a lactam having 6 to 12 carbon atoms or an aminocarboxylic acid is usually in the range of 0 to 50 mol%, preferably 0 to 30 mol%.

Preferred examples of the semi-aromatic polyamide of the present invention include (1) TA / AA / HMDA composition ratio: 60 to 45 mol% / 40 to 55 mol% / 100
Mol% (2) TA / IA / HMDA composition ratio: 85-60 mol% / 15-40 mol% / 100
Mol% (3) TA / IA / AA or SA / HMDA composition ratio: 85-55 mol% / 5-25 mol% / 5-20
Mol% / 100 mol% (4) TA / IA / 6 / HMDA composition ratio: 85-55 mol% / 5-25 mol% / 5-20
Mol% / 100 mol% (5) TA / 6 / HMDA composition ratio: 85 to 50 mol% / 15 to 50 mol% / 85
50 mol% (6) TA / AA / 6 / HMDA composition ratio 80-30 mol% / 15-65 mol% / 5-20
Mol% / 95-80 mol% and the like.

In the above semi-aromatic polyamide, "6" represents a component unit derived from ε-caprolactam. Further, "TA" represents a component unit derived from terephthalic acid, "IA" represents a component unit derived from isophthalic acid, and "AA" represents a component unit derived from adipic acid. Furthermore, “HMDA” represents a component unit derived from hexamethylenediamine.

In this reaction, the above components are mixed in an aqueous medium to prepare, for example, phosphoric acid, a salt thereof and a phosphoric acid ester compound; phosphorous acid, a salt and an ester compound thereof;
It can also be produced by heating the above components in the presence of a catalyst such as hypophosphorous acid, a salt thereof and an ester compound to produce a low-order condensate, and then melt-kneading the low-order condensate. Alternatively, the above components may be reacted under heating to directly form the semi-aromatic polyamide of the present invention. The conditions for polycondensing the above-mentioned dicarboxylic acid, diamine and lactam or aminocarboxylic acid are set to the usual conditions for producing a polyamide.

For example, in the semi-aromatic polyamide produced as described above, in addition to the desired semi-aromatic polyamide, there are usually unreacted dicarboxylic acids and unreacted dicarboxylic acids defined as MO components in the present invention. Low-order condensation of reacted diamine and unreacted lactam, or aminocarboxylic acid, and cyclic oligomer formed from one molecule of diamine and one molecule of dicarboxylic acid, especially cyclic hexamethylene adipamide, or other lower oligomer component. Things are contained. Such components are soluble in hot water (especially boiling water).

The content of this MO component in the semi-aromatic polyamide generally reaches several% by weight.
The semi-aromatic polyamide used in the present invention has a low content of the above-mentioned MO component, which usually reaches several% by weight.
The content of the components (content measured by extracting with boiling water at 100 ° C. for 24 hours) is 0.25% by weight or less,
Further, it is preferably 0.15% by weight or less, and particularly preferably 0.10% by weight or less.

In order to adjust the content of the MO component to the above range, the semiaromatic polyamide once produced is brought into contact with an aqueous medium, and the MO content contained in the semiaromatic polyamide is increased.
The components are transferred to an aqueous medium and removed. The aqueous medium used here is usually water, and this aqueous medium may optionally contain a water-soluble organic solvent such as alcohol.

The semi-aromatic polyamide and the aqueous medium are preferably brought into contact with each other while heating. At this time, the temperature of the aqueous medium is 30 to 100 ° C, preferably 50 to 100 ° C, particularly preferably 70 to 100 ° C. In addition, the contact time between the semi-aromatic polyamide and the aqueous medium (that is, the cleaning time)
Is usually 5 minutes to 24 hours, preferably 10 minutes to 8 hours, particularly preferably 30 minutes to 5 hours. When the semi-aromatic polyamide and the aqueous medium are brought into contact with each other in a container such as a drum, it is desirable to bring them into contact with each other while stirring or circulating water. The amount of the aqueous medium in contact with the semi-aromatic polyamide is usually 50 to 10000 parts by weight, preferably 200, relative to 100 parts by weight of the semi-aromatic polyamide to be treated.
~ 1000 parts by weight.

