WO2019035484A1

WO2019035484A1 - Semi-aromatic polyamide resin composition and molded body thereof

Info

Publication number: WO2019035484A1
Application number: PCT/JP2018/030519
Authority: WO
Inventors: 功鷲尾; 弘一佐野; 信宏滝沢; 晶規天野; 翔石川
Original assignee: 三井化学株式会社
Priority date: 2017-08-18
Filing date: 2018-08-17
Publication date: 2019-02-21
Also published as: JP6834006B2; JPWO2019035484A1

Abstract

This semi-aromatic polyamide resin composition contains a semi-aromatic polyamide resin (A), a modified olefin polymer (B) and a copper-based stabilizer (C), and satisfies condition (1) or (2) below. (1) The modified olefin polymer (B) includes a modified ethylene·α-olefin copolymer (B1) which contains 0.01-5 mass% of functional group structural units and has a density of 0.89-0.95 g/cm3, a melting point of 90-127ºC and a degree of crystallinity of 20-60%. (2) The modified olefin polymer (B) includes a modified ethylene·α-olefin copolymer (B2) which contains 0.01-5 mass% of functional group structural units and has a density of not less than 0.80 g/cm3 but less than 0.89 g/cm3, and the semi-aromatic polyamide resin composition further contains an unmodified copolymer of ethylene and an α-olefin having 3-20 carbon atoms as an unmodified olefin polymer (D).

Description

Semi-aromatic polyamide resin composition and molded article thereof

The present invention relates to a semiaromatic polyamide resin composition and a molded article thereof.

Conventionally, various proposals have been made for impact-resistant semi-aromatic polyamides. For example, Patent Document 1 discloses a dicarboxylic acid unit comprising 50 to 100% by mole of terephthalic acid unit and 0 to 40% by mole of an aromatic dicarboxylic acid other than terephthalic acid or a linear aliphatic dicarboxylic acid unit having 6 to 18 carbon atoms A polyamide composition is disclosed consisting of a semi-aromatic polyamide comprising a) and an alkylene diamine unit (b) and a modified elastic copolymer. Moreover, it is also known that the polyamide composition which consists of such semi-aromatic polyamide and a modification | denaturation elastic polymer is excellent in heat resistance and impact resistance (for example, patent documents 2 and 3).

In recent years, weight reduction by replacing metal members used for automobile parts with resin has been studied. Polyamide resins are significantly lighter than metals, and have excellent rigidity, heat resistance, oil resistance, and the like, and thus are suitably used as resin materials that constitute automobile parts.

Among automobile parts, automobile engine room parts are required to have higher heat resistance (high temperature resistance). On the other hand, a polyamide resin composition containing, for example, a polyamide resin and glass fiber (for example, Patent Document 4); a semiaromatic polyamide resin (A), a relatively low density modified polyolefin (B), and a copper compound A polyamide composition (for example, Patent Document 5) containing (C) and an organic stabilizer (D) has been proposed.

JP-A-4-108855 Unexamined-Japanese-Patent No. 2-41318 gazette Unexamined-Japanese-Patent No. 5-98152 Unexamined-Japanese-Patent No. 2-240160 JP, 2010-202724, A

As shown in Patent Document 5, a molded product is obtained by further blending a copper compound (C) into a polyamide composition containing a semiaromatic polyamide resin (A) and a relatively low density modified polyolefin (B). The rigidity at high temperatures and heat resistance (hereinafter also referred to as heat aging resistance) can be improved. However, the above polyamide composition further containing the copper compound (C) is particularly liable to form white powder derived from low molecular weight components such as unreacted monomers, lower oligomers or polymer decomposition components during molding, and mold contamination There was a new problem of being prone to White powder generated in the mold tends to cause clogging of the mold vent holes, and if it is clogged, it is necessary to stop the molding and clean the mold. In addition, when forming fine components such as electronic parts, particularly connectors, in particular, the white powder generated in the mold tends to damage the appearance or reduce the dimensional accuracy. Moreover, the molded object obtained from the said polyamide composition also had the problem that creep resistance under high temperature was also low.

Therefore, a semi-aromatic polyamide capable of suppressing mold contamination during molding and capable of producing a molded article excellent in heat resistance, creep resistance at high temperature and mechanical strength (such as rigidity, impact resistance, flexural strength, etc.) Resin compositions are desired.

The present invention has been made in view of the above circumstances, and it is a semi-conductor capable of producing a molded article which is less likely to cause mold contamination during molding and which is excellent in heat resistance, creep resistance at high temperatures and mechanical strength. An object of the present invention is to provide an aromatic polyamide resin composition.

