JP3453057B2 - Semi-aromatic polyamide resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a semi-aromatic polyamide capable of efficiently producing a molded product with less mold fouling during the production of the molded product, excellent creep resistance under high temperature and high humidity. It relates to a resin composition.

[0002]

2. Description of the Related Art Conventionally, various proposals have been made for a semi-aromatic polyamide having impact resistance. For example, Japanese Patent Application Laid-Open No. 4-108855 discloses a terephthalic acid unit 5
An aromatic dicarboxylic acid other than terephthalic acid or a dicarboxylic acid unit (a) consisting of 0 to 40 mol% of a linear aliphatic dicarboxylic acid unit having 6 to 18 carbon atoms and an alkylenediamine unit (b) It discloses a method for producing a polyamide composition comprising a semi-aromatic polyamide having: and a modified elastic copolymer.

It is also known that a composition comprising such a semi-aromatic polyamide and a modified elastic polymer is excellent in heat resistance and impact resistance. (JP-A-2-41
318, JP-A-5-98152).

[0004]

Such polyamides are remarkably excellent in impact resistance, heat resistance, mechanical properties and chemical-physical properties, but when injection molding is repeated using a mold. , White powder was sometimes deposited in the mold. Further, when used as an electronic device, creep characteristics under high temperature and high humidity are not sufficient, and improvement has been desired.

As a result of analysis of this powder by the present inventors, it was found that this powder was an unreacted monomer, a lower oligomer component and a polymer decomposition product. This unreacted monomer, lower oligomer or polymer decomposed product component is an electronic component,
In particular, when molding a fine component such as a connector, there are problems in that the appearance is impaired and the dimensional accuracy is not obtained.
Further, since white powder generated in the mold may clog the vent hole of the mold, it was necessary to stop the molding and clean the mold.

Therefore, it has excellent mechanical strength such as rigidity, impact resistance and bending strength, excellent creep characteristics, and excellent chemical and physical characteristics such as excellent impact resistance and heat resistance. It has been desired to develop a semi-aromatic polyamide resin composition that is less likely to cause the above-mentioned problems, has no vent of the mold, and is capable of producing a precision molded product having an excellent appearance.

The present invention provides a semi-aromatic polyamide resin composition capable of producing a molded product which is less likely to be contaminated by a mold during molding and has excellent properties such as creep properties under high temperature and high humidity. It is intended to be provided.

[0008]

That is, the present invention is
(A) A polyamide whose main constituent component unit is a repeating unit composed of a dicarboxylic acid component unit and a diamine component unit, wherein at least 45 mol% or more of the dicarboxylic acid component unit is a terephthalic acid component unit,
The melting point of the diamine component unit consisting of 55 to 99 mol% of a linear alkylenediamine component unit having 4 to 18 carbon atoms and 1 to 45 mol% of an alkylenediamine component unit having 4 to 18 carbon atoms having a side chain alkyl group. 280-33
99 to 60% by weight of a polyamide copolymer at 0 ° C., and (B) a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (i) the density is 0.89 to 0.9.
In the range of 5 g / cm ³ , (ii) the temperature (melting point; Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 90 to 127 ° C., and
(iii) an ethylene / α-olefin copolymer having a crystallinity of 20% to 60% measured by an X-ray diffraction method,
A semi-aromatic polyamide resin composition comprising 1 to 40% by weight of a modified ethylene / α-olefin copolymer having a graft amount of 0.01 to 5% by weight modified with an unsaturated carboxylic acid or a derivative thereof. Regarding things. The semi-aromatic polyamide resin composition of the present invention contains 55 mol% per all dicarboxylic acid units as the polyamide copolymer (A).
It is preferable to use those containing an aromatic carboxylic acid unit other than terephthalic acid and / or an aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms within the following range.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the specific semi-aromatic polyamide of the above (A) is selected among the semi-aromatic polyamides, and the modified ethylene / α-olefin copolymer of the above (B) is also selected. A characteristic is that a specific modified ethylene / α-olefin copolymer is selected and these are combined,
This reduces the amount of oligomers precipitated during molding, suppresses the clogging of the vent holes of the molding die, and enables molding for a long time. Further, the semi-aromatic polyamide resin composition of the present invention has excellent fluidity and brings about an advantage that the molding temperature can be lowered. Further, the semi-aromatic polyamide resin composition of the present invention has creep characteristics under high temperature and high humidity, heat aging resistance,
Excellent heat distortion resistance. Moreover, even by suppressing such a decrease in toughness, other excellent properties inherently possessed by the aromatic polyamide, such as mechanical strength and low water absorption, are not significantly deteriorated. is there.

[Polyamide (A)] The polyamide (A) used in the resin composition of the present invention comprises a specific dicarboxylic acid component unit [a] as a main constituent component unit and a specific aliphatic diamine component unit [b]. It is composed of repeating units consisting of.

When the total dicarboxylic acid component unit present in the polyamide used in the present invention is 100 mol%, the polyamide of the present invention has 4 terephthalic acid component units (a-1).
It is contained in an amount of 5 to 100 mol%, preferably 50 to 90 mol%, and more preferably 60 to 80 mol%. In addition, this polyamide contains 0 to 55 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol% of an aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid.
It is contained in the amount of. Furthermore, this polyamide contains the aliphatic dicarboxylic acid component unit (a-3) in an amount of 0 to 55 mol%. Since the polyamide has a small amount of the aliphatic dicarboxylic acid component unit (a-3), specifically, it is 10 to 50 mol%, more preferably 20 to 4
The moldability is improved by containing 0 mol%. The content of the aliphatic dicarboxylic acid component unit is 55
When it exceeds mol%, the content of the terephthalic acid component unit necessarily falls below 45 mol%, and such a polyamide tends to have a high water absorption and a melting point of less than 280 ° C. Therefore, the molded body formed from such a polyamide tends to have a large dimensional change due to water absorption or insufficient heat resistance.

The diamine component unit [b] forming a repeating unit together with the above dicarboxylic acid component unit is a linear aliphatic alkylenediamine component unit having 4 to 18 carbon atoms, and a carbon atom having a side chain alkyl group. Number 4 to 1
8 is an alkylenediamine component unit.