By contacting the semi-aromatic polyamide containing a large amount of MO component with the aqueous medium as described above, at least a part of the MO component in the semi-aromatic polyamide is extracted into the aqueous medium.

By separating the aqueous medium from which the MO component has been extracted in this way and the semiaromatic polyamide, the amount of the MO component in the semiaromatic polyamide can be reduced as described above. For separation of the aqueous medium and the semi-aromatic polyamide, known methods such as filtration and centrifugation can be used.

The semi-aromatic polyamide thus separated from the aqueous medium is dried in order to remove the aqueous medium normally present on the surface. Drying of this semi-aromatic polyamide is preferably performed under vacuum or under an inert gas flow (eg, nitrogen gas flow), and the drying temperature is generally set to a temperature lower than the melting temperature of the semi-aromatic polyamide. Usually 10
0 to 250 ° C., preferably 120 to 200 ° C., and by drying under such conditions, the water content of the semi-aromatic polyamide is usually 5000 ppm or less, preferably 3000 ppm or less, more preferably 1000 ppm or less. You can In addition, infrared rays or the like can be used or used in combination as a heating means for this drying.

The concentration of the MO component extracted and measured by immersing the semi-aromatic polyamide used in the present invention thus obtained in boiling water at 100 ° C. for 24 hours is 0.25% by weight or less. , Preferably 0.15% by weight
Below, it is reduced to 0.10% by weight or less.

The semi-aromatic polyamide produced as described above has the repeating unit as described above, and its glass transition temperature is usually in the range of 70 to 125 ° C, preferably 80 to 125 ° C. is there. Further, the semi-aromatic polyamide of the present invention usually has a melting point because it is crystalline, and this melting point is generally in the range of 260 to 360 ° C, and in most cases 280 to 330 ° C. The intrinsic viscosity [η] of this semi-aromatic polyamide measured in concentrated sulfuric acid at 30 ° C. is usually 0.5 to 3.0 dl / g, preferably 0.7 to 1.5 dl / g. It is inside.

Modified Elastic Polymer The semi-aromatic polyamide composition of the present invention contains a modified elastic polymer. As such a modified elastic polymer,
(I) Modified α-olefin-based elastic polymer or (ii) Modified aromatic vinyl-conjugated diene block copolymer or (i
ii) An ionomer is used.

(I) The modified α-olefin elastic polymer is an unsaturated carboxylic acid or its derivative component based on 100 parts by weight of a base α-olefin elastic polymer containing an α-olefin component unit as a main component. Unit is 0.01 ~
It is required to be graft-copolymerized in a range of 10 parts by weight, and its crystallinity must be within a range of 20% or less. Further, α-olefin which is a base containing an α-olefin component unit as a main component. The unsaturated carboxylic acid or its derivative component unit is added to 100 parts by weight of the olefinic elastic polymer.
Graft copolymerization in the range of 050 to 5 parts by weight, the crystallinity of which is in the range of 20% or less, and the melt flow rate at ₁₉₀ ° C. (MFR ₁₉₀ ° C.) is 0.01 to.
It is preferably in the range of 50 g / 10 min. Furthermore, other physical properties of the modified α-olefin-based elastic polymer are
The molecular weight distribution (Mw / Mn) is usually in the range of 1.5 to 50, preferably 2 to 30, and the glass transition temperature is usually -1.
It is in the range of 0 ° C or lower, preferably -20 ° C or lower.

When the graft ratio of the unsaturated carboxylic acid or its derivative component unit in the modified α-olefin-based elastic polymer is less than 0.01 parts by weight, the compatibility with the semi-aromatic polyamide deteriorates, and the polyamide composition. When the impact strength is less than 10 parts by weight, the degree of cross-linking of the graft-modified product increases, and the effect of improving the impact resistance of the composition even when compounded with polyamide may decrease. is there. If the crystallinity of the modified α-olefin-based elastic polymer is more than 20%, the impact resistance of the polyamide composition may decrease.

