JP2000080270A - Semi-aromatic polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a semi-aromatic polyamide resin composition which has excellent properties such as creep property at high temperature and humidity, seldom gives dirts in a metal mold upon molding, and has an improved mold- releasing property. SOLUTION: This composition consists of (A) 98-65 wt.% of a polyamide copolymer which consists of a dicarboxylic acid consisting of terephthalic acid at 45 mol.% or more and a diamine which consists of a linear alkylenediamine and/or an alkylene diamine having branched chain alkyl(s), (B) 1-10 wt.% of an aliphatic polyamide which contains a unit derived from a lactam, a unit derived from an amino carboxylic acid, or a unit derived from dodecanedioic acid and a diamine, and (C) 1-25 wt.% of a graft-modified ethylene-α-olefin copolymer, a graft-modified product from an aromatic vinyl compound- conjugated diene copolymer, or a graft-modified product from a hydride of the aromatic vinyl compound-conjugated diene copolymer.

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 resin composition having excellent creep resistance under a high temperature and a high humidity, and particularly having a small mold stain during molding and a good mold release property. About things.

[0002]

2. Description of the Related Art Various proposals have been made on semi-aromatic polyamides having impact resistance. For example, Japanese Patent Application Laid-Open No. 4-108855 discloses a terephthalic acid unit of 5 units.
A dicarboxylic acid unit (a) composed of 0 to 100 mol% and an aromatic dicarboxylic acid other than terephthalic acid or 0 to 40 mol% of a linear aliphatic dicarboxylic acid unit having 6 to 18 carbon atoms, and an alkylenediamine unit (b) A method for producing a polyamide composition comprising a semi-aromatic polyamide having the following formula and a modified elastic copolymer is disclosed.

It is also known that a composition comprising such a semi-aromatic polyamide and a modified elastic polymer has excellent 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 and physical properties, but when injection molding is repeated using a mold. In some cases, white powder was precipitated in the mold. Further, when used as electronic equipment, the creep characteristics under high temperature and high humidity are not sufficient, and improvement has been desired.

As a result of analyzing the powder by the present inventors, it was found that the powder was an unreacted monomer, a lower oligomer component and a polymer decomposition product. This unreacted monomer, lower oligomer or polymer decomposition product component is used for electronic parts,
In particular, when a fine component such as a connector is formed, a problem arises in that the appearance is impaired and dimensional accuracy is not obtained.
Further, since white powder generated in the mold may block the vent hole of the mold, it is necessary to stop molding and clean the mold.

[0006] The present inventors have previously proposed a semi-aromatic polyamide resin composition comprising a specific polyamide copolymer and a modified ethylene / α-olefin copolymer (Japanese Patent Application No. Hei.
0-52273). This resin composition has effectively improved the above-mentioned problems, and has excellent mechanical strength such as rigidity, impact resistance and bending strength, excellent creep characteristics, and excellent impact resistance and heat resistance. It has excellent physical properties, is less likely to cause mold contamination during molding, and is less likely to cause clogging of the mold vent, and has the advantage of being able to produce precision molded products with excellent appearance. .

However, the resin composition proposed above has a problem that the mold releasing force at the time of molding is high. For example, when a molded article such as a connector is manufactured, a mold having a complicated structure is required. Since molding is carried out using the mold, mold release failure often occurs, and there is still room for improvement. Accordingly, an object of the present invention is to provide a semi-aromatic polyamide resin which has excellent properties such as creep properties under high temperature and high humidity, hardly causes mold stains during molding, and has improved mold releasability. It is to provide a composition.

[0008]

According to the present invention, (A)
A polyamide whose main constituent unit is formed of a repeating unit composed of a dicarboxylic acid component unit and a diamine component unit, wherein at least 4
5 mol% or more is a terephthalic acid component unit, and the diamine component unit is a linear alkylene diamine component unit having 4 to 18 carbon atoms and / or an alkylene diamine having 4 to 18 carbon atoms having a side chain alkyl group. A polyamide copolymer comprising component units, (B) (i) having 12 carbon atoms
A structural unit derived from a lactam of (ii) having 1 carbon atom
And (ii) a structural unit derived from an aminocarboxylic acid
i) an aliphatic polyamide containing, as a constituent unit, at least one selected from the group consisting of constituent units derived from dodecanedioic acid and a diamine;
at least one selected from the group consisting of an α-olefin copolymer, a graft-modified aromatic vinyl compound / conjugated diene copolymer, and a graft-modified aromatic vinyl compound / conjugated diene copolymer hydride; A graft-modified product, wherein the component (A) is 98 to 65% by weight, preferably 88.5 to 76% by weight, based on the total amount of the components (A), (B) and (C). The component (B) is contained at 1 to 10% by weight, preferably 1.5 to 4% by weight, and the component (C) is contained at 1 to 25% by weight, preferably 10 to 20% by weight. A semi-aromatic polyamide resin composition is provided.

In the semi-aromatic polyamide resin composition of the present invention, 1. The polyamide copolymer (A) has a melting point measured by DSC in the range of 280 to 330 ° C; The polyamide copolymer (A) contains aromatic carboxylic acid units other than terephthalic acid and / or aliphatic dicarboxylic acid units having 4 to 20 carbon atoms in a range of 55 mol% or less per total dicarboxylic acid units. 3. 3. The polyamide (B) has a flexural modulus measured by ASTM D790 of 1300 MPa or more for a test piece obtained by injection molding; The graft modified product (C) has a density of 0.85 to 0.85.
In the range of 0.95 g / cm ³ .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, among the semi-aromatic polyamides, the above-mentioned specific semi-aromatic polyamide (A) is selected, and this semi-aromatic polyamide (A) is replaced with a specific polyamide (B) ( An important feature is the blending of, for example, nylon 12) and a specific graft-modified product (C). By adopting such a combination, the mold releasability is improved, and the oligomer precipitation amount in the molded product is improved. And the clogging of the vent hole of the molding die is suppressed, so that molding can be performed for a long time. Further, the semi-aromatic polyamide resin composition of the present invention has an advantage of being excellent in fluidity and capable of lowering a molding temperature. Furthermore, the semi-aromatic polyamide resin composition of the present invention is excellent in creep characteristics under high temperature and high humidity, heat aging resistance, heat deformation resistance, and impact resistance. Moreover,
Even by suppressing such a decrease in toughness, there is an advantage that other excellent properties inherent to the aromatic polyamide, such as properties such as mechanical strength and low water absorption, hardly decrease.

[Semi-Aromatic Polyamide (A)] The semi-aromatic polyamide (A) used in the present invention comprises a specific dicarboxylic acid component unit [a] and a specific aliphatic diamine component unit [b]. ] Is repeated.