The polyamide used in the present invention contains 5 mol of the linear aliphatic alkylenediamine component unit (b-1) having 4 to 18 carbon atoms based on 100 mol% of all diamine component units.
5 to 99 mol%, preferably 70 to 98 mol%, more preferably 80 to 95 mol%, and particularly preferably 85 to 9 mol%.
It is contained in an amount of 3 mol%. The alkylenediamine component unit (b-2) having a side chain alkyl group having 4 to 18 carbon atoms is 1 to 45 mol%, preferably 2 to 30 mol%, more preferably 5 to 20 mol%, particularly preferably Is contained in an amount of 7 to 15 mol%. Thus, by containing two kinds of specific alkylenediamine component units in the amounts as described above, the melting point of polyamide as the main component of the composition of the present invention is a molded article (or molten polyamide) during injection molding. Is so low that it does not cause gas burning. Also, the precipitation of white powder in the mold is reduced,
Moreover, the Tg of polyamide is as high as 80 ° C. or higher, the creep property under high temperature and high humidity is excellent, and the crystallization rate is fast.

That is, when the content of the linear alkylenediamine component unit (b-1) having 4 to 18 carbon atoms exceeds 99 mol%, white powder is likely to be generated during injection molding. Further, the number of carbon atoms having a side chain alkyl group is 4 to 18
Content of the alkylenediamine component unit (b-2) is 4
If it exceeds 5 mol%, the crystallization rate of the polyamide becomes slow and heat resistance becomes insufficient.

The polyamide repeating unit composed of the dicarboxylic acid component unit and the diamine component unit as described above is represented by the following formula. The repeating unit forming the polyamide has a terephthalic acid component unit (a-1) as a dicarboxylic acid component unit [a] which is an essential component unit. The repeating unit having such a terephthalic acid component unit (a-1) has the following formula [Ia]

[Chemical 1] In the formula, R ¹ has 4 to 4 carbon atoms which may have a side chain.
It can be represented by 18 alkylene groups. The dicarboxylic acid component unit [a] is entirely the above [Ia]
It is not necessary that the component unit is represented by the formula (1), and a part of the terephthalic acid component unit (a-1) as described above may be replaced with another dicarboxylic acid component.

The carboxylic acid component unit other than the terephthalic acid component includes an aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid and an aliphatic dicarboxylic acid component unit (a-3).

Examples of the aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid include an isophthalic acid component unit, a 2-methylterephthalic acid component unit and a naphthalenedicarboxylic acid component unit. As the component unit derived from an aromatic dicarboxylic acid other than terephthalic acid, an isophthalic acid component unit is particularly preferable.

Among the aromatic dicarboxylic acid component units (a-2) other than terephthalic acid, the repeating unit having an isophthalic acid component unit particularly preferred in the present invention is represented by the following formula [Ib].

[Chemical 2] In the formula, R ¹ has 4 to 1 carbon atoms which may have a side chain.
Which is an alkylene group of 8.

Aliphatic dicarboxylic acid component unit (a-3)
Is derived from an aliphatic dicarboxylic acid having an alkylene group of 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Examples of such aliphatic dicarboxylic acids include succinic acid,
Mention may be made of adipic acid, azelaic acid and sebacic acid. As the aliphatic dicarboxylic acid component unit, an adipic acid component unit and a sebacic acid component unit are particularly preferable.

A repeating unit having an aliphatic dicarboxylic acid component unit (a-3) as another dicarboxylic acid component unit constituting the dicarboxylic acid component unit [a] is represented by the following formula [II]

[Chemical 3] In the formula, R ¹ has 4 to 1 carbon atoms which may have a side chain.
8 is an alkylene group, and n is usually an integer of 2 to 18, preferably an integer of 4 to 10.

The diamine component unit [b] forming the polyamide used in the present invention is a linear alkylenediamine component unit (b-1) having 4 to 18 carbon atoms and 4 to 18 carbon atoms having a side chain alkyl group. Is an alkylenediamine component unit (b-2).

Specific examples of such a linear alkylenediamine component unit (b-1) include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane and 1,8-. Mention may be made of diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane. Among these, component units derived from 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane are preferable, and the polyamide of the present invention contains these component units. Plural kinds of component units may be contained.
Further, among these, a component unit derived from 1,6-diaminohexane is particularly preferable.

Specific examples of the alkylenediamine component unit (b-2) having a side chain alkyl group and having 4 to 18 carbon atoms include 1-butyl-1,2-diamino-ethane and 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,
And component units derived from 5-methyl-1,9-diamino-nonane.

In the present invention, the number of carbon atoms shown in the description of the alkylenediamine component unit having a side chain alkyl group, unless otherwise specified, is 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.

Among the alkylenediamine component units having a side chain alkyl group as described above, one or two side chain alkyl groups having 1 to 2 carbon atoms are contained and the main chain has 4 to 10 carbon atoms. Component units derived from the side chain alkyldiamine are preferred, with 2-methyl-1,5-diaminopentane component units being especially preferred.

Examples of repeating units having constituent units derived from 2-methyl-1,5-diaminopentane, which is a particularly preferred side chain alkyldiamine used in the present invention, are shown below.

[Chemical 4] In the formula, R ² is a p-phenylene group or m- under the condition that 45 to 100 mol% thereof is a p-phenylene group.
It is a divalent hydrocarbon group such as a phenylene group or an alkylene group.

The polyamide which can be used in the present invention is, as the dicarboxylic acid component unit, a terephthalic acid component unit which is the above main component unit, and a divalent aromatic carboxylic acid other than terephthalic acid represented by an isophthalic acid component unit. In addition to the acid-derived component unit and the above-mentioned aliphatic dicarboxylic acid component unit, a small amount of a component unit derived from a polybasic carboxylic acid of tribasic or higher such as trimellitic acid or pyromellitic acid is contained. May be. The component unit derived from such a polycarboxylic acid is usually contained in the polyamide in an amount of 0 to 5 mol%.

The intrinsic viscosity [η] of the polyamide used in the present invention measured in concentrated sulfuric acid at a temperature of 30 ° C. is usually 0.5 to 3.0 dl / g, preferably 0.5 to 2.8 d.
1 / g, particularly preferably in the range of 0.6 to 2.5 dl / g.

The polyamide used in the present invention has a higher melting point than the conventionally used aliphatic polyamide, but the melting point often does not exceed 310 ° C. That is, the polyamide used in the present invention is usually 280 to 3
Has a melting point of 05 ° C, often 290-30
It has a melting point in the range of 5 ° C. Further, the polyamide used in the present invention is particularly excellent in heat resistance, has a low water absorption rate, and has little post-crystallization due to annealing of a molded product. The glass transition temperature in the amorphous portion of the polyamide used in the present invention is usually 80 ° C or higher, preferably 90 to 150 ° C.