The present invention relates to the following semiaromatic polyamide resin composition and a molded article thereof.
[1] A semiaromatic polyamide resin (A) having a melting point of 280 to 330 ° C. as measured by differential scanning calorimetry (DSC) and a modified olefin polymer (B) containing a functional group structural unit containing a hetero atom A semi-aromatic polyamide resin composition comprising: and a copper-based stabilizer (C),
The semi-aromatic polyamide resin (A) contains a repeating unit consisting of a dicarboxylic acid component unit and a diamine component unit, and the dicarboxylic acid component unit is a terephthalic acid component with respect to the total number of moles of the dicarboxylic acid component unit. Contains 45 mol% or more of units,
The diamine component unit has 50 to 100% by mole of a linear alkylene diamine component unit having 4 to 18 carbon atoms and 4 to carbon atoms having a side chain alkyl group based on the total number of moles of the diamine component unit. Containing 18 to 50 mol% of alkylene diamine component units,
The said semi-aromatic polyamide resin composition is a semi-aromatic polyamide resin composition which satisfy | fills following (1) or (2).
(1): The modified olefin polymer (B) is
A modified ethylene / α-olefin copolymer (B1) obtained by modifying a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms with an unsaturated carboxylic acid or a derivative thereof,
The modified ethylene / α-olefin copolymer (B1) is
It contains 0.01 to 5% by mass of a functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or its derivative, and satisfies the following requirements (i) to (iii): (i) density is 0.89 in the range of ~ 0.95g / cm ³ (ii) the temperature of the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC) (melting point; Tm) is 90 ~ 127 ℃ (iii) X-ray The degree of crystallinity measured by diffraction method is 20 to 60% (2): The modified olefin polymer (B) is
A modified ethylene / α-olefin copolymer (B2) obtained by modifying a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms with an unsaturated carboxylic acid or a derivative thereof,
The modified ethylene / α-olefin copolymer (B2) is
It contains 0.01 to 5% by mass of the functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or its derivative, and satisfies the following requirement (iv), and (iv) the density is 0.80 g / cm ^The semi-aromatic polyamide resin composition in the range of ³ or more and less than 0.89 g / cm ³ contains unmodified ethylene and 3 to 7 carbon atoms as the unmodified olefin polymer (D) not containing the functional group structural unit. Further included are copolymers with 20 alpha-olefins.

That is, the first of the present invention relates to the following semiaromatic polyamide resin composition and a molded article thereof.
[2] The semi-aromatic polyamide resin composition according to [1], which satisfies the above (1).
[3] The modified olefin polymer (B) is a copolymer of ethylene and an α-olefin of 3 to 20 carbon atoms modified with an unsaturated carboxylic acid or a derivative thereof to obtain a modified ethylene / α-olefin copolymer The modified ethylene / α-olefin copolymer (B2) further comprises a combination (B2), in which the functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or its derivative is 0.01 to 5 mass %, And the semi-aromatic polyamide resin composition as described in [2] which satisfy | fills following requirements (iv).
(Iv) The polymer further includes an unmodified olefin polymer (D) not having a functional group structural unit containing a hetero atom, the density of which is in the range of 0.80 g / cm ^{3 to} 0.89 g / cm ³ [4] The semi-aromatic polyamide resin composition according to [2] or [3], wherein the unmodified olefin polymer (D) is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.
[5] The dicarboxylic acid component unit is an aromatic carboxylic acid component unit other than terephthalic acid and / or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms relative to the total number of moles of the dicarboxylic acid component unit The semi-aromatic polyamide resin composition according to any one of [2] to [4], further comprising 55 mol% or less in total.
[6] The diamine component unit has 50 to 99 mol% of the linear alkylene diamine component unit having 4 to 18 carbon atoms and the side chain alkyl group with respect to the total number of moles of the diamine component unit. The semi-aromatic polyamide resin composition according to any one of [2] to [5], containing 1 to 50 mol% of an alkylene diamine component unit having 4 to 18 carbon atoms.
[7] The semiaromatic polyamide resin composition according to any one of [2] to [6], wherein the linear alkylene diamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit .
[8] The alkylene diamine component unit having 4 to 18 carbon atoms having a side chain alkyl group is a 2-methyl-1,5-diaminopentane component unit according to any one of [2] to [7]. Semi-aromatic polyamide resin composition.
[9] The semi-aromatic polyamide resin (A) has an intrinsic viscosity [η] measured at 30 ° C. in concentrated sulfuric acid of 0.9 dl /, based on 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A). 35 to 100 parts by mass of a semi-aromatic polyamide resin (A1) having a g or more, and a semi-aromatic polyamide resin (A1) having a limiting viscosity [.eta.] of 0.7 dl / g or more and less than 0.9 dl / g The semi-aromatic polyamide resin composition according to any one of [2] to [8], comprising 0 to 65 parts by mass of the aromatic polyamide resin (A2).
[10] The semiaromatic polyamide resin composition according to any one of [2] to [9], further comprising 1 to 200 parts by mass of an inorganic filler (E) with respect to 100 parts by mass of the resin component.
[11] The semiaromatic polyamide resin composition according to [10], wherein the inorganic filler (E) contains a fibrous inorganic filler or talc.
[12] 50 to 98 parts by mass of the semiaromatic polyamide resin (A), 1 to 40 parts by mass of the modified olefin polymer (B), and 0.0001 to 1 of the copper stabilizer (C) Parts by mass, 0 to 40 parts by mass of an unmodified olefin polymer (D) not containing a functional group structural unit containing a hetero atom, and 0 to 50 parts by mass of an inorganic filler (E) (however, The total amount of the semi-aromatic polyamide resin (A), the modified olefin polymer (B), the copper stabilizer (C), the unmodified olefin polymer (D), and the inorganic filler (E) is 100 mass The semiaromatic polyamide resin composition according to any one of [2] to [11].
[13] A molded body obtained from the semiaromatic polyamide resin composition according to any one of [2] to [12].