This semi-aromatic polyamide (A) has a terephthalic acid component unit (a-1) of 45 to 45% when the total dicarboxylic acid component unit present in the polyamide is 100 mol%.
It is contained in an amount of 100 mol%, preferably 50 to 90 mol%, more preferably 60 to 80 mol%. Also,
This semi-aromatic polyamide contains the aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid in an amount of 0 to 55 mol%, preferably 0 to 40 mol%, more preferably 0 to 30 mol%. ing. Further, it contains the aliphatic dicarboxylic acid component unit (a-3) in an amount of 0 to 55 mol%. The semi-aromatic polyamide has a small amount of the aliphatic dicarboxylic acid component unit (a-3), so that it is specifically contained in an amount of 10 to 50 mol%, more preferably 20 to 40 mol%. Thereby, it has excellent moldability. The content of the aliphatic dicarboxylic acid component unit is 55
If it exceeds mol%, the content of the terephthalic acid component unit will necessarily fall below 45 mol%, and such a semi-aromatic polyamide tends to have a high water absorption and a melting point below 280 ° C. . Therefore, a molded article formed from such a semi-aromatic polyamide tends to have a large dimensional change due to water absorption or insufficient heat resistance, and is unsuitable for the present invention.

The diamine component unit [b], which forms a repeating unit together with the dicarboxylic acid component unit, is a linear alkylenediamine component unit having 4 to 18 carbon atoms and / or a carbon atom having a side chain alkyl group. Number 4-1
8 alkylene diamine component units.

Among these, the semi-aromatic polyamide used in the present invention contains 55 to 55 linear aliphatic alkylenediamine component units (b-1) having 4 to 18 carbon atoms per 100 mol% of all diamine component units. 99 mol%, preferably 70
More preferably, it is contained in an amount of from 98 to 98 mol%, particularly preferably from 80 to 95 mol%. The alkylene diamine component unit (b-2) having 4 to 18 carbon atoms having a side chain alkyl group is contained in an amount of 1 to 45 mol%, preferably 2 to 3 mol%.
It is contained in an amount of 0 mol%, particularly preferably 5 to 20 mol%. When the two types of specific alkylenediamine component units are contained in the above amounts, the melting point of the semi-aromatic polyamide which is the main component of the composition of the present invention is determined by injection molding at the time of injection molding. Or melted polyamide) is particularly preferred because it is reduced to such an extent that gas burning does not occur. In addition, the advantage that the precipitation of white powder in the mold, that is, the amount of deposits on the mold (Mold Deposit) is reduced, and the Tg of the polyamide is as high as 100 ° C. or more, and the creep characteristics under high temperature and high humidity are excellent. Having.

That is, if the content of the linear alkylenediamine component unit (b-1) having 4 to 18 carbon atoms is 99 mol% or less, white powder at the time of injection molding, that is, adhesion to a mold (Mold) Deposit) is less likely to occur. Also,
When the content of the alkylene diamine component unit (b-2) having 4 to 18 carbon atoms having a side chain alkyl group is 45 mol% or less, the crystallization speed of the semi-aromatic polyamide is reduced, and the heat resistance is particularly good. .

The above-mentioned semiaromatic polyamide repeating unit composed of a dicarboxylic acid component unit and a diamine component unit is represented by the following formula. The repeating unit forming the semi-aromatic 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) is represented by the following formula [I-
a]:

Embedded image In the formula, R ¹ has 4 to 4 carbon atoms which may have a side chain.
Which is 18 alkylene groups. The dicarboxylic acid component unit [a] is entirely composed of the above [I-a]
Is not necessary, 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 units other than the terephthalic acid component include 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 isophthalic acid component unit, 2-methylterephthalic acid component unit and naphthalenedicarboxylic acid component unit. As such a 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, a repeating unit having an isophthalic acid component unit particularly preferred in the present invention is represented by the following formula [Ib]:

Embedded image In the formula, R ¹ has 4 to 1 carbon atoms which may have a side chain.
8, which is an alkylene group.

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

The repeating unit having the 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 [I]
I]:

Embedded image In the formula, R ¹ has 4 to 1 carbon atoms which may have a side chain.
And n is an integer of usually 2 to 18, preferably 4 to 10.

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

Specific examples of such a linear alkylenediamine component unit (b-1) include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane and 1,8-diaminoheptane. Diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane can be mentioned. Among these, component units derived from 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane are preferred, and among the semi-aromatic polyamides used in the present invention, May contain a plurality of these component units. Further, among these, a component unit derived from 1,6-diaminohexane is particularly preferred.

Specific examples of the alkylene diamine component unit (b-2) having 4 to 18 carbon atoms having a side chain alkyl group include 1-butyl-1,2-diamino-ethane, 1,1 -Dimethyl-1,4-diamino-butane,
1-ethyl-1,4-diamino-butane, 1,2-dimethyl-1,4-diamino-butane, 1,3-dimethyl-
1,4-diamino-butane, 1,4-dimethyl-1,4
-Diamino-butane, 2,3-dimethyl-1,4-diamino-butane, 2-methyl-1,5-diaminopentane, 2,5-dimethyl-1,6-diamino-hexane,
2,4-dimethyl-1,6-diamino-hexane, 3,
3-dimethyl-1,6-diamino-hexane, 2,2-
Dimethyl-1,6-diamino-hexane, 2,2,4-
Trimethyl-1,6-diamino-hexane, 2,4,4
-Trimethyl-1,6-diamino-hexane, 2,4-
Diethyl-1,6-diamino-hexane, 2,3-dimethyl-1,7-diamino-heptane, 2,4-dimethyl-1,7-diamino-heptane, 2,5-dimethyl-
1,7-diamino-heptane, 2,2-dimethyl-1,
7-diamino-heptane, 2-methyl-4-ethyl-
1,7-diamino-heptane, 2-ethyl-4-methyl-1,7-diamino-heptane, 2,2,5,5-tetramethyl-1,7-diamino-heptane, 3-isopropyl-1,7 -Diamino-heptane, 3-isooctyl-1,7-diamino-heptane, 2-methyl-1,8-
Diamino-octane, 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-
Mention may be made of component units derived from trimethyl-1,8-diamino-octane, 2,4-diethyl-1,8-diamino-octane, and 5-methyl-1,9-diamino-nonane.

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

Among the alkylene diamine component units having a side chain alkyl group as described above, one or two side chain alkyl groups having 1 to 2 carbon atoms and a main chain having 4 to 10 carbon atoms. Component units derived from the side chain alkyl diamine are preferred, and 2-methyl-1,5-diaminopentane component units and 2-methyl-1,8-diamino-octane component units are particularly preferred.

The following formula [III] shows an example of a repeating unit having a component unit derived from 2-methyl-1,5-diaminopentane which is a particularly preferred side-chain alkyldiamine used in the present invention.

Embedded image In the formula, R ² represents a p-phenylene group, 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 semi-aromatic polyamide used in the present invention includes, as dicarboxylic acid component units, terephthalic acid component units which are the above-mentioned main component units, and divalent aromatic carboxylic acids other than terephthalic acid represented by isophthalic acid component units. In addition to the component units derived from an acid and the above-described aliphatic dicarboxylic acid component units, a small amount of component units derived from a tribasic or higher polycarboxylic acid such as trimellitic acid or pyromellitic acid is contained. May be. In the polyamide, the component unit derived from such a polycarboxylic acid can be usually contained in an amount of 0 to 5 mol%.