The polyamide used in the present invention can be produced by polycondensation of a dicarboxylic acid component and a diamine component. Specifically, this polyamide comprises terephthalic acid, or an aromatic dicarboxylic acid other than terephthalic acid, an aliphatic dicarboxylic acid, a linear dialkylenediamine, and an alkylenediamine having a side chain alkyl group as described above. By mixing in an aqueous medium in an amount, in the presence of a catalyst such as sodium hypophosphite, heated under pressure to first produce a polyamide precursor, and then by melt-kneading the polyamide precursor. You can When producing the polyamide precursor, a molecular weight modifier such as benzoic acid may be added.

Further, the polyamide used in the present invention is produced by separately producing a polyamide having a side chain alkyl group and a polyamide having no side chain, and melt-kneading these to carry out an amide exchange reaction. You can also

The polyamide used in the present invention is melt-kneaded by adjusting the compounding amount of at least two kinds of polyamides having different compositions so that the dicarboxylic acid component unit and the diamine component unit are within the above range. It can also be manufactured by

For example, the polyamide (A) used in the present invention
(A-1): a dicarboxylic acid component unit is 45 to 100 mol% of a terephthalic acid component unit, 0 to 55 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid, and / or a carbon atom. Number 4 to 20 aliphatic dicarboxylic acid component unit 0 to
55 mol% and the diamine component unit is a linear alkylenediamine component unit having 4 to 18 carbon atoms.
0 mol% of polyamide (hereinafter referred to as “linear polyamide”)
And (A-2): the dicarboxylic acid component unit is 45 to 100 mol% of a terephthalic acid component unit, 0 to 55 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid, and / or 4 carbon atoms. ~ 20 aliphatic dicarboxylic acid component units 0 ~
55 mol% and the diamine component unit is a straight chain alkylenediamine component unit having 4 to 18 carbon atoms.
95 mol% and 4 carbon atoms having a side chain alkyl group
To 18 alkylenediamine component units of 5 to 95 mol% (hereinafter referred to as "side chain polyamide")
The linear polyamide (A-1) and the side chain polyamide (A-2) may be combined by melt kneading or the like.

The following may be mentioned as examples of the linear polyamide (A-1). (A-1-1): Polyamide comprising the constituent component units of the above formulas [Ia] and [II]. However, the formulas [Ia] and [I
The R ¹ groups in [I] are all linear alkylene groups (C number:
4-18). In this case, the [Ia] unit is 45 mol% or more, preferably 45 to 70 mol%, most preferably 45 to 60 mol%, and the [II] unit is 55 mol% or less, preferably 55 to 30 mol%, Most preferably 5
It is preferably in the range of 5 to 40 mol%.

(A-1-2): Formulas [Ia] and [I]
-A polyamide comprising the constituent component units of [b] and [II].
However, the R ¹ groups in the formulas [Ia], [Ib] and [II] are all linear alkylene groups (C number: 4 to 18). In this case, the [Ia] unit is 50 to 80 mol%,
Preferably, it is 60 to 70 mol%, and the [Ib] unit is 10
To 40 mol%, preferably 20 to 30 mol%, [I
I] unit is 30 to 5 mol%, preferably 20 to 10
It should be in the range of mol%.

Examples of the side chain polyamide (A-2) include the following. (A-2-1): Polyamide comprising the constituent component units of the above formulas [Ia] and [III]. However, R in the formula [Ia]
^One group is a linear alkylene group (C number: 4 to 18)
The R ² group in [III] is a p-phenylene group. In this case, the [I-a] unit is 5 to 95 mol%, preferably 3
0 to 70 mol%, most preferably 40 to 60 mol%, [III] unit is 95 to 5 mol%, preferably 70
It is preferably in the range of 30 to 30 mol%, most preferably 60 to 40 mol%.

(A-2-2): Formulas [Ia] and [I
-A polyamide composed of the constituent units of [b] and [III].
However, R ¹ groups in the formulas [Ia] and [Ib] are both linear alkylene groups (C number: 4 to 18), and the formula [III]
The R ² group therein is a p-phenylene group. . in this case,
[Ia] unit is 25 to 65 mol%, preferably 30
To 50 mol%, the [Ib] unit is 5 to 30 mol%,
It is preferably 10 to 20 mol%, and the content of the [III] unit is 30 to 70 mol%, preferably 40 to 60 mol%.

Polyamide (A) obtained by combining the above linear polyamide (A-1) and side chain polyamide (A-2).
When used as, the linear polyamide (A-1) is used in an amount of 45 parts by weight or more, particularly 50 to 95 parts by weight, and the side chain polyamide (A-2) is used in an amount of 5 parts by weight or more, particularly 5 to 50 parts by weight. Is preferred. Among these, (A-1-
When the polyamide (A) is prepared from the linear polyamide of (1) and the side chain polyamide of (A-2-1), (A-1-
1) 45 to 95% by weight, preferably 60 to 90% by weight, most preferably 70 to 85% by weight, (A-2-1)
Is used in an amount of 55 to 5% by weight, preferably 40 to 10% by weight, and most preferably 30 to 15% by weight.
Within this range, it is possible to obtain a semi-aromatic polyamide resin composition having excellent creep and less generation of white powder.

[Modified Ethylene / α-Olefin Copolymer (B)] The modified ethylene / α-olefin copolymer (B) used in the present invention is obtained by converting the ethylene / α-olefin copolymer [B1] into an unsaturated carboxylic acid. It is graft-modified with an acid or a derivative thereof.

The ethylene / α-olefin copolymer [B1] before graft modification has ethylene and 3 to 10 carbon atoms.
It consists of 20 α-olefins. This ethylene α-
The ethylene content of the olefin copolymer [B1] is 70
It is at least mol%, preferably 80 to 98 mol%.

Specific examples of the α-olefin include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-
For example, decene. Among them, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferably used. These α-olefins can be used alone or in combination of two or more.

The ethylene / α-olefin copolymer [B1] has a density of 0.89 to 0.95 g / cm ³ , preferably 0.90 to 0.94 g / cm ³ , and particularly preferably 0.91. To 0.93 g / cm ³ . Within this range, it is possible to obtain a composition having excellent creep properties and less generation of white powder.