The α-olefin-based elastic polymer which is a base material of the modified α-olefin-based elastic polymer is a low-crystalline elastic polymer containing an α-olefin component unit as a main component, and is composed of two or more components. In some cases, it may be composed of only the α-olefin component unit, or may contain a small amount of a diene component unit in addition to the α-olefin component.

The content of the α-olefin component unit constituting the base α-olefin elastic polymer is usually 65 mol%.
Or more, preferably 70 mol% or more, and the content of the diene component is usually 0 to 20 mol%, preferably 0 to 1
It is in the range of 5 mol%.

The other physical properties of the base α-olefin-based elastic polymer are that the crystallinity is usually 20% or less, preferably 19 to 20%.
It is in the range of 1%, and the melt flow rate at ₁₉₀ ° C. [MFR ₁₉₀ ° C.] is usually 0.01 to 50 g / 10 min,
It is preferably in the range of 0.05 to 20 g / 10 min,
The glass transition temperature is usually −10 ° C. or lower, preferably −20.
It is below ° C.

Here, as the α-olefin component unit of the constituent component, ethylene, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1 -Dodecene etc. can be exemplified,
The diene component unit, 1,4-hexadiene, dicyclopentadiene, 5-ethylidene 2-norbornene, non-conjugated diene components such as 2,5-norbornadiene, butadiene,
Examples thereof include conjugated diene components such as isoprene and piperylene. As the base α-olefin elastic polymer, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 1-hexene copolymer ,ethylene·
1-octene copolymer, ethylene / 1-decene copolymer, propylene / ethylene copolymer, propylene / 1-butene copolymer, propylene / 4-methyl-1-pentene copolymer,
Α such as propylene / 1-octene copolymer, propylene / 1-decene copolymer, propylene / 1-dodecene copolymer
-Olefin elastic copolymer, ethylene / propylene / 1
4-hexadiene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5-
Ethylidene-2-norbornene copolymer, ethylene / propylene / 2,5-norbornadiene copolymer, ethylene / 1-
Butene / dicyclopentadiene copolymer, ethylene / 1
Α-such as butene / 1,4-hexadiene copolymer, ethylene / 1-butene / 5-ethylidene 2-norbornene copolymer
Examples thereof include olefin / non-conjugated diene elastic copolymers. The modified α-olefin-based elastic polymer is obtained by reacting the base α-olefin-based elastic polymer with the unsaturated carboxylic acid or its derivative described below by the method described below.

Examples of the unsaturated carboxylic acid or its derivative component unit of the graft monomer component constituting the modified α-olefin polymer include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid and itacone. Acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, endocis-bicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic acid (Nadic acid ^TM ), methyl-endocis-bicyclo [2.2.1] Hept-
Unsaturated dicarboxylic acids such as 5-ene-2,3-dicarboxylic acid (methyl nadic acid ^TM ), derivatives of unsaturated dicarboxylic acids such as acid halides, amides, imides, acid anhydrides and esters of the unsaturated dicarboxylic acids Specific examples thereof include maleenyl chloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, and glycidyl maleate. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid or acid anhydrides thereof are particularly preferable.

In order to produce the modified α-olefin-based elastic polymer by graft-copolymerizing a graft monomer selected from the unsaturated carboxylic acid or its derivative with the α-olefin-based elastic polymer, various conventionally known methods are available. The method can be adopted. For example, there is a method of melting the α-olefin-based elastic polymer and adding a graft monomer for graft copolymerization, or a method of dissolving it in a solvent and adding a graft monomer for graft copolymerization.
In any case, it is preferable to carry out the reaction in the presence of a radical initiator in order to efficiently graft-copolymerize the graft monomer. Grafting reaction is usually 6
It is performed at a temperature of 0 to 350 ° C. The proportion of the radical initiator used is usually in the range of 0.01 to 20 parts by weight with respect to 100 parts by weight of the α-olefin elastic polymer. As the radical initiator, organic peroxides, organic peresters, azo compounds and the like can be used.