The semi-aromatic polyamide used in the present invention has an intrinsic viscosity [η] measured in concentrated sulfuric acid at a temperature of 30 ° C., usually from 0.5 to 3.0 dl / g, preferably from 0.5 to 2.0 dl / g. 8
dl / g, particularly preferably in the range of 0.6 to 2.5 dl / g.

The above-mentioned semi-aromatic polyamide has a higher melting point than the conventionally used aliphatic polyamide, but the melting point is often in the range of 280 to 330 ° C., preferably 280 to 310 ° C. C, more preferably in the range of 290-305C. When the semi-aromatic polyamide is produced by blending two or more polyamides as described later, the melting point can be observed by DSC measurement of a blend of two or more polyamides. DSC measurement may be performed on a composition containing all of the components (A) to (C). Further, the semi-aromatic polyamide has particularly excellent heat resistance, low water absorption, and little post-crystallization due to annealing of the molded product. The glass transition temperature in the amorphous part is usually 80 ° C. or higher, preferably 90 to 150 ° C., and more preferably 100 to 150 ° C. Therefore, this semi-aromatic polyamide is excellent in creep deformability and hardly causes mold stains.

The semi-aromatic polyamide used in the present invention can be produced by polycondensation of a dicarboxylic acid component and a diamine component. Specifically, this semi-aromatic polyamide is made of terephthalic acid or an aromatic dicarboxylic acid other than terephthalic acid, an aliphatic dicarboxylic acid, a linear dialkylenediamine, and / or an alkylene having a side chain alkyl group. The diamine and the above amount are blended in an aqueous medium, and heated under pressure in the presence of a catalyst such as sodium hypophosphite to produce a polyamide precursor first, and then melt-knead the polyamide precursor. Can be manufactured. When producing the polyamide precursor, a molecular weight modifier such as benzoic acid may be blended.

The semi-aromatic polyamide may be produced by separately producing a polyamide having a side chain alkyl group and a polyamide having no side chain, and kneading and kneading them to carry out a transamidation reaction. Can also.

The semiaromatic polyamide used in the present invention is prepared 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 fall within the above ranges. It can also be produced by melt-kneading.

For example, typical examples of the above-mentioned semi-aromatic polyamide (A) include: (A-1) a dicarboxylic acid component unit having 45 to 100 mol% of terephthalic acid component unit and an aromatic compound other than terephthalic acid; 0 to 55 mol% of dicarboxylic acid component units and / or 0 to 55 aliphatic dicarboxylic acid component units having 4 to 20 carbon atoms
55 mol%, and the diamine component unit is a linear alkylene diamine component unit having 10 to 18 carbon atoms.
0 mol% of polyamide (hereinafter referred to as “linear polyamide”)
And (A-2): a dicarboxylic acid component unit having 45 to 100 mol% of a terephthalic acid component unit and 0 to 55 mol% of an aromatic dicarboxylic acid component unit other than terephthalic acid and / or having 4 carbon atoms. ~ 20 aliphatic dicarboxylic acid component units 0
55 mol%, and the diamine component unit is a linear alkylene diamine component unit having 4 to 18 carbon atoms.
95 mol% and 4 carbon atoms having a side chain alkyl group
Polyamide consisting of 5 to 95 mol% of alkylene diamine component units (hereinafter referred to as “side-chain polyamide”)
And the linear polyamide (A-1) and the side chain polyamide (A-2) may be combined by melt kneading or the like.

The following can be exemplified as the linear polyamide (A-1). (A-1-1): A polyamide comprising the constituent units of the formulas [Ia] and [II]. However, the formulas [Ia] and [I
I] R ¹ groups in are all straight-chain alkylene group (C stars
4 to 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): The above formulas [Ia] and [I
-B] and a polyamide comprising constituent units of [II].
However, each of the R ¹ groups in the formulas [Ia], [Ib] and [II] is a linear alkylene group (C number: 4 to 18). In this case, [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 mol%
It should be in the mole% range. (A-1-3): a polyamide comprising constituent units of the formulas [Ia] and [Ib]. Where the formula [Ia],
Each of the R ¹ groups in [Ib] is a linear alkylene group (C number: 4 to 18). In this case, the [Ia] unit is in the range of 50 to 80 mol%, preferably 60 to 70 mol%, and the [Ib] unit is in the range of 10 to 40 mol%, preferably 20 to 30 mol%. Good.

As the side chain polyamide (A-2), the following can be exemplified. (A-2-1): A polyamide comprising constituent units of the 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 content of the [Ia] unit is 5 to 95 mol%, preferably 3 to 95 mol%.
0 to 70 mol%, most preferably 40 to 60 mol%, and [III] unit is 95 to 5 mol%, preferably 70 to 70 mol%.
It is preferably in the range of from 30 to 30 mol%, most preferably in the range of 60 to 40 mol%.

(A-2-2): The formulas [Ia] and [I
-B] and a polyamide comprising the constituent units of [III].
However, each of the R ¹ groups in the formulas [Ia] and [Ib] is a linear alkylene group (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%, and the unit [Ib] is 5 to 30 mol%,
The content is preferably in the range of 10 to 20 mol%, and the unit of [III] is in the range of 30 to 70 mol%, preferably 40 to 60 mol%. As specific examples, (A-1-1): TA / AA / HMDA, (A-1-2): TA / IA / HMDA, (A-1-3): TA / IA / AA or SA / HMD
A, (A-2-1): TA / HMDA / MPMDA, TA /
AA / HMDA / MPMDA, TA / NMDA / MDA
O, TA / AA / NMDA / MDAO, (A-2-2): TA / IA / HMDA / MPMDA,
TA / IA / NMDA / MDAO, and the like. Here, TA: terephthalic acid, IA: isophthalic acid, AA: adipic acid, SA: sebacic acid, HMDA: hexamethylenediamine (1,6-diaminohexane), MPMDA: 2-methyl-1,5-pentamethylenediamine NMDA: nonamethylenediamine (1,9-diaminononane); MDAO: 2-methyl-1,8-diaminooctane. In the present invention, among the above polyamides (A), (A-2-1) and (A-2-2) can be preferably used.