Further, the ethylene / α-olefin copolymer [B1] has a temperature (melting point; Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) of 90 ° C to 127 ° C, preferably Is in the range of 95 to 120 ° C.

Furthermore, the ethylene / α-olefin copolymer [B1] has a crystallinity of 20 to 60%, more preferably 25 to 55%, preferably 30 to 50% as measured by an X-ray diffraction method. It is in the range and is resinous.

Further, the melt flow rate (MFR; ASTM D) of the ethylene / α-olefin copolymer [B1] is
1238, 190 ° C., 2.16 kg load) is usually 0.01 to 100 g / 10 minutes, preferably 0.1 to 50.
g / 10 minutes, more preferably 0.2 to 20 g / 10 minutes.

Ethylene.α-having the above physical properties
The olefin copolymer [B1] can be produced by a conventionally known method using a catalyst of titanium (Ti) type, vanadium (V) type, zirconium (Zr) type, or the like.

In the modified ethylene / α-olefin copolymer (B) used in the present invention, the graft amount of the unsaturated carboxylic acid or its derivative is 100% by weight of the modified ethylene / α-olefin copolymer (B). In the range of 0.01 to 5% by weight, preferably 0.1 to 3% by weight.

The unsaturated carboxylic acid grafted to the ethylene / α-olefin copolymer [B1] is as follows:
Specifically, acrylic acid, methacrylic acid, maleic acid,
Examples include fumaric acid and itaconic acid. Examples of unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, and metal salts. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid. Monomethyl ester, fumaric acid dimethyl ester, itaconic acid monomethyl ester, itaconic acid diethyl ester, acrylamide, methacrylamide,
Maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, fumaric acid Acid diamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide,
Examples thereof include N-butyl maleimide, N-phenyl maleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate and the like. Of these grafting monomers it is most preferred to use maleic anhydride.

Graft modification to the ethylene / α-olefin copolymer [B1] using the above unsaturated carboxylic acid or its derivative (graft monomer) can be carried out by various conventionally known methods. For example, a melt modification method in which ethylene / α-olefin copolymer [B1] is melted using an extruder, and a graft monomer is added to perform graft copolymerization, or ethylene / α-olefin copolymer [B1] is used as a solvent. There is a solution modification method in which a graft monomer is added to the solution, and a graft monomer is added to carry out graft copolymerization.
In any case, in order to efficiently graft-copolymerize the graft monomer, it is preferable to start the reaction in the presence of a radical initiator.

As the radical initiator, organic peroxide, organic perester and the like are preferably used. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-
Butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3,1,4-
Organic peroxides such as bis (tert-butylperoxyisopropyl) benzene and lauroyl peroxide;
tert-butyl peracetate, 2,5-dimethyl-
2,5-di (tert-butylperoxy) hexyne-
3,2,5-Dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, te
Organic peresters such as rt-butyl perisobutyrate, tert-butyl per-sec-octoate, tert-butyl perpivalate, cumyl pervivarate, tert-butyl perdiethyl acetate; azoisobutyronitrile, dimethylazoiso An azo compound such as butyrate is used. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,
5-dimethyl-2,5-di (peroxybenzoate)
Hexin-3,2,5-dimethyl-2,5-di (ter
t-Butylperoxy) hexane, 1,4-bis (te
Dialkyl peroxides such as rt-butylperoxyisopropyl) benzene are preferred. The above radical initiator is an ethylene / α-olefin copolymer [B
1] It is usually used in a proportion of 0.001 to 1 part by weight with respect to 100 parts by weight.

In addition, other monomers such as styrene may coexist in the above graft reaction.

[Semi-Aromatic Polyamide Resin Composition] The semi-aromatic polyamide resin composition of the present invention has the following formula [IV] prepared from brominated styrene monomer:

[Chemical 5] In the formula, m is a number of 1 or more and 5 or less, and an organic flame retardant such as a polybrominated styrene, a bromide of polyethylene ether, a bromide of polystyrene or the like having a structural unit of as a main constituent can be blended.

The polybrominated styrene preferably contains dibrominated styrene units in an amount of 60% by weight or more.
Those containing at least wt% are particularly preferable. In addition to dibrominated styrene, polybrominated styrene obtained by copolymerizing 40% by weight or less, preferably 30% by weight or less, of monobrominated styrene and / or tribrominated styrene may be used.

The amount of the organic flame retardant added is 0 to 60 parts by weight, preferably 1 to 20 parts by weight, and particularly preferably 2-1 to 100 parts by weight of the semiaromatic polyamide resin.
5 parts by weight. Also, in order to obtain more sufficient flame retardancy, 4
It is preferable to add about 0 to 60 parts by weight. If it is less than 0.5 part by weight, the flame retardant effect is insufficient, and if it is more than 60 parts by weight, mechanical and thermal properties are deteriorated, which is not preferable.

In the semiaromatic polyamide resin composition of the present invention, in addition to the above organic flame retardant, at least one flame retardant selected from antimony oxide, sodium antimonate, tin oxide, iron oxide, zinc oxide and zinc nitrate. Fuel aids can be used, especially sodium antimonate, especially 550
Substantially anhydrous sodium antimonate, which has been heat-treated at a high temperature of ℃ or more, is preferable. The amount of the flame retardant aid added is 0 to 10 parts by weight, preferably 2 to 8 parts by weight.

In the semi-aromatic polyamide resin composition of the present invention, PPS (polyphenylene sulfide), PPE (polyphenyl ether), PES (polyether sulfone), PEI (polyether imide), LCP ( A heat resistant resin such as a liquid crystal polymer) or a modified product of these resins may be blended, and polyphenylene sulfide is particularly preferable. The amount of the heat resistant resin in the semi-aromatic polyamide resin composition of the present invention is usually less than 50% by weight, preferably 0 to 40% by weight.

Further, the semi-aromatic polyamide resin composition of the present invention contains an antioxidant (heat-resistant stabilizer, such as a phosphorus-based antioxidant, a phenol-based antioxidant, an amine-based antioxidant and a sulfur-based antioxidant. ) Can be blended.