The second of the present invention relates to the following semiaromatic polyamide resin composition and a molded article thereof.
[14] The semiaromatic polyamide resin composition as described in [1], which satisfies the above (2).
[15] The modified olefin polymer (B) is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms modified with an unsaturated carboxylic acid or a derivative thereof to obtain a modified ethylene / α-olefin copolymer Further includes combining (B1),
The modified ethylene / α-olefin copolymer (B1) contains 0.01 to 5% by mass of a functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or its derivative, and the following requirements (i The semi-aromatic polyamide resin composition according to [14], satisfying (1) to (iii).
(I) the density is in the range of 0.89 to 0.95 g / cm ³ (ii) the temperature (melting point; Tm) of the maximum peak position of the endothermic curve measured by differential scanning calorimetry (DSC) is 90 to 127 ° C (iii) The degree of crystallinity measured by X-ray diffraction method is 20 to 60%. [16] The dicarboxylic acid component unit is other than terephthalic acid relative to the total number of moles of the dicarboxylic acid component unit. The semi-aromatic polyamide resin composition according to [14] or [15], further comprising 55 mol% or less in total of an aromatic carboxylic acid component unit and / or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms.
[17] The diamine component unit has 50 to 99 mol% of the linear alkylene diamine component unit having 4 to 18 carbon atoms and the side chain alkyl group with respect to the total number of moles of the diamine component unit. The semi-aromatic polyamide resin composition according to any one of [14] to [16], containing 1 to 50 mol% of an alkylene diamine component unit having 4 to 18 carbon atoms.
[18] The semiaromatic polyamide resin composition according to any one of [14] to [17], wherein the linear alkylene diamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit. .
[19] The alkylene diamine component unit having 4 to 18 carbon atoms having a side chain alkyl group is a 2-methyl-1,5-diaminopentane component unit according to any one of [14] to [17]. Semi-aromatic polyamide resin composition.
[20] The semi-aromatic polyamide resin (A) has an intrinsic viscosity [η] measured at 30 ° C. in concentrated sulfuric acid of 0.9 dl /, based on 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A). 35 to 100 parts by mass of a semi-aromatic polyamide resin (A1) having a g or more, and a semi-aromatic polyamide resin (A1) having a limiting viscosity [.eta.] of 0.7 dl / g or more and less than 0.9 dl / g The semi-aromatic polyamide resin composition according to any one of [14] to [19], comprising 0 to 65 parts by mass of the aromatic polyamide resin (A2).
[21] The semiaromatic polyamide resin composition according to any one of [14] to [20], further comprising 1 to 200 parts by mass of an inorganic filler (E) with respect to 100 parts by mass of the resin component.
[22] The semiaromatic polyamide resin composition according to [21], wherein the inorganic filler (E) contains a fibrous inorganic filler or talc.
[23] 50 to 97 parts by mass of the semiaromatic polyamide resin (A), 1 to 40 parts by mass of the modified olefin polymer (B), and 0.0001 to 1 of the copper stabilizer (C) (A semi-aromatic polyamide resin (A), including: parts by mass, 1 to 40 parts by mass of the unmodified olefin polymer (D), and 0 to 50 parts by mass of the inorganic filler (E)) The total of the modified olefin polymer (B), the copper stabilizer (C), the unmodified olefin polymer (D), and the inorganic filler (E) is 100 parts by mass), [14] to [14] 22. The semi-aromatic polyamide resin composition according to any one of 22.
[24] A molded article obtained from the semiaromatic polyamide resin composition according to any one of [14] to [23].

According to the present invention, there is provided a semi-aromatic polyamide resin composition capable of producing a molded article which is less likely to cause mold contamination during molding and which is excellent in heat resistance, creep resistance at high temperatures and mechanical strength. be able to.

The inventors of the present invention conducted intensive studies and found that the semi-aromatic polyamide resin composition containing the semi-aromatic polyamide resin (A) and the copper-based stabilizer (C) It is preferable to further contain a high density modified ethylene / α-olefin copolymer (B1) (structure of the above (1)) or “a relatively low density modified ethylene · α- as a modified olefin polymer (B)” By further containing the olefin copolymer (B2) and the unmodified olefin polymer (D) (structure of the above (2)), white powder is generated in the mold at the time of molding while heat resistance is enhanced. It has been found that it is possible to suppress mold contamination and to well suppress mold contamination.

Although the reason for this is not clear, it is presumed as follows. That is, as described above, a relatively high density modified ethylene / α-olefin copolymer (B1) is further contained, or a relatively low density modified ethylene / α-olefin copolymer (B2), By further containing the unmodified olefin polymer (D), the melt flowability at the time of molding of the semi-aromatic polyamide resin composition is improved to the extent that the creep resistance of the molded article at high temperatures is not impaired, The heat of shear can be reduced. As a result, the amount of generation or scattering of low molecular weight components such as unreacted monomers, lower oligomers or polymer decomposition products is reduced, and white powder is formed, without impairing the creep resistance of the resulting molded article at high temperatures. Is considered to be suppressed (the mold deposit is reduced). That is, it is considered that the heat resistance can be enhanced and the mold contamination at the time of molding can be suppressed without impairing the creep resistance at high temperature of the molded body.

Furthermore, mold contamination is caused by combining the semiaromatic polyamide resin (A1) having a relatively high intrinsic viscosity with the semiaromatic polyamide resin (A2) having a relatively low intrinsic viscosity as the semiaromatic polyamide resin (A). Was found to be able to suppress more highly. The present invention has been made based on these findings.