The modified aromatic vinyl-conjugated diene copolymer or hydride thereof used in the present invention is a graft modified product of a block copolymer of an aromatic vinyl hydrocarbon and a conjugated diene compound. In the present invention, graft modified products of hydrides of these copolymers can also be used.

Specific examples of the aromatic vinyl-conjugated diene copolymer or hydride thereof used here include:
Styrene / butadiene block copolymer rubber, styrene /
Butadiene / styrene block copolymer rubber, styrene /
Isoprene block copolymer rubber, styrene / isoprene / styrene block copolymer rubber, hydrogenated styrene /
Butadiene / styrene block copolymer rubber, and
Examples thereof include hydrogenated styrene / isoprene / styrene block copolymer rubber.

In these copolymers, the molar ratio of the repeating unit derived from aromatic vinyl to the repeating unit derived from conjugated diene (aromatic vinyl hydrocarbon / conjugated diene) is usually 10/90. ˜70 / 30. The hydrogenated copolymer rubber is a copolymer obtained by hydrogenating a part or all of the double bonds remaining in the above-mentioned copolymer rubber.

The intrinsic viscosity [η] of this aromatic vinyl-conjugated diene copolymer or its hydrogenated product measured in decalin at 135 ° C. is usually 0.01 to 10 dl / g, preferably 0.08 to It is in the range of 7 dl / g and the glass transition temperature (Tg) is usually 0 ° C or lower, preferably -10 ° C or lower, and particularly preferably -20 ° C or lower. The crystallinity measured by the X-ray diffraction method is in the range of 0 to 10%, preferably 0 to 7%, particularly preferably 0 to 5%.

The modified aromatic vinyl-conjugated diene copolymer used in the present invention is obtained by converting the unmodified aromatic vinyl-conjugated diene copolymer as described above into the modified α-olefin random elastic copolymer. Similar to the production method, it is produced by graft modification with an unsaturated carboxylic acid, an unsaturated carboxylic acid anhydride or an unsaturated carboxylic acid derivative.

Examples of the unsaturated carboxylic acid, unsaturated carboxylic acid anhydride or unsaturated carboxylic acid derivative used here are compounds used in producing the above graft-modified α-olefin random elastic copolymer. These graft modifiers can be used alone or in combination.

Of these graft modifiers, it is preferable to use unsaturated carboxylic acid anhydrides, and maleic anhydride or nadic acid anhydride is particularly preferable. To graft polymerize such a graft modifier to the unmodified copolymer or a hydride thereof as described above, the above α
-Methods such as the solution method and the melting method described in the modification of the olefin random elastic copolymer can be employed.

In the graft reaction, the amount of the graft modifier used is set in consideration of its reactivity. Generally, the amount of the graft modifier is 100 parts by weight of the unmodified aromatic vinyl-conjugated diene copolymer or hydride. And used in a proportion of 1 to 10 parts by weight. In performing the graft reaction, a radical initiator such as an organic peroxide, an organic perester, and an azo compound can be used in the same manner as described above.

By carrying out the graft reaction in this way,
The graft modifier is usually added to 100 parts by weight of the unreacted aromatic vinyl-conjugated diene copolymer or hydride.
It is possible to obtain a graft-modified aromatic vinyl-conjugated diene copolymer or a hydrogenated product thereof, which is graft-polymerized in a proportion of 01 to 10 parts by weight, preferably 0.05 to 5 parts by weight.