The above linear polyamide (A-1) and side chain polyamide (A-2) can be used alone as the component (A) depending on the composition. When the semi-aromatic polyamide (A) is used by combining the side chain polyamide (A-2) with the side chain polyamide (A-2), the amount of the linear polyamide (A-1) is at least 45 parts by weight, especially 50 to 95 parts by weight. 5 chain polyamide (A-2)
It is preferably used in an amount of not less than 5 parts by weight, especially 5 to 50 parts by weight. Among them, when the semi-aromatic polyamide (A) is prepared from the linear polyamide (A-1-1) and the side chain polyamide (A-2-1), (A-1-1) is converted to 4
5 to 95% by weight, preferably 60 to 90% by weight, most preferably 70 to 85% by weight, (A-2-1) 55 to 5% by weight, preferably 40 to 10% by weight, most preferably Is preferably used in an amount of 30 to 15% by weight. Within this range, a semi-aromatic polyamide resin composition having particularly excellent creep and less generation of white powder can be obtained.
The above-mentioned semi-aromatic polyamide (A) has a total amount (A + B) of a polyamide (B) described later and a graft-modified product (C).
+ C) 98 to 65% by weight, especially 88.5 to 7
It is used in an amount of 6% by weight.

[Polyamide (B)] In the present invention, the polyamide (B) used in combination with the above-mentioned semi-aromatic polyamide (A) comprises (i) a structural unit derived from a lactam having 12 carbon atoms; It has at least one of ii) a structural unit derived from an aminocarboxylic acid having 12 carbon atoms and (iii) a structural unit derived from dodecanedioic acid and a diamine. Here, an aliphatic diamine is preferably used as the diamine. As the aliphatic diamine, the same diamine as described for the component (A) is used, and a straight-chain diamine is preferable, and the number of carbon atoms is 6
~ 12 diamines are more preferred. Examples of the polyamide (B) include nylon 12 obtained by ring-opening polycondensation of lactam 12-aminododecanoate and polycondensation of 12-aminododecanoic acid, and nylon 6 obtained by polycondensation of hexamethylenediamine and dodecanediacid. , 12 and the like. In the present invention, those having a structural unit derived from a lactam having 12 carbon atoms and an aminocarboxylic acid are particularly preferable. According to the present invention, mold releasability during molding can be improved by using such a polyamide (B) in combination with the above-mentioned semi-aromatic polyamide (A). For example, as shown in a comparative example described later, when a polyamide obtained from a lactam or aminocarboxylic acid having a different number of carbon atoms is used (Comparative Example 3), a diamine and a dicarboxylic acid such as nylon 6,6 are used. When the polyamide obtained from the acid was used (Comparative Example 2), the mold releasability could not be improved, and as compared with the case where the semi-aromatic polyamide (A) was used alone (Comparative Example 2). Example 1), mold releasability rather deteriorates.

In the present invention, it is important to blend the above-mentioned polyamide (B) with the semi-aromatic polyamide (A) and the modified ethylene / α-olefin copolymer (C) described later. B) is used in an amount of 1 to 10% by weight, especially 1.5 to 4% by weight, based on the total amount (A + B + C) of the semi-aromatic polyamide (A) and the modified ethylene / α-olefin copolymer (C). used.
If the amount of the polyamide (B) is less than the above range, it is difficult to sufficiently improve the mold releasability. If the amount of the polyamide (B) is larger than the above range, the generation of white powder can be prevented. Inconveniences such as difficulty and creep resistance are lowered. In the case where the unit derived from the lactam or aminocarboxylic acid having 12 carbon atoms described above is merely incorporated into the semi-aromatic polyamide (A) by copolymerization and the component (B) is not separately added, ,
As shown in Comparative Example 4, it is difficult to improve the mold releasability.

The polyamide (B) described above may be a lactam having 12 carbon atoms or a lactam other than an aminocarboxylic acid having 12 carbon atoms, as long as the object of the present invention to improve mold release properties is not impaired. Aminocarboxylic acid,
Alternatively, it may contain units derived from various diamines, dicarboxylic acids and the like other than the constitutional unit consisting of dodecane diacid and diamine.
It may contain 0 mol% or less, preferably less than 20 mol%, more preferably less than 5 mol%, and most preferably less than 1 mol%. Particularly preferably, other components are not substantially copolymerized. That is, the constituent unit composed of a lactam having 12 carbon atoms, an aminocarboxylic acid having 12 carbon atoms, or dodecane diacid and a diamine is 50 mol% or more, preferably 80 mol% or more, more preferably 9 mol% or more.
It is at least 5 mol%, most preferably at least 99 mol%.
The polyamide (B) used in the present invention generally has an intrinsic viscosity [η] of 0.3 to 4 measured in concentrated sulfuric acid at a temperature of 30 ° C.
dl / g, preferably in the range of 0.4 to 3 dl / g, most preferably 0.6 to 1.5 dl / g. The polyamide (B) has a flexural modulus of 1 as measured by ASTM D790 for a test piece obtained by injection molding.
300MPa or more, especially 1400MPa-2000MPa
Those that are a are preferred.

[Graft-modified product (C)] In the present invention, in addition to the above-mentioned semi-aromatic polyamides (A) and (B), a graft-modified ethylene / α-olefin copolymer (C-1), A modified aromatic vinyl compound / conjugated diene copolymer (C-2) and a hydride of a graft-modified aromatic vinyl compound / conjugated diene copolymer (C-
At least one graft-modified product (C) selected from the group consisting of 3) can be used, and such a graft-modified product (C) can be used.
By blending the components, generation of white powder during molding can be more effectively prevented, and mold contamination can be effectively prevented. This graft-modified product (C) is obtained by the above (A)
The amount is preferably 1 to 25% by weight, more preferably 10 to 20% by weight, based on the total amount (A + B + C) with the component (B).

This graft-modified product (C) is made of ethylene.
α-olefin copolymer [C1], aromatic vinyl compound
.Conjugated diene copolymer [C2] or the aromatic vinylation
Unsaturated compound / conjugated diene copolymer hydride [C3]
Graft-modified with carboxylic acids or their derivatives
It is. Graft-modified product (C), especially graft-modified ethyl
The ren / α-olefin copolymer has a density of 0.85-0.9.
5g / cm³, Preferably 0.89 to 0.95 g / cm
³, More preferably 0.90 to 0.94 g / cm³,
Most preferably 0.91-0.93 g / cm³In the range
Things. Excellent creep properties in this range, white powder
Can be obtained.

Ethylene-α-ole for graft modification
The fin copolymer [C1] is composed of ethylene and α-olefin.
And especially α-olefins having 3 to 20 carbon atoms.
You. This ethylene / α-olefin copolymer [C1]
The ethylene content is 70 mol% or more, preferably 80 to
98 mol%. Specific examples of the α-olefin include
Specifically, propylene, 1-butene, 1-pentene, 1-
Hexene, 4-methyl-1-pentene, 1-octene,
1-decene and the like. Among them, 1-butene, 1
-Hexene, 4-methyl-1-pentene, 1-octene
Is preferably used. These α-olefins are simply
Can be used alone or in combination of two or more
You. Further, an ethylene / α-olefin copolymer [C1]
Density is almost unchanged before and after the graft modification.
It has been certified. Therefore, ethylene used as a raw material
The α-olefin copolymer has the same density as the graft-modified product.
Degree, specifically, the density is 0.85-0.95 g / cm
³, Preferably 0.89 to 0.95 g / cm ³And more
0.90 to 0.94 g / cm³, Most preferred
0.91 to 0.93 g / cm³Use in the range of
Is preferred.