1. Semi-Aromatic Polyamide Resin Composition The semi-aromatic polyamide resin composition of the present invention comprises at least a semi-aromatic polyamide resin (A), a modified olefin polymer (B), and a copper stabilizer (C).

The modified olefin polymer (B) contains a relatively high density modified ethylene / α-olefin copolymer (B1) or a relatively low density modified ethylene / α-olefin copolymer (B2). When the modified olefin polymer (B) contains a relatively low density modified ethylene / α-olefin copolymer (B2), in order to suppress mold contamination, the unmodified olefin polymer (D) is further combined Is preferred.

That is, the first semiaromatic polyamide resin composition of the present invention comprises a semiaromatic polyamide resin (A) and a relatively high density modified ethylene / α-olefin copolymer (A) as a modified olefin polymer (B) B1) and a copper stabilizer (C). The second semiaromatic polyamide resin composition of the present invention comprises a semiaromatic polyamide resin (A) and a modified ethylene / α-olefin copolymer (B2) having a relatively low density as the modified olefin polymer (B) And a copper stabilizer (C) and an unmodified olefin polymer (D).

1-1. Semi-aromatic polyamide resin (A)
The semi-aromatic polyamide resin (A) used in the resin composition of the present invention is composed of a repeating unit composed mainly of a specific dicarboxylic acid component unit [a] and a specific diamine component unit [b]. There is.

The dicarboxylic acid component unit [a] contains 45 to 100 moles of terephthalic acid component unit (a-1), assuming that the total number of moles of the dicarboxylic acid component unit contained in the semiaromatic polyamide resin (A) is 100 mol%. %, And may optionally be contained in an amount of 50 to 90 mol%, preferably 55 to 80 mol%.
The dicarboxylic acid component unit [a] is a dicarboxylic acid component unit other than terephthalic acid, that is, an aromatic dicarboxylic acid component unit other than terephthalic acid (a-2) and / or an aliphatic dicarbon having 4 to 20 carbon atoms. The acid component unit (a-3) is contained in a total amount of 0 to 55 mol%, and may be contained in an amount of 10 to 50 mol%, preferably 20 to 45 mol%, as needed. For example, when the dicarboxylic acid component unit [a] contains a small amount of the aliphatic dicarboxylic acid component unit (a-3), the moldability of the semiaromatic polyamide resin (A) can be further improved. When the content of aliphatic dicarboxylic acid component units is 55 mol% or less, the content of terephthalic acid component units inevitably exceeds 45 mol%, and the resulting semi-aromatic polyamide resin (A) Has a low water absorption rate, and the melting point tends to be 280 ° C. or more. Therefore, the molded object formed from such a semi-aromatic polyamide resin (A) has few dimensional changes by water absorption, and heat resistance may also be enough.

Examples of the aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid include component units derived from isophthalic acid, 2-methylterephthalic acid, naphthalene dicarboxylic acid and the like. Among these, an isophthalic acid component unit is preferable.

The aliphatic dicarboxylic acid component unit (a-3) is derived from an aliphatic dicarboxylic acid having an alkylene group of 4 to 20, preferably 6 to 12 carbon atoms. Examples of such aliphatic dicarboxylic acid component units (a-3) include component units derived from succinic acid, adipic acid, azelaic acid and sebacic acid. Among these, an adipic acid component unit and a sebacic acid component unit are preferable.

The semi-aromatic polyamide resin (A) comprises terephthalic acid component unit (a-1), aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid represented by isophthalic acid component unit, and aliphatic dicarboxylic acid component In addition to the unit (a-3), component units derived from tribasic or higher polybasic carboxylic acids such as a small amount of trimellitic acid or pyromellitic acid may be further contained. Component units derived from such a polyvalent carboxylic acid may be contained usually in an amount of 0 to 5 mol% based on 100 mol% in total of the dicarboxylic acid component units [a].

The diamine component unit [b] contains a linear alkylene diamine having 4 to 18 carbon atoms (linear alkylene diamine) component unit (b-1), and has an alkyl group having a side chain alkyl group and having 4 to 18 carbon atoms It is preferable to further include a diamine component unit (b-2).

The diamine component unit [b] is a linear alkylene diamine component unit having 4 to 18 carbon atoms (b−, when the total number of moles of the diamine component unit contained in the semi-aromatic polyamide resin (A) is 100 mol%. 1) in an amount of 50 to 100 mol%, optionally 50 to 99 mol%, preferably 50 to 98 mol%, more preferably 50 to 95 mol%, still more preferably 50 to 93 mol You may contain in the quantity of%.
Further, the diamine component unit [b] contains an alkylene diamine component unit (b-2) having 4 to 18 carbon atoms having a side chain alkyl group in an amount of 0 to 50% by mole, as necessary It may be contained in an amount of 1 to 45 mol%, preferably 2 to 50 mol%, more preferably 5 to 50 mol%, still more preferably 7 to 50 mol%.
Thus, when the diamine component unit [b] contains two specific alkylene diamine component units in the amount as described above, the melting point of the semiaromatic polyamide resin (A) can be made semiaromatic during molding It may be reduced to such an extent that the polyamide resin composition does not cause gas burning. In addition, the melt flowability of the semi-aromatic polyamide resin composition at the time of molding can be enhanced, and the creep resistance at high temperature of the molded article can be enhanced.