Examples of phosphorus antioxidants include 9,10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenylphosphite, 2-
Ethylhexyl acid phosphate, dilauryl phosphite, tri-iso-octyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trilauryl phosphite, trilauryl-di-thiophosphite, trilauryl-tri- Thiophosphite, trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite, trioctadecylphosphite,
1,1,3-tris (2-methyl-di-tridecylphosphite-5-tert-butylphenyl) butane,
4,4'-butylidene-bis (3-methyl-6-ter
t-butyl) tridecyl phosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butyl-di-tridecyl) phosphite, bis (2,4-di-te)
rt-Butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-tert-butyl-4)
-Methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-bisphenylene diphosphite, distearyl pentaerythritol diphosphite, tridecylphosphite, tri Stearyl phosphite,
2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, sorbit-tris-phosphite-distearyl-mono-C30-diol ester and bis (2,4,6-tri-tert. −
Butylphenyl) pentaerythritol diphosphite may be mentioned. Among these, bis (2,4-
Di-tert-butylphenyl) pentaerythritol-di-phosphite and bis (2,6-di-tert.
-Butyl-4-methylphenyl) pentaerythritol-di-phosphite and other pentaerythritol-di-
Phosphite-based phosphorus antioxidant and tetrakis (2,4-di-tert-butylphenyl) 4,4 '
-Bisphenylenediphosphite may be mentioned.

Examples of phenolic antioxidants include:
3,9-bis {2- [3- (3-tert-butyl-4
-Hydroxy-5-methylphenyl) propionyl]-
1,1-Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 2,6-di-te
rt-butyl-p-cresol, 2,4,6-tri-t
ert-butylphenol, n-octadecyl-3-
(4'-Hydroxy-3 ', 5'-di-tert-butylphenol) propionate, styrenated phenol, 4-hydroxy-methyl-2,6-di-tert-
Butylphenol, 2,5-di-tert-butyl-hydroquinone, cyclohexylphenol, butylhydroxyanisole, 2,2'-methylene-bis- (4-
Methyl-6-tert-butylphenol), 2,2 '
-Methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4'-iso-propylidenebisphenol, 4,4'-butylidene-bis (3-methyl-)
6-tert-butylphenol), 1,1-bis-
(4-Hydroxy-phenyl) cyclohexane, 4,
4'-methylene-bis- (2,6-di-tert-butylphenol), 2,6-bis (2'-hydroxy-
3'-tert-butyl-5'-methylmethylbenzyl) 4-methyl-phenol, 1,1,3-tris (2
-Methyl-4-hydroxy-5-tert-butyl-
Phenyl) butane, 1,3,5-tris-methyl-2,
4,6-Tris (3,5-di-tert-butyl-4-
Hydroxy-benzyl) benzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydrooxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydrooxyphenyl) ) Isocyanurate, tris [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanate, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2, 2'-thiobis (4-methyl-6-tert
-Butylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), and N,
N'-hexamethylene bis (3,5-di-tert-butylphenol-4-hydroxycinnamamide) can be mentioned.

Further, as an example of the amine type antioxidant,
4,4'-bis (α, α-dimethylbenzyl) diphenylamine, phenyl-α-naphthylamine, phenyl-
β-naphthylamine, N, N′-diphenyl-p-phenylenediamine, N, N′-di-β-naphthyl-p-phenylenediamine, N-cyclohexyl-N′-phenyl-p-phenylenediamine, N-phenyl- N'-isopropyl-p-phenylenediamine, aldol-α
-Naphthylamine, 2,2,4-trimethyl-1,2-
Polymers of dihydroquinone and 6-ethoxy-2,
2,4-trimethyl-1,2-dihydroquinoline can be mentioned.

Further, examples of sulfur antioxidants include thiobis (β-naphthol), thiobis (N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, dodecylmercaptan, tetramethyl. Mention may be made of thiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, dilaurylthiodipropionate and distearylthiodipropionate.

These antioxidants can be used alone or in combination. Among such antioxidants, it is particularly preferable to use a phosphorus-based antioxidant alone or in combination with other antioxidants.

These antioxidants are used in an amount of 0.05 to 2 parts by weight with respect to 100 parts by weight of the resin component.
Particularly, it is preferably used in an amount within a range of 0.1 to 1.5 parts by weight, and particularly preferably used in an amount within a range of 0.2 to 1.0 parts by weight.

In addition, the semi-aromatic polyamide resin composition of the present invention contains, as an inorganic reinforcing material, fibrous, powdery, granular,
Various inorganic fillers having a plate shape, a needle shape, a cloth shape, a mat shape, or the like can be blended.

For example, suitable examples of the fibrous inorganic filler include glass fiber, carbon fiber, asbestos fiber and boron fiber. Of these, glass fiber is particularly preferable. By using the glass fiber, the moldability is improved, and the mechanical strength of the molded product containing the inorganic reinforcing material, such as tensile strength, bending strength, and bending elastic modulus, and heat resistance such as heat deformation temperature are improved. The average length of the above glass fibers is usually 0.1 to 20 m.
m, preferably in the range of 0.3 to 6 mm, and the aspect ratio is usually 10 to 2000, preferably 30 to 60.
It is in the range of 0. It is preferable to use glass fibers having an average length and aspect ratio within such a range. Such glass fiber is usually used in an amount of 200 parts by weight or less, preferably 5 to 100 parts by weight of the resin component.
It is added in an amount of 180 parts by weight, more preferably 5 to 150 parts by weight.

In addition to the above-mentioned fibrous inorganic filler, examples of various fillers used in the present invention having a powdery, granular, plate-like, needle-like, cloth-like, matte-like, etc. Powder or plate-like inorganic compounds such as silica, silica-alumina, alumina, calcium carbonate, titanium dioxide, talc, wollastonite, diatomaceous earth, clay, kaolin, spherical glass, mica, gypsum, red iron oxide, magnesium oxide and zinc oxide And acicular inorganic compounds such as potassium titanate.

Two or more kinds of these fillers can be mixed and used. Further, these fillers may be treated with a silane coupling agent or a titanium coupling agent before use.

The average particle size of such a filler is usually 0.1 to 200 μm, preferably 1 to 100 μm.

Such a filler is used in an amount of usually 200 parts by weight or less, preferably 100 parts by weight or less, particularly preferably 1 to 50 parts by weight, based on 100 parts by weight of the resin component. To be done.

In addition to the above components, the polyamide resin composition of the present invention contains an organic filler, a heat stabilizer, a weather resistance stabilizer, an antistatic agent, and an antislip agent, as long as the characteristics are not impaired. Additives such as anti-blocking agents, anti-fog agents, lubricants, pigments, dyes, natural oils, synthetic oils and waxes may be added.