Further, the ethylene / α-olefin copolymer [C1] has a temperature (melting point; Tm) at the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC).
However, it is usually 90 ° C to 127 ° C, preferably 95 to 12 ° C.
Although it is in the range of 0 ° C., it is also possible to use an amorphous ethylene / α-olefin copolymer which does not show a melting point. Furthermore, an ethylene / α-olefin copolymer [C1]
Usually has a crystallinity measured by X-ray diffraction method of 20 to
60%, more preferably 25-55%, preferably 3
Although it is in the range of 0 to 50%, an amorphous material can be used as described above. Also, the melt flow rate (MFR; ethylene-α-olefin copolymer [C1])
(ASTM D1238, 190 ° C, 2.16 kg load) is usually 0.01 to 100 g / 10 min, preferably 0.1 to 50 g / 10 min, more preferably 0.2 to 2 g / min.
It is in the range of 0 g / 10 minutes.

Ethylene α-having the above physical properties
The olefin copolymer [C1] can be produced by a conventionally known method using a titanium (Ti) -based, vanadium (V) -based, zirconium (Zr) -based catalyst, or the like.

The graft-modified aromatic vinyl hydrocarbon / conjugated diene copolymer (C-
2) or its hydride (C-3) is a random copolymer or a block copolymer of an aromatic vinyl hydrocarbon and a conjugated diene compound, or an unsaturated carboxylic acid of a hydride of these copolymers Or a graft-modified product thereof. Here, the aromatic vinyl hydrocarbon / conjugated diene copolymer [C2] used for the preparation of the modified product
And hydride [C3] thereof 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, hydrogenated styrene / isoprene / styrene block copolymer rubber and styrene / butadiene random copolymer Rubber and the like can be mentioned.

In these copolymers, the molar ratio between the repeating unit derived from an aromatic vinyl hydrocarbon and the repeating unit derived from a conjugated diene (aromatic vinyl hydrocarbon / conjugated diene) is usually 10 / 90-70 / 30
It is. 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 hydrocarbon / conjugated diene copolymer or its hydrogenated product measured in decalin at 135 ° C. is usually from 0.01 to 10
dL / g, preferably in the range of 0.08 to 7 dL / g, and the glass transition temperature (Tg) is usually 0 ° C or lower, preferably -10 ° C or lower, particularly preferably -20 ° C or lower. The crystallinity measured by the X-ray diffraction method is 0 to
10%, preferably 0 to 7%, particularly preferably 0 to 5%
Within the range.

The graft-modified product (C) used in the present invention comprises:
The amount of grafting of the unsaturated carboxylic acid or derivative thereof is 0.01 to 100% by weight based on the graft-modified product (C).
It is in the range of 5% by weight, preferably 0.1-3% by weight.

The above base polymer [C1, C2, C3]
Specific examples of the unsaturated carboxylic acid to be grafted onto acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like. Examples of the derivative of the unsaturated carboxylic acid 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, monoethyl maleate, diethyl maleate, 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 Acid-N-monobutylamide, maleic acid-
N, N-dibutylamide, fumaric acid monoamide, fumaric acid diamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, Examples include sodium methacrylate, potassium acrylate, potassium methacrylate and the like. It is most preferred to use maleic anhydride among these graft monomers.

The graft modification to the base polymer [C1, C2, C3] using the above unsaturated carboxylic acid or its derivative (graft monomer) can be performed by various conventionally known methods. For example, a melt modification method in which a base polymer [C1, C2, C3] is melted using an extruder and a graft monomer is added to carry out graft copolymerization, or a base polymer [C1, C2, C3]
3] is dissolved in a solvent, 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 peroxides, organic peresters and the like are preferably used. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-
Butyl peroxide, 2,5-dimethyl-2,5-di (peroxidebenzoate) hexyne-3,1,4-
Organic peroxides such as bis (tert-butylperoxyisopropyl) benzene, 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 pervivalate, tert-butyl perdiethyl acetate; azoisobutyronitrile, dimethylazoiso An azo compound such as butyrate is used. Of these, dicumyl peroxide, di-tert-butyl peroxide, 2,2
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 radical initiator as described above is a base polymer [C1, C2, C3] 1
It is usually used at a ratio of 0.001 to 1 part by weight with respect to 00 parts by weight.

In the grafting reaction, other monomers such as styrene may coexist.

[Polyamide Resin Composition] The polyamide resin composition of the present invention contains the above components (A) and (B) as essential components, and if necessary, melt blends the component (C). Prepared. In the polyamide resin composition, preferably, a differential scanning calorimeter (DSC) is used.
, A melting point (Tm) is observed in the range of 165 to 230 ° C, preferably 165 to 185 ° C. This melting point can be observed both in the state of the composition and in the state of the molded article. In addition, the composition further optionally contains the following formula [IV] produced from a brominated styrene monomer:

Embedded image 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 brominated product of polyethylene ether, a brominated product of polystyrene or the like having a structural unit as a main component can be blended.

The polybrominated styrene preferably contains at least 60% by weight of dibrominated styrene units.
Those containing at least 10 wt% are particularly preferred. In addition to dibrominated styrene, polybrominated styrene obtained by copolymerizing monobrominated styrene and / or tribrominated styrene to 40% by weight or less, preferably 30% by weight or less may be used.

The amount of the organic flame retardant to be added is 0 to 60 parts by weight, preferably 1 to 20 parts by weight, particularly preferably 2 to 1 part by weight, per 100 parts by weight of the semi-aromatic polyamide (A).
5 parts by weight. In addition, 4
It is preferable to add about 0 to 60 parts by weight.

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

The semi-aromatic polyamide resin composition of the present invention may further comprise PPS (polyphenylene sulfide), PPE (polyphenyl ether), PES (polyether sulfone), PEI (polyether imide), LCP (polyether imide), if necessary. Liquid crystal polymers) and heat-resistant resins such as modified products of these resins can also 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 a phosphorus-based antioxidant, a phenol-based antioxidant, an amine-based antioxidant, a sulfur-based antioxidant, a copper compound, and an alkali metal halide compound. Such as an antioxidant (heat stabilizer) can be added.

Examples of the phosphorus-based antioxidants include 9, 10
-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenylphosphite, 2-
Ethylhexyl phosphate, dilauryl phosphite, tri-iso-octyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, trilauryl phosphite, trilauryl-di-thiophosphite, trilauryl-tri- Thiophosphite, trisnonylphenyl phosphite, distearylpentaerythritol 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'-bisphenylenediphosphite, distearylpentaerythritol diphosphite, tridecyl phosphite, tridecyl Stearyl phosphite,
2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, sorbitol-tris-phosphite-distearyl-mono-C30-diol ester and bis (2,4,6-tri-tert. −
(Butylphenyl) pentaerythritol diphosphite. Among them, bis (2,4-
Di-tert-butylphenyl) pentaerythritol-di-phosphite and bis (2,6-di-tert)
-Butyl-4-methylphenyl) pentaerythritol-di-, such as pentaerythritol-di-phosphite
A phosphite-based phosphorus-based antioxidant, and tetrakis (2,4-di-tert-butylphenyl) 4,4 ′
-Bisphenylenediphosphites.