The diamine component unit [b] is a linear alkylene diamine component unit (b-1) having 4 to 18 carbon atoms and an alkylene diamine component unit (b-2) having 4 to 18 carbon atoms having a side chain alkyl group In the case where both are included, when the content of the linear alkylene diamine component unit (b-1) having 4 to 18 carbon atoms is 99 mol% or less, a remarkable decrease in melt flowability at the time of molding hardly occurs. In addition, when the content of the alkylene diamine component unit (b-2) having 4 to 18 carbon atoms having a side chain alkyl group is 50 mol% or less, the crystallization rate of the semiaromatic polyamide resin (A) is slow. It is difficult to become hard and heat resistance tends to be sufficient.

Examples of linear alkylene diamine component unit (b-1) include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, Component units derived from 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane are included. Among these, component units derived from 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane are preferred, and derived from 1,6-diaminohexane Component units are more preferred. These component units may be contained in plural kinds in the semi-aromatic polyamide resin (A).

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 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 2,4-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-diaminooctane, 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- Component units derived from diethyl-1,8-diamino-octane and 5-methyl-1,9-diamino-nonane are included. Among these, component units derived from a side chain alkyl diamine having 1 to 2 side chain alkyl groups having 1 to 2 carbon atoms and having 4 to 10 carbon atoms in the main chain are preferable, Component units derived from methyl-1,5-diaminopentane are more preferred. These component units may be contained in plural kinds in the semi-aromatic polyamide resin (A).

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

The repeating unit represented by the following formula is contained in the example of the repeating unit which consists of the dicarboxylic acid component unit [a] and the diamine component unit [b] as described above. That is, the repeating unit constituting the semi-aromatic polyamide resin (A) contains terephthalic acid component unit (a-1) as the dicarboxylic acid component unit [a]. The repeating unit having such terephthalic acid component unit (a-1) can be represented by the following formula [I-a]. In the following formulae, R ¹ is an alkylene group having 4 to 18 carbon atoms which may have a side chain.

It is not necessary that all of the repeating units constituting the semi-aromatic polyamide resin (A) are the repeating units represented by the above [Ia], and a part of the terephthalic acid component unit (a-1) as described above May further contain a repeating unit replaced with another dicarboxylic acid component.

Examples of other carboxylic acid component units other than terephthalic acid component include, as described above, aromatic dicarboxylic acid component units (a-2) other than terephthalic acid and aliphatic dicarboxylic acid component units (a-3) .

The repeating unit having an aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid is preferably a repeating unit having an isophthalic acid component unit, and can be represented by the following formula [Ib]. In the following formulae, R ¹ is an alkylene group having 4 to 18 carbon atoms which may have a side chain.

The repeating unit having an aliphatic dicarboxylic acid component unit (a-3) can be represented by the following formula [II]. In the following formulas, R ¹ is an alkylene group having 4 to 18 carbon atoms which may have a side chain, and n is an integer of usually 2 to 18, preferably 4 to 10.

The repeating unit constituting the semi-aromatic polyamide resin (A) is a linear alkylene diamine component unit (b-1) having 4 to 18 carbon atoms as the diamine component unit [b] and the number of carbon atoms having a side chain alkyl group And 4 to 18 alkylene diamine component units (b-2). Among them, the repeating unit having a side chain alkyl diamine component unit is preferably a repeating unit having a component unit derived from 2-methyl-1,5-diaminopentane, and is represented by the following formula [III] it can. In the following formulae, R ² is a divalent hydrocarbon group such as a p-phenylene group, a m-phenylene group or an alkylene group under the condition that 45 to 100 mol% thereof is a p-phenylene group.

The intrinsic viscosity [η] of the semiaromatic polyamide resin (A) measured at a temperature of 30 ° C. in concentrated sulfuric acid is usually 0.5 to 3.0 dl / g, preferably 0.5 to 2.8 dl / g More preferably, it is in the range of 0.6 to 2.5 dl / g.

The semiaromatic polyamide resin (A) may be a combination of two or more semiaromatic polyamide resins having different intrinsic viscosities. For example, the semiaromatic polyamide resin (A) is a semiaromatic polyamide resin (A1) having an intrinsic viscosity [η] of 0.9 dl / g or more, and an intrinsic viscosity [η] of 0.7 dl / g or more and 0. 0. It may be a mixture with a semiaromatic polyamide resin (A2) which is less than 9 dl / g. That is, the semi-aromatic polyamide resin composition comprises 35 to 100 parts by mass of the semi-aromatic polyamide resin (A1) and the semi-aromatic polyamide resin (A2) based on 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A). Is preferably contained in an amount of 0 to 65 parts by mass; preferably 45 to 100 parts by mass of the semiaromatic polyamide resin (A1) and 0 to 55 parts by mass of the semiaromatic polyamide resin (A2). If the content ratio of the semiaromatic polyamide resin (A1) and the semiaromatic polyamide resin (A2) is within the above range, the melt flow of the semiaromatic polyamide resin composition can be achieved without impairing the mechanical strength and the heat aging resistance. Because it can improve the quality, it is easier to control mold contamination to a higher degree. The intrinsic viscosity [η] of the semiaromatic polyamide resin (A) is adjusted by the molecular weight; the molecular weight can be adjusted by the amount of the molecular weight modifier compounded in the synthesis of the semiaromatic polyamide resin.