The graft-modified aromatic vinyl-conjugated diene copolymer or hydride thereof thus obtained is a low crystalline or amorphous copolymer, and preferably substantially amorphous. That is, the crystallinity measured by the X-ray diffraction method is 10% or less, preferably 7% or less,
Particularly preferably, a modified copolymer of 5% or less is used, and further, a modified copolymer having a crystallinity of substantially 0% is preferably used. Therefore, many of the modified aromatic vinyl-conjugated diene copolymers or hydrides thereof do not show a clear melting point. Furthermore, because of its low crystallinity, this graft-modified aromatic vinyl-conjugated diene copolymer or its hydride is soft, and its tensile modulus is usually in the range of 0.1 kg / cm ^{2 to} less than 20000 kg / cm ^2. , preferably in the range of ^{1kg / cm 2 ~15000kg / cm 2} .

The melt index (value measured and measured at 190 ° C.) of this graft-modified aromatic vinyl-conjugated diene copolymer or its hydride is usually 0.1-1.0.
It is in the range of 30 g / 10 minutes, preferably 1.0 to 20 g / 10 minutes, and particularly preferably 2.0 to 15 g / 10 minutes.

Further, this graft-modified aromatic vinyl
The glass transition temperature (Tg) of the conjugated diene copolymer or a hydride thereof is usually -150 to + 50 ° C, preferably-.
The intrinsic viscosity [η] measured in decalin at 135 ° C. in the range of 80 to −20 ° C. is usually 0.01 to 10 dl /
It is in the range of g, preferably 1-5 dl / g.

Graft-modified aromatic vinyl as described above
By using a conjugated diene copolymer or a hydride thereof, a molded article having excellent toughness can be obtained. In the polyamide composition of the present invention, the blending ratio of the modified α-olefin polymer or the modified aromatic vinyl-conjugated diene block copolymer is in the range of 0.5 to 50 parts by weight with respect to 100 parts by weight of the polyamide. Preferably,
More preferably, it is in the range of 1.0 to 40 parts by weight. If the blending ratio of the modified α-olefin-based elastic polymer is less than 0.5 parts by weight, the impact resistance of the polyamide composition will decrease, and if it exceeds 50 parts by weight, the tensile strength of the polyamide composition will increase. The strength, bending strength, elastic modulus, and heat resistance may decrease.

Ionomer The ionomer used in the present invention is an ethylene-unsaturated carboxylic acid copolymer partially neutralized with a divalent metal ion or a monovalent metal ion. The ethylene-unsaturated carboxylic acid copolymer constituting the ionomer is
It is a copolymer of ethylene and an unsaturated carboxylic acid, and the unsaturated carboxylic acid is an unsaturated carboxylic acid having 3 to 8 carbon atoms, specifically acrylic acid, methacrylic acid, itaconic acid, maleic anhydride. Acid, maleic acid monomethyl ester, maleic acid monoethyl ester and the like are used. Of these unsaturated carboxylic acids, acrylic acid,
Methacrylic acid is particularly preferably used.

The ethylene-unsaturated carboxylic acid copolymer used in the present invention may contain a third component in addition to ethylene and the above-mentioned unsaturated carboxylic acid. As such a third component, Is a polar vinyl compound having about 3 to 12 carbon atoms, for example, ethyl acrylate, isobutyl acrylate, n-butyl acrylate, unsaturated carboxylic acid ester such as methyl acrylate, vinyl ester such as vinyl acetate.

In the ethylene unsaturated carboxylic acid copolymer used in the present invention, ethylene is usually present in an amount of 50 to 99% by weight, preferably 70 to 98% by weight, and the unsaturated carboxylic acid is usually present. It is present in an amount of 1 to 50% by weight, preferably 2 to 30% by weight.

When the ethylene-unsaturated carboxylic acid copolymer contains a third component in addition to the ethylene component and the unsaturated carboxylic acid, the third component is usually 40% by weight or less, preferably 30% by weight. Present in an amount of less than or equal to%.

The ionomer used in the present invention is a metal ion in which at least a part of the carboxyl groups in the ethylene-unsaturated carboxylic acid copolymer is a divalent metal ion or a monovalent metal ion, preferably a divalent transition metal ion. Have been neutralized by.