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
tert-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'-isopropylidenebisphenol, 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-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxyphenyl) ) 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'-hexamethylenebis (3,5-di-tert-butylphenol-4-hydroxycinnamamide) can be mentioned.

Examples of the amine antioxidant include:
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.

Examples of sulfur-based antioxidants include thiobis (β-naphthol), thiobis (N-phenyl-β-
Naphthylamine), 2-mercaptobenzothiazole,
2-mercaptobenzimidazole, dodecylmercaptan, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyl dithiocarbamate, nickel isopropyl xanthate,
Mention may be made of dilaurylthiodipropionate and distearylthiodipropionate.

Examples of the copper compound include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, and pyrophosphoric acid. Examples thereof include copper salts of organic carboxylic acids such as cupric, copper sulfide, copper nitrate, and copper acetate. Examples of the alkali metal halide compounds include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, sodium bromide, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, and potassium iodide. Can be mentioned.
Of these, potassium iodide is particularly preferred.

These antioxidants can be used alone or in combination. Among these antioxidants, it is particularly preferable to use a phosphorus-based antioxidant alone or in combination with another antioxidant. It is preferable to use a copper compound and an alkali metal halide compound in combination.

Among these antioxidants, phosphorus-based antioxidants, phenol-based antioxidants, amine-based antioxidants and sulfur-based antioxidants are used in an amount of 0.05 to 100 parts by weight of polyamide (A). ~ 2 parts by weight, preferably 0.1 ~
It is preferred to use 1.5 parts by weight, most preferably in the range of 0.2 to 1.0 part by weight.

The semi-aromatic polyamide resin composition of the present invention may be used as an inorganic reinforcing material in the form of fibrous, powdery, granular,
Various inorganic fillers having a shape such as a plate shape, a needle shape, a cloth shape, and a mat shape can be blended.

For example, preferred examples of the fibrous inorganic filler include glass fiber, carbon fiber, asbestos fiber and boron fiber. Among them, glass fiber is particularly preferred. By using glass fiber, the moldability is improved, and the mechanical properties such as tensile strength, bending strength and flexural modulus of the molded article containing the inorganic reinforcing material, and the heat resistance properties such as thermal deformation temperature are improved. The average length of the glass fiber as described above 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 an aspect ratio within such ranges. Such a glass fiber is used in an amount of usually not more than 200 parts by weight, preferably not more than 5 parts by weight, based on 100 parts by weight of the resin component.
It is blended in an amount of 180 parts by weight, more preferably in an amount of 5 to 150 parts by weight.

In addition to the above-mentioned fibrous inorganic filler, examples of various fillers having a shape such as powder, granule, plate, needle, cloth, and mat used in the present invention include: Powdery 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, redwood, magnesium oxide and zinc oxide , Potassium-titanate and the like.

These fillers can be used as a mixture of two or more kinds. Further, these fillers can be used after being treated with a silane coupling agent or a titanium coupling agent.

The average particle diameter of such a filler is usually in the range of 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. Is done.

The polyamide resin composition of the present invention may further contain, in addition to the above components, an organic filler, a heat stabilizer, a weather resistance stabilizer, an antistatic agent and an anti-slip agent, as long as the properties are not impaired. And additives such as anti-blocking agents, anti-fogging agents, lubricants, pigments, dyes, natural oils, synthetic oils and waxes.

Examples of the organic filler include polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, a condensate of diaminodiphenyl ether and terephthalic acid (isophthalic acid), and para-phenylene terephthalamide. Wholly aromatic polyamides such as condensates of (meth) aminobenzoic acid; wholly aromatic polyamide-imides such as condensates of diaminodiphenyl ether with 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 materials formed from polytetrafluoroethylene and the like. Door can be.

Using the semi-aromatic polyamide resin composition prepared as described above, a usual melt molding method, for example, a compression molding method, an injection molding method or an extrusion molding method is used to obtain a desired shape. A molded article can be manufactured.

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

The semi-aromatic polyamide resin composition of the present invention is particularly excellent in mold releasability at the time of molding, and thus interconnects products molded using a complex mold, for example, electronic circuits. It is extremely useful for manufacturing connectors and the like, and such products can be produced efficiently. Moreover, the connector manufactured from the semi-aromatic polyamide resin composition of the present invention has not only excellent heat resistance but also an advantage that this connector is less deformed under stress under high temperature and high humidity. is there. Of course, the shape of the molded article produced using the semi-aromatic resin composition of the present invention is not particularly limited, and for example, electric tools and general industrial parts, mechanical parts such as gears and cams, and printed wiring boards It is also possible to produce various forms of molded articles such as electronic parts such as housings for electronic parts, and is particularly suitable as a resin for forming automobile interior / exterior parts, engine room parts and automobile electric parts. is there.

[0080]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples unless it exceeds the gist thereof. In the examples,
The measurement of the melting point and the crystallinity and the performance evaluation of the obtained resin composition were performed by the following methods.

Density: The strand obtained at the time of melt flow rate (MFR) measurement at a load of 2.16 kg at 190 ° C. is heat-treated at 120 ° C. for 1 hour, gradually cooled to room temperature over 1 hour, and measured with a density gradient tube. did. Melting point: The endothermic curve of DSC was determined, and the temperature at the maximum peak position was defined as the melting point (Tm). The endothermic curve was determined by filling the sample in an aluminum pan, rapidly raising the temperature to 340 ° C., maintaining the temperature at 340 ° C. for 5 minutes, then lowering the temperature to room temperature at 20 ° C./min.
It was determined by increasing the temperature at a rate of ° C./min. Glass transition point (Tg): determined according to ASTM D3418. Crystallinity: A 1 mm press sheet was prepared using the sample, and measured at 23 ° C. by the X-ray diffraction method.

Mechanical strength: Flexural modulus (FM) Measured according to the method of ASTM D-790. Izod impact strength (IZ) Measured by the method of ASTM D-256 (with notch). Flexural creep characteristics: Performed according to the method of JIS K7116. However, the test atmosphere was a temperature of 40 ° C. and a relative humidity of 93% as specified in JIS C0022,
Evaluation was made based on the amount of strain after one day.