The intrinsic viscosity [η] of the semiaromatic polyamide resin (A) can be measured as follows. 0.5 g of the semiaromatic polyamide resin (A) is dissolved in 50 ml of a 96.5% sulfuric acid solution to prepare a sample solution. The number of seconds of flow of the resulting solution under 25 ° C. ± 0.05 ° C. is measured using a Ubbelohde viscometer, and calculated based on the following equation.
[Η] = ηSP / (C * (1 + 0.205ηSP))
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
t: Seconds of flow of sample solution (seconds)
t ₀ : Blank sulfuric acid flow down seconds (seconds)
ηSP = (t−t ₀ ) / t ₀

In addition, the melting point of the semiaromatic polyamide resin (A) often does not exceed 330 ° C. That is, the melting point of the semiaromatic polyamide resin (A) is usually 280 to 330 ° C., preferably 290 to 305 ° C. Furthermore, the semi-aromatic polyamide resin (A) is particularly excellent in heat resistance, has a low water absorption rate, and has less post-crystallization due to annealing of a molded article.

The glass transition temperature of the semiaromatic polyamide resin (A) is usually 80 ° C. or higher, preferably 90 to 150 ° C.

For example, the following (PA-i) and (PA-ii) can be illustrated as a typical thing of semi-aromatic polyamide resin (A).

(PA-i): A polyamide comprising repeating units of the formula [I-a] and the formula [III].
However, R ¹ in the formula [Ia] is a linear alkylene group (C number: 4 to 18), and R ² in the formula [III] is a p-phenylene group. In this case, the repeating unit of the formula [I-a] is 5 to 95 mol%, preferably 30 to 70 mol%, most preferably 40 to 60 mol%, and the repeating unit of the formula [III] is 95 to 5 mol% Preferably, it is in the range of 70 to 30 mol%, most preferably 60 to 40 mol%.

(PA-ii): A polyamide comprising repeating units of the formula [I-a], the formula [I-b] and the formula [III].
However, R ¹ in Formula [I-a] and Formula [I-b] is a linear alkylene group (C number: 4 to 18), and R ^{2 in} Formula [III] is p- It is a phenylene group. In this case, the repeating unit of the formula [I-a] is 25 to 65 mol%, preferably 30 to 50 mol%, and the repeating unit of the formula [I-b] is 5 to 30 mol%, preferably 10 to 20 mol% The repeating unit of the formula [III] is in the range of 30 to 70 mol%, preferably 40 to 60 mol%.

The semiaromatic polyamide resin (A) contained in the semiaromatic polyamide resin composition may be of one type or of two or more types. For example, a semi-aromatic polyamide containing only terephthalic acid component unit (a-1) as dicarboxylic acid component unit [a], terephthalic acid component unit (a-1) and other component units (a-2) or A semiaromatic polyamide resin containing (a-3) may be combined; a semiaromatic polyamide containing only the linear alkylene diamine component unit (b-1) as the diamine component unit [b]; A semiaromatic polyamide resin containing a chain alkylene diamine component unit (b-1) and a side chain alkylene diamine component unit (b-2) may be combined.
For example, as the dicarboxylic acid component unit [a], only terephthalic acid component unit (a-1) is contained, and as the diamine component unit [b], linear alkylene diamine component unit (b-1) and side chain alkylene diamine component unit A semi-aromatic polyamide resin containing (b-2) and, as a dicarboxylic acid component unit [a], a terephthalic acid component unit (a-1) and the other component units (a-2) or (a-3) And a semiaromatic polyamide resin containing only the linear alkylene diamine component unit (b-1) as the diamine component unit [b].

The semi-aromatic polyamide resin (A) can be produced by polycondensation of a dicarboxylic acid component and a diamine component. Specifically, the semiaromatic polyamide resin (A) comprises terephthalic acid, aromatic dicarboxylic acid other than (optional) terephthalic acid and / or aliphatic dicarboxylic acid, linear dialkylene diamine and side chain alkyl Group-containing alkylene diamine in the above amount in an aqueous medium and heating under pressure in the presence of a catalyst such as sodium hypophosphite to produce a polyamide precursor; then this polyamide precursor Can be produced by melt-kneading. In addition, when manufacturing a polyamide precursor, a molecular weight modifier like benzoic acid can also be mix | blended.

In addition, the semi-aromatic polyamide resin (A) is produced by separately producing a polyamide having a side chain alkyl group and a polyamide having no side chain, and performing a transamidation reaction by melt-kneading these. You can also.

In the semi-aromatic polyamide resin (A), the blending amounts of at least two types of polyamides different in composition are adjusted so that the dicarboxylic acid component unit [a] and the diamine component unit [b] fall within the above ranges. It can also be produced by melt-kneading this.

1-2. Modified olefin polymer (B)
The modified olefin polymer (B) is an olefin polymer containing a functional group structural unit containing a hetero atom (hereinafter, also simply referred to as “functional group structural unit”). Specifically, the modified olefin polymer (B) is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, which contains a functional group structural unit containing a hetero atom (modified ethylene / α-olefin copolymer Polymer). The modified olefin polymer (B) has high dispersibility in the semiaromatic polyamide resin (A) than the unmodified olefin polymer (D), so it is excellent in mechanical strength such as impact strength, and is a copper-based stabilizer The combination with (C) can give a molded article having high high temperature resistance.