The metal ions used in such ionomers include alkali metal ions such as Na ⁺ , Li ⁺ and K ⁺ , Zn ⁺⁺ , Co ⁺⁺ , Ni ⁺⁺ , Pb ⁺⁺ and Cu ⁺⁺ . Divalent transition metal ions or alkaline earth metal ions such as Ca ⁺⁺ and Mg ⁺⁺ are preferable, and Zn ⁺⁺ is particularly preferable.

The degree of neutralization of the carboxyl group of the ethylene-unsaturated carboxylic acid copolymer with the above divalent metal ion, preferably the divalent transition metal ion, is 3 to 95%.
It is preferred that

The type of metal forming the ionomer is not limited to one type, and the ionomer used in the present invention may have two or more types of metal ions. Such an ionomer is used in the same amount as in the case of using the modified elastic copolymer.

Fibrous Reinforcing Material The semiaromatic polyamide composition of the present invention preferably contains a fibrous reinforcing material. Examples of such a fibrous reinforcing material include glass fiber, potassium titanate fiber, An inorganic fibrous reinforcing material or an organic fibrous reinforcing material such as a metal-coated glass fiber, a ceramic fiber, a wollastonite, a carbon fiber, a metal carbide fiber, and a hardened metal fiber is used. The surface of such a fibrous reinforcing material may be treated with a silane compound such as vinyltriethoxysilane, 2-aminopropyltriethoxysilane, 2-glycidoxypropyltrimethoxysilane. Among these, the inorganic fibrous reinforcing material is preferable from the viewpoint of heat resistance, and particularly glass fiber is preferable because it has the most excellent reinforcing effect.

If necessary, such a fibrous reinforcing material may be added in an amount of 5 to 2 with respect to 100 parts by weight of the semi-aromatic polyamide.
It is desirable that the amount is 50 parts by weight, preferably 10 to 220 parts by weight, more preferably 15 to 150 parts by weight.

Other Components In the polyamide composition of the present invention, in addition to the above components, other heat stabilizers, weather resistance stabilizers, plasticizers, thickeners, antistatic agents may be added to the polyamide composition in the range not impairing the object of the present invention. Various known compounding agents such as a release agent, a pigment, a dye, an inorganic or organic filler, a nucleating agent, an inorganic compound such as carbon black, talc, clay and mica may be added.

Furthermore, other various polymers, for example, polyolefins such as polyethylene, polypropylene, poly-4-methyl-1-pentene, ethylene / propylene copolymers, ethylene / 1-butene copolymers, propylene / ethylene copolymers. An olefin copolymer such as a propylene / 1-butene copolymer, polystyrene, polyamide, polycarbonate, polyacetal, polysulfone, polyphenylene oxide, a fluororesin, a silicone resin, and an aliphatic polyamide may be blended.

To prepare the semi-aromatic polyamide composition of the present invention, the respective components are mixed by various known methods such as a Henschel mixer, a V-blender, a ribbon blender, a tumbler blender, or after mixing, A method of melt kneading with a single-screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like and then granulating or pulverizing may be adopted.

The semi-aromatic polyamide contained in the semi-aromatic polyamide composition of the present invention has a low MO component content, so that mold stains due to the MO component are unlikely to occur, and venting of the mold is unlikely to occur, which is stable. The molded body can be manufactured in this state. Further, the characteristics of the semiaromatic polyamide are not deteriorated even by decreasing the content of the MO component, and the molded article formed by using the semiaromatic polyamide composition of the present invention has a semiaromatic polyamide It has excellent properties such as heat resistance, mechanical strength, low water absorption and low abrasion, which are essential properties, as well as excellent impact resistance and bending strength.

Further, the semi-aromatic polyamide composition of the present invention can be heated to a temperature above the melting point of the semi-aromatic polyamide and below the decomposition temperature, and can be molded into a desired shape using an ordinary molding device. .