Evaluation of mold clogging: (1) A mold for preparing a test piece as shown in FIG. 1 (A) was provided with a gas vent (air vent) having a depth of 10 μm and a width of 3 mm at the end. Then, injection molding was performed under the following molding conditions. (2) Molding conditions a. Molding machine: SG50-M manufactured by Sumitomo Heavy Industries, Ltd.
III b. Molding condition Cylinder setting temperature: 320 ° C Mold temperature: 120 ° C Injection speed: 60 mm / sec (3) Judgment of vent clogging When molding of polyamide containing many components such as unreacted monomers, low-order oligomers, and polymer decomposition products is repeated, These components accumulate on the vent and block the vent. Further, when the vent is closed, the air in the mold becomes difficult to escape, and the gas undergoes adiabatic compression in the final filling portion, resulting in a high temperature. When the temperature of the gas becomes high, the resin that is in contact with the carbonized material is blackened by carbonization, so that "gas burning" occurs, and the tip of the obtained test piece becomes black as shown in FIG. 1 (B). When the test piece obtained in this way turns black, it is determined that vent blocking has occurred. Heat distortion temperature (HDT): Measured according to the method of ASTM D648.

Mold release force: A product mold having a large number of pins and a large surface area, such as a connector, is used.
The mold was opened, and the pressure required for ejecting the molded product from the mold (movable side) by the ejection mechanism was measured by a sensor.

Reference Example 1 Production of Semi-Aromatic Polyamide 139.3 g (1.20 mol) of 1,6-diaminohexane, 2-methyl-1,5-diaminopentane
3 g (1.20 mol), terephthalic acid 365.5 g
(2.2 mol), sodium hypophosphite 0.1 as a catalyst.
55 g (5.2 × 10 ⁻³ mol) and ion-exchanged water 6
4 ml into a 1 liter reactor, and after purging with nitrogen,
The reaction was performed at 250 ° C. and 35 kg / cm ² for 1 hour. 1,6-diaminohexane and 2-methyl-1,5
The molar ratio with diaminopentane is 50:50. 1
After a lapse of time, the reaction product generated in the reactor is connected to the reactor, and the pressure is reduced to about 10 kg / cm ^2.
Pull out to the receiver set low, the limiting viscosity [η] is 0.1
561 g of a 5 dl / g polyamide precursor were obtained.

Next, the polyamide precursor is dried,
Using a twin-screw extruder, melt polymerization was performed at a cylinder set temperature of 330 ° C. to obtain a semi-aromatic polyamide (PA-1). The composition of this aromatic polyamide is as follows. The 1,6-diaminohexane component unit content in the diamine component unit was 50 mol%, and the 2-methyl-1,5-diaminopentane component unit content was 50 mol%.

Reference Example 2 Production of Semi-Aromatic Polyamide 269.3 g (2.32 mol) of 1,6-diaminohexane, 205.6 g (1.24 mol) of terephthalic acid, 148.0 g of adipic acid (1. 0.48 g (4.50 × 10 ⁻³ mol) of sodium hypophosphite as a catalyst and 3.43 g (2.8 of benzoic acid) as a molecular weight regulator.
1 × 10 ⁻² mol) and 62 ml of ion-exchanged water
Liter reactor, purged with nitrogen, 250 ° C, 3
The reaction was performed under the condition of 5 kg / cm ² for 1 hour. The molar ratio of terephthalic acid to adipic acid is 55:45. 1
After a lapse of time, the reaction product generated in the reactor is connected to the reactor, and the pressure is reduced to about 10 kg / cm ^2.
Pull out to the receiver set low, the limiting viscosity [η] is 0.1
559 g of a 5 dl / g polyamide precursor were obtained.

Next, the polyamide precursor is dried,
Using a twin-screw extruder, melt polymerization was performed at a cylinder set temperature of 330 ° C. to obtain a semi-aromatic polyamide (PA-2). The composition of this aromatic polyamide is as follows. The terephthalic acid component unit content in the dicarboxylic acid component unit is
55 mol%, adipic acid component unit content is 45 mol%
It is.

Reference Example 3 Production of Modified Ethylene / 1-Butene Copolymer Ethylene-1-butene copolymer prepared using a Ti-based catalyst [abbreviated as (PE-1); density = 0.92 g / cm
³ , melting point (Tm) = 124 ° C., crystallinity = 48%, M
FR (ASTM D 1238, 190 ° C, 2.16kg load) = 1.0g
/ 10 min, ethylene content = 96 mol%] 100 parts by weight, maleic anhydride 0.8 part by weight, and peroxide [trade name: Perhexin-25B, manufactured by NOF Corporation] 0.0
7 parts by weight were mixed with a Hexchel mixer, and the resulting mixture was melt-grafted and modified with a single-screw extruder having a diameter of 65 mm 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 to be 0.8% by weight. MFR (AS
TM D 1238, 190 ° C, 2.16kg load) 0.27g / 1
It was 0 minutes and the melting point was 122 ° C. The density is 0.92
g / cm ³ .

Reference Example 4 The modified ethylene / propylene copolymer had a production density of 0.87 g / cm ³ and an MFR (ASTM D 1238, 19
Modified ethylene / propylene copolymer graft-modified with maleic anhydride in exactly the same manner as in Reference Example 3, except that an ethylene / propylene copolymer having a temperature of 0 ° C. and a load of 2.16 kg) of 1 g / 10 min was used. (Abbreviated as (MAH-PE-2)). The grafted amount of maleic anhydride of this modified ethylene / propylene copolymer (MAH-PE-2)
It was 1.0% by weight as measured by R analysis. Also M
FR (ASTM D 1238, 190 ° C, 2.16kg load) is 0.3g
/ 10 min and the melting point was 118 ° C. The density is 0.
Was 87~0.88g / cm ^3.

Examples 1-3 The semi-aromatic polyamides PA-1, PA-2 obtained in Reference Examples 1 and 2, and the modified ethylene / 1-butene copolymer obtained in Reference Example 3 (MAH- P
E-1), and nylon 12 (abbreviated as (PA-3)),
Talc was mixed in the proportions shown in Table 1 and then 30 mm
300 to 3 using a vented twin screw extruder with φ
The mixture was melt-mixed at a cylinder temperature of 35 ° C. to produce pellets of the semi-aromatic polyamide resin composition. in this case,
As for the dicarboxylic acid component in the component composed of polyamide (PA-1) and polyamide (PA-2),
The terephthalic acid component unit content was 72 mol%, the adipic acid component unit content was 28 mol%, and regarding the diamine component, the 1,6-diaminohexane component unit content was 81 mol% and 2-methyl-1 The unit content of the 5,5-diaminopentane component was 19 mol%. The melting point derived from the blend of polyamide (PA-1) and polyamide (PA-2) was 3 based on the result of DSC of the whole composition.
05 ° C. Tg was 105 ° C. The nylon 12 used was UBENY12, manufactured by Ube Industries, Ltd.
3014B (flexural modulus of 1450 MPa). Injection molded test pieces were prepared using the pellets thus obtained, and the performance of the test pieces was evaluated. Table 1 shows the evaluation results. For the semi-aromatic polyamide resin composition prepared in Example 2, the endothermic curve measured by DSC is shown in FIG.