Examples of organic fillers include polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, condensates of diaminodiphenyl ether and terephthalic acid (isophthalic acid), and paraparaphenylene terephthalamide. Wholly aromatic polyamides such as condensates of (meth) aminobenzoic acid; wholly aromatic polyamideimides such as condensates of diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride; wholly aromatic polyesters; wholly aromatic polyimides; Heterocycle-containing compounds such as polybenzimidazole and polyimidazophenanthroline; and secondary processed products such as powdery, plate-like, fibrous or cloth-like products formed from polytetrafluoroethylene and the like. Door can be.

The semi-aromatic polyamide resin composition prepared as described above is used to obtain a desired shape by using a usual melt molding method such as compression molding method, injection molding method or extrusion molding method. A molded body can be manufactured.

For example, the semi-aromatic polyamide resin composition of the present invention is put into an injection molding machine in which the cylinder temperature is adjusted to about 350 to 300 ° C. to be in a molten state, and then introduced into a mold having a predetermined shape. By doing so, a molded body can be manufactured.

The shape of the molded article produced using the semi-aromatic polyamide resin composition of the present invention is not particularly limited, and examples thereof include electric tools and general industrial parts, mechanical parts such as gears and cams, and prints. It is possible to manufacture molded articles of various forms such as wiring boards and electronic parts such as housings of electronic parts, and especially as a resin for forming automobile interior / exterior parts, engine room parts, automobile electrical parts, etc. It is suitable.

Further, the semi-aromatic polyamide resin composition of the present invention is highly useful as a resin for producing a connector for interconnecting electronic circuits. That is, the connector manufactured from the semi-aromatic polyamide resin composition as described above has excellent heat resistance, and of course, this connector is less likely to be deformed under stress under high temperature and high humidity.

[0076]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not exceeded. In the examples,
The melting point and crystallinity were measured, and the performance of the obtained resin composition was evaluated by the following methods.

Melting point: A DSC endothermic curve was determined and the temperature at the maximum peak position was taken as the melting point (Tm). The endothermic curve was measured by packing the sample in an aluminum pan and rapidly raising the temperature to 200 ° C.
After the temperature was kept at 0 ° C. for 5 minutes, the temperature was lowered to room temperature at 20 ° C./min, and then the temperature was raised at 10 ° C./min. Crystallinity: A 1 mm pressed sheet was prepared using the sample and measured at 23 ° C. by an X-ray diffraction method.

1. Mechanical Strength Flexural Modulus (FM) Measured by the method of ASTM D-790. Izod impact strength (IZ) It was measured by the method of ASTM D-256 (with notch). 2. Bending creep property It carried out according to the method of JIS K7116. However, the test atmosphere is a temperature of 40 ° C specified by JIS C0022,
The condition of relative humidity 93% was adopted, and the strain amount after 7 days was evaluated. In addition, the measurement atmosphere is 23 ° C, 50% RH, or 40
C., 95% RH, the elapsed time (days) and the creep deformation amount (m) for the test pieces obtained in each Example and Comparative Example.
The relationship with m) is shown in FIGS. 2 and 3. 3. Evaluation of mold clogging (1) A mold as shown in FIG. 1 (A) for making a test piece was provided with a gas vent (air vent) of a mold having a depth of 10 μm and a width of 3 mm at the end, and Injection molding was performed under the molding conditions shown. (2) Molding conditions a. Molding machine: Sumitomo Heavy Industries, Ltd. SG50-M
III b. Molding conditions Cylinder set temperature: 330 ° C Mold temperature: 120 ° C Injection speed: 60mm / sec (3) Judgment of vent clogging Repeated molding of polyamide containing many components such as unreacted monomers, lower oligomers and polymer decomposition products, These components deposit on the vent and block the vent. Further, when the vent is closed, it becomes difficult for the air in the mold to escape, and the gas undergoes adiabatic compression at the final filling portion, resulting in a high temperature. When the temperature of the gas becomes high, the resin that is in contact with electricity is carbonized and blackened, so that “gas burn” occurs, and the tip of the obtained test piece becomes black as shown in FIG. 1 (B). 4. Heat distortion temperature (HDT) Measured by the method of ASTM D 648.

Reference Example 1 1,6-diaminohexane 1
39.3 g (1.20 mol), 2-methyl-1,5-diaminopentane 139.3 g (1.20 mol), terephthalic acid 365.5 g (2.2 mol), sodium hypophosphite as a catalyst 0 0.55 g (5.2 × 10 ⁻³ mol) and 64 ml of ion-exchanged water were charged into a 1-liter reactor, and after purging with nitrogen, the reaction was carried out at 250 ° C. and 35 kg / cm ² for 1 hour. 1,6-diaminohexane and 2-
The molar ratio with methyl-1,5-diaminopentane is 50:
50. After 1 hour, the reaction product formed in the reactor was connected to the reactor and the pressure was adjusted to about 10
561 g of polyamide precursor having an intrinsic viscosity [η] of 0.15 dl / g, which was taken out to a receiver set to a lower kg / cm ²
Got

Then, the polyamide precursor is dried,
Aromatic polyamide (PA-1) was obtained by melt polymerization at a cylinder temperature of 330 ° C. using a twin-screw extruder. The composition of this aromatic polyamide is as follows. The content rate of the 1,6-diaminohexane component unit in the diamine component unit is
The content of 50 mol% and 2-methyl-1,5-diaminopentane component unit was 50 mol%.

Reference Example 2 1,6-diaminohexane 2
69.3 g (2.32 mol), terephthalic acid 205.6
g (1.24 mol), adipic acid 148.0 g (1.0
1 mol) 0.48 g (4.50 g) of sodium hypophosphite as a catalyst
X10 ^-3 mol), and benzoic acid 3.43 as a molecular weight regulator
g (2.81 × 10 ^-2 mol) and ion-exchanged water 62 m
l, was charged into a 1 liter reactor, and after purging with nitrogen, 25
The reaction was carried out for 1 hour at 0 ° C. and 35 kg / cm ² .
The molar ratio of terephthalic acid to adipic acid is 55:45. After 1 hour, the reaction product formed in the reactor was connected to the reactor and the pressure was about 10 kg / c.
It was extracted into a receiver set to have a lower m ² and 559 g of a polyamide precursor having an intrinsic viscosity [η] of 0.15 dl / g was obtained.

Then, the polyamide precursor is dried,
Aromatic polyamide (PA-2) was obtained by melt polymerization using a twin screw extruder at a cylinder set temperature of 330 ° C. The composition of this aromatic polyamide is as follows. The terephthalic acid component unit content in the dicarboxylic acid component unit is 5
5 mol%, adipic acid component unit content is 45 mol%.