[0084]

In the semiaromatic polyamide composition of the present invention, the concentration of the MO component contained in the semiaromatic polyamide is reduced by bringing the semiaromatic polyamide and the aqueous medium into contact with each other. By using the semi-aromatic polyamide composition of the present invention, which is less contaminated and is less likely to be clogged with the mold vent, precise electronic parts that require impact resistance, bending strength, heat resistance, etc. can be stably and accurately maintained for a long period of time. A molded product can be manufactured well.

[0085]

Next, the present invention will be described in more detail with reference to examples of the present invention. However, the present invention should not be construed as being limited to these examples.

[0086]

[Reference Example 1] 1,6-diaminohexane 99.
8 kg (859 mol), terephthalic acid 63.8 kg (384
And adipic acid 68.6 kg
(470 mol) was polycondensed to give 45 parts by weight of the repeating unit consisting of 1,6-diaminohexane and terephthalic acid and 55 parts by weight of the repeating unit consisting of 1,6-diaminohexane and adipic acid. A pellet of a semi-aromatic polyamide was prepared.

The MO component content in the semi-aromatic polyamide pellets was 0.45% by weight. The measuring method of the MO component in the present invention is as follows. [Measurement method of MO component] 20 to 30 g of polyamide pellets which have been dried under reduced pressure at 110 ° C. for 24 hours to remove water, and 200 ml of distilled water are placed in a 300 ml Erlenmeyer flask.
The mixture was stirred at 0 ° C. for 24 hours and extracted.

After the extract was cooled, it was filtered, the filtrate was transferred to an eggplant-shaped flask, while 50 cc of water was poured into the filtered pellet from above, and then 50 cc of isopropanol was poured thereinto to wash the pellet and the flask.

The obtained filtrate was transferred to the eggplant flask,
The solvent was distilled off under reduced pressure and the solid was dried to obtain an MO component.
The weight of this MO component was weighed together with the tare by a precision balance. M
The content (% by weight) of the O component was calculated by the following formula.

B / A × 100 = X B: Weight of MO component A: Weight of polyamide pellet before test X: Content of MO component (%)

[0091]

Reference Example 2 The semi-aromatic polyamide pellets of Reference Example 1 and 300 parts by weight of boiling water (100 ° C.) per 100 parts by weight of the semi-aromatic polyamide pellets were put in a drum, and the temperature of 100 ° C. was maintained. While stirring, the contact was made for 24 hours with stirring.

Next, the semi-aromatic polyamide pellets and water were separated and the pellets were dried. The MO component content in the semi-aromatic polyamide pellets thus treated was 0.05% by weight.

[0093]

Comparative Example 1 95 parts by weight of the semi-aromatic polyamide of Reference Example 1 and 5 parts by weight of maleated polyethylene were mixed in a tumbler, and a common twin-screw extruder (PCM- manufactured by Ikegai Tekko KK) was mixed.
45) was used to obtain extruded pellets at a cylinder temperature of 310 ° C. Table 1 shows the results of evaluation of mold stains and the amount of MO components of these pellets.

[0094]

[Example 1] The same as Example 1 except that the semi-aromatic polyamide of Reference Example 2 was used in place of Reference Example 1 in Comparative Example 1 above. [Evaluation method of mold stains] According to various resin standard injection conditions,
The resins of Examples and Comparative Examples were actually injection-molded using a spiral mold as shown in FIG. 1, and the number of times until the gas vent was clogged was measured.

[0095]

[Comparative Example 2] 95 parts by weight of the semi-aromatic polyamide of Reference Example 1 and 5 parts by weight of a maleinized ethylene / α-olefin copolymer (manufactured by Mitsui Petrochemical Industry Co., Ltd., Tuffmer) were mixed with a tumbler to prepare a mixture. Twin-screw extruder (Ikegai Tekko Co., Ltd.)
Extruded pellets at a cylinder temperature of 310 ° C. Table 1 shows the results of evaluation of mold stains and the amount of MO components of these pellets.