The modified olefin polymer (B) comprises 0.1 to 1.5 parts by mass, preferably 0.1 to 3 parts by mass of functional group structural units containing a hetero atom, per 100 parts by mass of the modified olefin polymer (B). Part included. The functional group structural unit includes a functional group containing a hetero atom, and examples of the functional group include a carboxylic acid group (including a carboxylic acid anhydride group), an ester group, an ether group, an aldehyde group, a ketone group and the like. included. Among them, a carboxylic acid group (carboxylic acid anhydride group) is preferable, and a maleic anhydride group is more preferable.

When the modified olefin polymer (B) is contained in the semiaromatic polyamide resin composition, the above-mentioned functional groups react or interact with the terminal groups of the semiaromatic polyamide resin (A). At this time, the semiaromatic polyamide resin (A) and the modified olefin polymer (B) bond or interact when the amount of functional group structural units of the modified olefin polymer (B) is in the above range. Thus, the impact resistance of the resulting molded article is enhanced. In addition, when the amount of functional group structural units is excessive, the bonding and interaction become too strong, and the melt flowability of the semi-aromatic polyamide resin composition may decrease, but the amount of functional group structural units is If it is 1.5 parts by mass or less, the melt flowability of the semiaromatic polyamide resin composition is sufficiently maintained.

The amount of functional group structural unit contained in the modified olefin polymer (B) can be specified by a known means such as preparation ratio at the time of preparation of the modified olefin polymer (B), ¹³ C-NMR measurement or ¹ H-NMR measurement can do.

Concretely, the following conditions can be illustrated as an example of the conditions which specify the quantity of a functional group structural unit.
^In the case of ¹ H-NMR measurement, the solvent is deuterated ortho-dichlorobenzene using an ECX 400 nuclear magnetic resonance apparatus manufactured by JEOL. The sample concentration is 20 mg / 0.6 mL, the measurement temperature is 120 ° C, the observed nucleus is ¹ H (400 MHz), the sequence is a single pulse, the pulse width is 5.12 μs (45 ° pulse), the repetition time is 7.0 The number of integrations shall be 500 times or more. The standard chemical shift is 0 ppm of hydrogen of tetramethylsilane, but the same result can be obtained by setting the peak derived from the residual hydrogen of deuterated orthodichlorobenzene to 7.10 ppm as a standard value of chemical shift. You can get The peaks such as ¹ H derived from the functional group-containing compound can be assigned by a conventional method.

^In the case of ¹³ C-NMR measurement, the measuring apparatus is an ECP 500 nuclear magnetic resonance apparatus manufactured by Nippon Denshi Co., Ltd., and the solvent is a mixed solvent of orthodichlorobenzene / heavy benzene (80/20% by volume). The measurement temperature is 120 ° C, the observed nucleus is ¹³ C (125 MHz), single pulse proton decoupling, 45 ° pulse, the repetition time is 5.5 seconds, the integration number is 10,000 times or more, and 27.50 ppm chemical shift Set as a reference value. Assignment of various signals can be performed based on an ordinary method, and quantification can be performed based on the integrated value of signal intensity.

As such modified olefin polymer (B), relatively high density modified ethylene / α-olefin copolymer (B1) and relatively low density modified ethylene / α-olefin copolymer (B2) included.

[Modified ethylene / α-olefin copolymer (B1)]
The modified ethylene / α-olefin copolymer (B1) is a modified ethylene / α-olefin copolymer having a higher density than the modified ethylene / α-olefin copolymer (B2) described later. The modified ethylene / α-olefin copolymer (B1) can impart high elastic modulus to the semiaromatic polyamide resin composition, and can enhance creep resistance at high temperatures. Further, since the decrease in melt flowability at the time of molding is less than in the case of the modified ethylene / α-olefin copolymer (B2), mold contamination can be reduced.

Specifically, the modified ethylene / α-olefin copolymer (B1) preferably satisfies the following requirements (i) to (iii). Such a modified ethylene / α-olefin copolymer (B1) is likely to increase the creep resistance of the resulting molded article at high temperatures and to be less likely to cause decomposition during molding, so that little white powder is generated during molding. It can.

(I) The density of the modified ethylene / α-olefin copolymer (B1) measured according to JIS K7112 is 0.89 to 0.95 g / cm ³ , preferably 0.90 to 0.94 g / cm ³ , More preferably, it is in the range of 0.91 to 0.93 g / cm ³ . The density of the modified ethylene / α-olefin copolymer (B1) depends on the composition of ethylene and α-olefin, polymerization temperature, hydrogen concentration, etc. at the time of synthesis of the ethylene / α-olefin copolymer (B01) before graft modification. It can be adjusted.

(Ii) The temperature (melting point; Tm) of the maximum peak position of the endothermic curve measured with a differential scanning calorimeter (DSC) of the modified ethylene / α-olefin copolymer (B1) is preferably 90 to 127 ° C. Is in the range of 95-125.degree. The melting point of the modified ethylene / α-olefin copolymer (B1) can be adjusted, for example, by the composition of ethylene or α-olefin at the time of synthesis of the ethylene / α-olefin copolymer before graft modification, the catalyst species, the polymerization temperature, etc. .

(Iii) The crystallinity of the modified ethylene / α-olefin copolymer (B1) measured by X-ray diffraction method is 20 to 60%, preferably 25 to 55%, and more preferably 30 to 50%. is there. The crystallinity of the modified ethylene / α-olefin copolymer (B1) can be adjusted, for example, by the composition of ethylene or α-olefin at the time of synthesis of the ethylene / α-olefin copolymer before graft modification. The crystallinity of the modified ethylene / α-olefin copolymer (B1) can be measured by the same method as in the examples described later.