Example 4 Example 2 was repeated except that the modified ethylene / propylene copolymer (MAH-PE-2) prepared in Reference Example 4 was used instead of MAH-PE-1.
Injection-molded test pieces made of a semi-aromatic polyamide resin composition were prepared in the same manner as described above, and their performance was evaluated. Table 1 shows the results.

[Comparative Example 1] Without using nylon 12,
Injection molded test pieces composed of a semi-aromatic polyamide resin composition were prepared in the same manner as in Examples 1 to 3 with the composition shown in Table 1,
The performance was evaluated. Table 1 shows the results.

[Comparative Examples 2 and 3] Nylon 12 (PA-
Instead of 3), nylon 6,6 (hereinafter abbreviated as PA-66) or nylon 11 (hereinafter abbreviated as PA-11)
Was performed in the same manner as in Example 2 except that Table 1 shows the results. As nylon 6,6, Amilan CM3007 manufactured by Toray Industries, Inc. was used, and as nylon 11, Rilsan BMN-0 manufactured by Toray Industries, Inc. was used.

Comparative Example 4 Semiaromatic polyamide (PA-
Instead of blending 1, PA-2) and nylon 12 (PA-12), a copolymer composition containing these poarimid units (hereinafter abbreviated as COPA) was used. This copolymer composition (COPA) was produced as follows.

In Reference Example 2, the aromatic polyamide (PA
-2) has an intrinsic viscosity [η] of 0.1.
Using a 15 dl / g polyamide precursor, this precursor and an aminododecanoic acid monomer were blended in a weight ratio of 93: 7, and melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to form a copolymer. A polymerized polyamide was obtained. The composition of the copolymerized polyamide is as follows. The terephthalic acid component unit content in the dicarboxylic acid component unit is
55 mol%, the adipic acid component unit content is 45 mol%, and the aminododecanoic acid component unit content in the copolymerized polyamide is 7% by weight.

Next, the polyamide (P
A-1) and the copolymerized polyamide obtained above were used in 36.
The mixture was blended at a weight ratio of 1: 63.9, and was melt-extruded at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain a copolymerized polyamide composition (COPA). The composition of each component unit of this composition is as follows. The 1,6-diaminohexane component unit content in the diamine component unit is 82
Mol%, the content of the 2-methyl-1,5-diaminopentane component unit was 18 mol%. The terephthalic acid component unit content in the dicarboxylic acid component unit is 71%.
The mol%, the adipic acid component unit content was 29 mol%, and the aminododecanoic acid component unit content was 4.5% by weight.

The above copolymerized polyamide composition (COP)
A) was mixed with the modified ethylene / 1-butene copolymer (MAH-PE-1) obtained in Reference Example 3 and talc in the proportions shown in Table 1, and was completely the same as Examples 1 to 3. In this way, pellets of the semi-aromatic polyamide resin composition were produced, and then injection molded test pieces made of the resin composition were prepared, and their performance was evaluated. Table 1 shows the results. FIG. 3 shows an endothermic curve of the semi-aromatic polyamide resin composition obtained above measured by DSC.

[0099]

[Table 1]

[0100]

Industrial Applicability The semi-aromatic polyamide resin composition of the present invention is particularly excellent in mold releasability at the time of molding, and is suitable for production of connector parts molded using a mold having a complicated structure, for example. Used particularly effectively. Further, the resin composition of the present invention has a small oligomer precipitation amount during molding, so that the vent holes of the molding die are hardly clogged, and are suitable for long-time molding,
Furthermore, it has excellent heat aging resistance, heat deformation resistance, creep resistance, and impact resistance.

[Brief description of the drawings]

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view of a mold used for evaluation of clogging of a mold in an embodiment (A) and a diagram (B) showing "gas burning" of a molded product.

FIG. 2 is a graph showing an endothermic curve by DSC of the semi-aromatic polyamide resin obtained in Example 3.

FIG. 3 is a diagram showing an endothermic curve by DSC of the semi-aromatic polyamide resin obtained in Comparative Example 4.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 51:06)

Claims (10)

[Claims] (A) A polyamide whose main constituent 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 terephthalic acid. A polyamide copolymer, wherein the diamine component unit is a linear alkylene diamine component unit having 4 to 18 carbon atoms and / or an alkylene diamine component unit having 4 to 18 carbon atoms having a side chain alkyl group. (B) (i) a structural unit derived from a lactam having 12 carbon atoms, (ii) a structural unit derived from an aminocarboxylic acid having 12 carbon atoms, and (iii) a structural unit derived from dodecanedioic acid and a diamine. Aliphatic polyamides containing at least one selected from the group consisting of the following structural units as a structural unit: (C) graft-modified ethylene / α At least one graft modification selected from the group consisting of olefin copolymers, graft-modified aromatic vinyl compound / conjugated diene copolymers, and graft-modified hydrides of the aromatic vinyl compound / conjugated diene copolymers The component (A) is 98 to 65% by weight and the component (B) is 1% by weight based on the total amount of the components (A), (B) and (C).
A semi-aromatic polyamide resin composition comprising the component (C) in an amount of 1 to 25% by weight and the above component (C) in an amount of 1 to 25% by weight. 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 a range of 55 mol% or less based on all dicarboxylic acid units. The semi-aromatic polyamide resin composition according to claim 1, wherein the composition comprises: 3. The semi-aromatic polyamide resin composition according to claim 1, wherein a melting point (Tm) is observed in a range of 165 to 230 ° C. in a measurement by a differential scanning calorimeter (DSC). 4. The polyamide copolymer (A) wherein the diamine component unit has 55 to 99 mol% of a linear alkylene diamine component unit having 4 to 18 carbon atoms and / or a C 4 to C 4 atom having a side chain alkyl group. The semi-aromatic polyamide resin composition according to claim 1, comprising 1 to 45 mol% of 18 alkylene diamine component units. 5. The aliphatic polyamide (B) comprises (i) a structural unit derived from a lactam having 12 carbon atoms, (ii) a unit derived from an aminocarboxylic acid having 12 carbon atoms, and (iii) dodecane. The semi-aromatic polyamide resin composition according to claim 1, wherein the aliphatic polyamide contains at least 50 mol% or more of at least one selected from the group consisting of structural units derived from a diacid and a diamine. object. 6. The aromatic polyamide (A) has a melting point of 28.
The semi-aromatic polyamide resin composition according to claim 1, wherein the temperature is 0 to 330 ° C. 7. The polyamide (B) has a flexural modulus measured by ASTM D790 of 1300 MPa or more for a test piece obtained by injection molding.
The semi-aromatic polyamide resin composition according to any one of the above. 8. The semi-aromatic polyamide according to claim 1, wherein the graft-modified product (C) has a density in a range of 0.85 to 0.95 g / cm ^3. Resin composition. 9. The polyamide resin composition comprising a resin component 10
The semi-aromatic polyamide resin composition according to any one of claims 1 to 8, further comprising 1 to 200 parts by weight of an inorganic filler with respect to 0 parts by weight. 10. A connector molded from the semi-aromatic polyamide resin composition according to claim 1.