[0096]

Example 2 The procedure of Example 1 was repeated except that the semi-aromatic polyamide of Reference Example 2 was used instead of Reference Example 1 in Comparative Example 2 above.

[0097]

[Comparative Example 3] Ordinary twin-screw extruder (Ikegai Tekko KK, P
CM-45), and 81 parts by weight of the semi-aromatic polyamide of Reference Example 1 and a maleated ethylene / α-olefin copolymer (manufactured by Mitsui Petrochemical Industry Co., Ltd., Tuffmer) 1
A mixture in which 9 parts by weight was mixed with a tumbler was charged from a hopper, 15 parts by weight of glass fiber was further charged from a side feeder, and a cylinder temperature was set to 310 ° C. to obtain extruded pellets. Table 1 shows the results of evaluation of mold stains and the amount of MO components of these pellets.

[0098]

Example 3 The procedure of Example 3 was repeated except that the semi-aromatic polyamide of Reference Example 2 was used instead of Reference Example 1 in Comparative Example 3 above.

[0099]

[Table 1]

[Brief description of drawings]

FIG. 1 is a diagram showing a spiral mold used for evaluating mold stains.

Claims (4)

[Claims] 1. [I] (A) terephthalic acid and 4 to 12 carbon atoms
A repeating unit derived from an aliphatic diamine of (B)
Repeating unit derived from isophthalic acid and aliphatic diamine having 4 to 12 carbon atoms, (C) repeating unit derived from aliphatic dicarboxylic acid having 4 to 12 carbon atoms and aliphatic diamine having 4 to 12 carbon atoms , And (D) 6 to 20 carbon atoms
Of semi-aromatic polyamide having a repeating unit derived from lactam or aminocarboxylic acid of 99 to 30% by weight and [II] modified elastic polymer of 1 to 70% by weight. The repeating unit (A) is 40
-90 mol%, repeating unit (B) 0-50 mol%, repeating unit (C) 0-60 mol%, repeating unit (D) 0
A low molecular weight water-soluble component (M) which is bound in an amount of ˜50 mol% and which is contained in the semi-aromatic polyamide and measured by immersion in boiling water at 100 ° C. for 24 hours.
The semi-aromatic polyamide composition is characterized in that the content of (O component) is 0.25% by weight or less. 2. A semi-aromatic polyamide composition comprising [I] the semi-aromatic polyamide according to claim 1, [II] a modified elastic polymer, and [III] a fibrous reinforcing material. 3. The semiaromatic according to claim 1, wherein the amount of the low molecular weight boiling water-soluble component (MO component) contained in the semiaromatic polyamide is 0.15% by weight or less. Group polyamide composition. 4. A semi-aromatic polyamide [I] comprising terephthalic acid, and optionally isophthalic acid, an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, and 4 to 12 carbon atoms.
60-90 mol% of repeating units derived from (A) terephthalic acid and an aliphatic diamine having 4 to 12 carbon atoms by contacting the aliphatic diamine of (4) with lactam or aminocarboxylic acid, if necessary. , (B) 0 to 50 mol% of repeating units derived from isophthalic acid and an aliphatic diamine having 4 to 12 carbon atoms, (C) aliphatic dicarboxylic acid having 4 to 12 carbon atoms and 4 to 12 carbon atoms 0 to 60 mol% of repeating units derived from an aliphatic diamine, and
(D) A semi-aromatic polyamide containing a repeating unit derived from a lactam having 6 to 12 carbon atoms or an aminocarboxylic acid in an amount of 0 to 50 mol% is produced, and then the semi-aromatic polyamide is contacted with an aqueous medium. The semiaromatic according to claim 1, 2 or 3, characterized in that the content of the low molecular weight boiling water-soluble component (MO component) contained in the polyamide is 0.25% by weight or less. Group polyamide composition.