Example 1 After drying the polyamide having [η] of 1.05 dl / g produced in Reference Example 1 and the polyamide having [η] produced in Reference Example 2 of 1.00 dl / g, respectively. , 25:75 by weight and melt-extruded at a cylinder temperature of 330 ° C. using a twin-screw extruder to obtain an aromatic polyamide composition having a methyl group in the side chain. The composition of this aromatic polyamide is as follows. The 1,6-diaminohexane component unit content in the diamine component unit is 88 mol%, and the 2-methyl-1,5-diaminopentane component unit content is 12 mol%.
The terephthalic acid component unit content in the dicarboxylic acid component unit was 66 mol%, and the adipic acid component unit content was
It is 34 mol%.

[Production of modified ethylene / 1-butene copolymer] Ethylene / 1-butene copolymer prepared using a Ti-based catalyst [abbreviated as (PE-1); density = 0.920 g /
cm ³ , melting point (Tm) = 124 ° C., crystallinity = 48%,
MFR (ASTM D 1238, 190 ° C, 2.16kg load) = 1.0
g / 10 minutes, ethylene content = 96 mol%] 100 parts by weight, maleic anhydride 0.8 parts by weight, and peroxide [trade name Perhexin-25B, manufactured by NOF Corporation] 0.0
7 parts by weight are mixed with a hexshell mixer, and the resulting mixture is subjected to melt graft modification with a uniaxial extruder of 65 mmφ set at 230 ° C. to obtain modified ethylene-1.
A butene copolymer [abbreviated as (MAH-PE-1)] was obtained. This modified ethylene / 1-butene copolymer (MAH-
The amount of maleic anhydride grafted on PE-1) was measured by IR analysis and found to be 0.8% by weight. In addition, MFR (AS
TM D 1238, 190 ℃, 2.16kg load) is 0.27g / 1
It was 0 minutes and the melting point was 122 ° C.

[Production of Resin Composition] Modified ethylene / 1-butene copolymer (MAH-P) obtained as described above.
E-1) 20 parts by weight, 80 parts by weight of the semi-aromatic polyamide composition obtained by the above method, and 2 parts by weight of talc are shown in Table 1.
Were mixed in the proportions shown in Table 1 and then melt-mixed using a 30 mmφ bent type twin screw extruder at a cylinder temperature of 300 to 335 ° C. Injection-molded test pieces were prepared using the pellets thus obtained, and the performance of these test pieces was evaluated. The evaluation results are shown in Table 1.

Example 2 1,6-diaminohexane 2
46.0 g (2.116 mol), 2-methyl-1,5-
34.4 g (0.302 mol) of diaminopentane, 249.4 g (1.50 mol) of terephthalic acid, 1 adipic acid
13.5 g (0.77 mol), 0.45 g (4.25 × 10 ⁻³ mol) of sodium hypophosphite as a catalyst, and 65 ml of ion-exchanged water were charged into a 1-liter reactor, and after replacement with nitrogen, 250 The reaction was carried out for 1 hour at 35 ° C. and 35 kg / cm ² . After 1 hour, the reaction product formed in the reactor was connected to the reactor and the pressure was about 10
554 g of a polyamide precursor having an intrinsic viscosity [η] of 0.15 dl / g, which was extracted into a container set to have a lower kg / cm ²
Got Next, this polyamide precursor was dried and melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain an aromatic polyamide (PA-3). The composition of this aromatic polyamide is as follows. The 1,6-diaminohexane component unit content in the diamine component unit was 88.
The mol% and 2-methyl-1,5-diaminopentane component unit content are 12 mol%. The terephthalic acid component unit content rate in the dicarboxylic acid component unit is 66 mol%, and the adipic acid component unit content rate is 34 mol%.
The procedure of Example 1 was repeated except that the polyamide (PA-3) thus obtained was used. The results are shown in Table 1.

Comparative Example 1 The procedure of Example 1 was repeated except that only the polyamide resin produced in Reference Example 1 was used as the semi-aromatic polyamide resin. The results are shown in Table 1.

Comparative Example 2 The procedure of Example 1 was repeated except that only the polyamide resin produced in Reference Example 2 was used as the semi-aromatic polyamide resin. The results are shown in Table 1.

[Comparative Example 3] [Production of modified ethylene / 1-butene copolymer elastomer] Ethylene / 1-butene copolymer prepared using a V catalyst [Density = 0.88 g / cm ³ , MFR (ASTM D 1
238, 190 ° C, 2.16 kg load) = 3.6 g / 10 minutes, ethylene content = 90 mol%, melting point (Tm) = 72 ° C., crystallinity = 16%] 100 parts by weight, maleic anhydride 0.5 parts by weight Parts and peroxide [trade name: Perhexin-25B, manufactured by NOF CORPORATION] 0.045 parts by weight, were mixed with a hexshell mixer, and the resulting mixture was set to 230 ° C. 6
A modified ethylene / 1-butene copolymer [MAH-P] was obtained by melt graft modification with a 5 mmφ uniaxial extruder.
Abbreviated as E-2]. The amount of maleic anhydride grafted on the modified ethylene / 1-butene copolymer (MAH-PE-2) was measured by IR analysis and found to be 0.5% by weight. The MFR (ASTM D 1238, 190 ° C., 2.16 kg load) was 2.1 g / 10 minutes, and the melting point was 71 ° C.
The same procedure as in Example 1 was performed except that this MAH-PE-2 was used. The results are shown in Table 1.

Example 3 A polyamide precursor having an [η] of 1.05 dl / g produced in Reference Example 1 and a polyamide precursor having an [η] of 1.00 dl / g produced in Reference Example 2 were each dried. After that, the weight ratio of 37.5: 62.5 was blended, and the cylinder temperature was set to 330 ° C using a twin-screw extruder.
Was melt-extruded to obtain an aromatic polyamide composition having a methyl group in the side chain. The composition of this aromatic polyamide is as follows. The 1,6-diaminohexane component unit content in the diamine component unit was 81 mol%, and the 2-methyl-1,5-diaminopentane component unit content was 19%.
Mol%. The terephthalic acid component unit content rate in the dicarboxylic acid component unit was 72 mol%, and the adipic acid component unit content rate was 28 mol%.

[Production of Resin Composition] Modified ethylene / 1-butene copolymer (MAH-PE-1) 2 used in the examples.
0 parts by weight, 80 parts by weight of the semi-aromatic polyamide composition obtained by the above method, and 1 part by weight of talc were mixed in the proportions shown in Table 1, and then a 30 mmφ bent twin screw extruder was used. It was melt-mixed at a cylinder temperature of 300 to 335 ° C. Injection-molded test pieces were prepared using the pellets thus obtained, and the performance of these test pieces was evaluated. The evaluation results are shown in Table 1.

Comparative Example 4 MAHPE in Example 1
Example 1 was repeated except that -1 was not added. The results are shown in Table 1.

[0093]

[Table 1]

[0094]

The semi-aromatic polyamide resin composition of the present invention has excellent fluidity and can lower the molding temperature. Further, the resin composition of the present invention is suitable for long-time molding because the amount of oligomers deposited during molding is small and the vent holes of the molding die are less likely to be clogged. Furthermore, the resin composition of the present invention,
Excellent heat aging resistance and heat distortion resistance. Utilizing such characteristics, the resin composition of the present invention is suitable as a thermoplastic resin for electric tools, general industrial parts, mechanical parts, electronic parts, automobile interior / exterior parts, engine room parts, and automobile electrical parts. Can be used for By using the semi-aromatic polyamide resin composition of the present invention, it is possible to produce a molded article having good toughness as described above, and also by suppressing such a decrease in toughness,
There is an advantage that other excellent properties inherently possessed by the aromatic polyamide, such as mechanical strength and low water absorption, are hardly deteriorated.

[Brief description of drawings]

FIG. 1 is a cross-sectional view (A) of a mold used for evaluation of mold clogging and a view (B) showing “gas burning” of a molded product in Examples.

FIG. 2 shows a measurement atmosphere of 23 in each of Examples and Comparative Examples.
9 is a graph showing the relationship between elapsed time (days) and creep deformation amount (mm) at 50 ° C. and 50% RH.

FIG. 3 shows a measurement atmosphere of 40 in Examples and Comparative Examples.
9 is a graph showing the relationship between the elapsed time (days) and the creep deformation amount (mm) under the condition of ° C and 95% RH.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 77/06 C08L 23/26 C08K 3/00-13/08

Claims (10)

(57) [Claims] 1. A polyamide comprising (A) a repeating unit composed of a dicarboxylic acid component unit and a diamine component unit as a main constituent component unit, wherein at least 45 mol% or more of the dicarboxylic acid component unit is terephthalic acid. The component is a diamine component unit, and the diamine component unit is 55 to 99 mol% of a linear alkylenediamine component unit having 4 to 18 carbon atoms and an alkylenediamine component unit 1 to 45 having 4 to 18 carbon atoms having a side chain alkyl group. Melting point 280-33 consisting of mol%
99 to 60% by weight of a polyamide copolymer at 0 ° C., and (B) a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, wherein (i) the density is 0.89 to 0.95 g. / in the range of cm ^3, (ii) the temperature at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC) (melting point; Tm) is 90 to 127 ° C., and (iii) X-ray diffraction An ethylene / α-olefin copolymer having a crystallinity of 20% to 60% measured by a
A semi-aromatic polyamide resin composition comprising 1 to 40% by weight of a modified ethylene / α-olefin copolymer having a graft amount of 0.01 to 5% by weight modified with an unsaturated carboxylic acid or a derivative thereof. object. 2. The polyamide copolymer (A) contains an aromatic carboxylic acid unit other than terephthalic acid and / or an aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms in an amount of 55 mol% or less based on all dicarboxylic acid units. The semi-aromatic polyamide resin composition according to claim 1, which contains. 3. The semi-aromatic polyamide resin composition according to claim 1, wherein the linear alkylenediamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit. 4. A carbon atom having a side chain alkyl group with 4 to 4 carbon atoms.
18 alkylenediamine component units are 2-methyl-
The semi-aromatic polyamide resin composition according to claim 1, which is a 1,5-diaminopentane component unit. 5. The polyamide copolymer (A) comprises:
(A) melt-kneading a side chain alkyl group-containing polyamide precursor obtained by reacting the dicarboxylic acid component with the straight chain alkylenediamine component and the alkylenediamine component having a side chain alkyl group, or (b) A polyamide having a side chain alkyl group and a polyamide not having a side chain are separately produced and melt-kneaded to perform an amide exchange reaction, or (c) the dicarboxylic acid component unit and the diamine component unit are claimed. The semi-aromatic polyamide according to claim 1, which is obtained by melt-kneading at least two kinds of polyamides having different compositions so that the composition has 1 composition. Resin composition. 6. The polyamide copolymer (A) has a dicarboxylic acid component unit and a terephthalic acid component unit of 45 to 100.
Mol% and aromatic dicarboxylic acid component units other than terephthalic acid 0 to 55 mol% and / or 4 to 20 carbon atoms
Of the aliphatic dicarboxylic acid component unit of 0 to 55 mol%, and the diamine component unit is 5 to 95 mol% of a linear alkylenediamine component unit of 4 to 18 carbon atoms and the number of carbon atoms having a side chain alkyl group. 5 to 50 parts by weight of a side chain-containing polyamide composed of 5 to 95 mol% of 4 to 18 alkylenediamine component units, and a dicarboxylic acid component unit,
45-100 mol% of terephthalic acid component units and 0-55 mol% of aromatic dicarboxylic acid component units other than terephthalic acid
And / or an aromatic dicarboxylic acid component unit having 4 to 20 carbon atoms and 0 to 55 mol%, and the diamine component unit is 100 mol% of a linear alkylenediamine component unit having 4 to 18 carbon atoms. Group polyamide 50-
The semi-aromatic polyamide resin composition according to claim 5, which is a composition comprising 95 parts by weight. 7. The semi-aromatic polyamide resin composition according to claim 6, wherein the linear alkylenediamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit. 8. A carbon atom having a side chain alkyl group with 4 to 4 carbon atoms.
18 alkylenediamine component units are 2-methyl-
The semi-aromatic polyamide resin composition according to claim 6 or 7, which is a 1,5-diaminopentane component unit. 9. A polyamide resin composition comprising a resin component 10
The semi-aromatic polyamide resin composition according to claim 1, which contains 1 to 200 parts by weight of an inorganic filler with respect to 0 parts by weight. 10. The semi-aromatic polyamide resin composition according to claim 9, wherein the inorganic filler is talc.