The melt flow rate (MFR) of the modified ethylene / α-olefin copolymer (B1) at a load of 190 ° C. and a load of 2.16 kg according to ASTM D 1238 is usually 0.01 to 100 g / 10 min, preferably 0.1 to It is 50 g / 10 min, more preferably 0.2 to 20 g / 10 min.

Such a modified ethylene / α-olefin copolymer (B1) is obtained by graft-modifying an ethylene / α-olefin copolymer (B01) with an unsaturated carboxylic acid or a derivative thereof.

(Ethylene-α-olefin copolymer (B01))
The ethylene / α-olefin copolymer (B01) before graft modification is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. The content of structural units derived from ethylene in the ethylene / α-olefin copolymer (B01) is 70 mol% or more, preferably 80 to 98 mol%.

Examples of α-olefins include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene and the like. Among these, 1-butene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable. These α-olefins can be used alone or in combination of two or more. The content of structural units derived from α-olefin in the ethylene / α-olefin copolymer (B01) is 0.5 to 30 mol%, preferably 2 to 20 mol%.

(I) The density of ethylene / α-olefin copolymer (B01) measured according to JIS K7112 is 0.89 to 0.95 g / cm ³ , preferably 0.90 to 0.94 g / cm ³ , Preferably, it is in the range of 0.91 to 0.93 g / cm ³ . The density of the ethylene / α-olefin copolymer (B01) can be adjusted by the same method as described above.

(Ii) The temperature (melting point; Tm) of the maximum peak position of the endothermic curve measured by differential scanning calorimetry (DSC) of the ethylene / α-olefin copolymer (B01) is 90 to 127 ° C., preferably It is in the range of 95-125 ° C. The melting point of the ethylene / α-olefin copolymer (B01) can be adjusted by the same method as described above.

(Iii) The degree of crystallinity of the ethylene / α-olefin copolymer (B01) measured by the X-ray diffraction method is 20 to 60%, preferably 25 to 55%, more preferably 30 to 50%. . The crystallinity of the ethylene / α-olefin copolymer (B01) can be adjusted by the same method as described above.

The ethylene / α-olefin copolymer (B01) having the above physical properties is produced by a conventionally known method using a catalyst of titanium (Ti), vanadium (V), zirconium (Zr) and the like. can do.

(Unsaturated carboxylic acid or its derivative)
Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and the like. Examples of unsaturated carboxylic acid derivatives include acid anhydrides, esters, amides, imides, metal salts, etc. Specifically, maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, methacrylic acid Acid methyl ester, ethyl acrylate, ethyl methacrylate, acrylic acid glycidyl, 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, Fumarate dia Such as fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, N-butyl maleimide, N-phenyl maleimide, sodium acrylate, sodium methacrylate, sodium acrylate, potassium acrylate, potassium methacrylate etc. included. Of these, maleic anhydride is most preferred.

The graft modification to the ethylene / α-olefin copolymer using the unsaturated carboxylic acid or its derivative (grafting monomer) can be carried out by various methods known in the prior art. For example, a melt modification method in which an ethylene / α-olefin copolymer (B01) is melted using an extruder and a graft monomer is added for graft copolymerization, or an ethylene / α-olefin copolymer (B01) as a solvent In the solution modification method, the solution is dissolved in water, and graft copolymerization is performed by adding a graft monomer. In any case, it is preferable to initiate the reaction in the presence of a radical initiator in order to graft copolymerize the graft monomer efficiently.

Examples of radical initiators include organic peroxides, organic peresters, etc. Specifically, benzoyl peroxide, dichloro benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2 Organic peroxides such as 1,5-di (peroxide benzoate) hexyne-3, 1,4-bis (tert-butylperoxyisopropyl) benzene, lauroyl peroxide, etc .; tert-butyl peracetate, 2,5-dimethyl-2,5-di (Tert-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl perisobutyrate, tert- Organic peresters such as chilper-sec-octoate, tert-butyl perpivalate, cumyl pervivalate, tert-butyl perdiethyl acetate; azo compounds such as azoisobutyronitrile, dimethyl azoisobutyrate etc. . Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexyne-3,2,5-dimethyl-2,5-di (tert-butyl) Preferred are dialkyl peroxides such as peroxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene. The radical initiator is generally used in a ratio of 0.001 to 1 part by mass with respect to 100 parts by mass of the ethylene / α-olefin copolymer (B01) before graft modification.

[Modified ethylene / α-olefin copolymer (B2)]
The modified ethylene / α-olefin copolymer (B2) is a modified ethylene / α-olefin copolymer having a density lower than that of the modified ethylene / α-olefin copolymer (B1). The modified ethylene / α-olefin copolymer (B2) can impart good impact resistance to the semiaromatic polyamide resin composition.

Specifically, the modified ethylene / α-olefin copolymer (B2) preferably satisfies the following requirement (iv). Such a modified ethylene / α-olefin copolymer (B2) tends to impart impact resistance to a molded article.

(Iv) The density of the modified ethylene / α-olefin copolymer (B2) measured according to JIS K7112 is 0.80 g / cm ³ or more and less than 0.89 g / cm ³ , preferably 0.85 g / cm ³ or more It is less than 0.89 g / cm ³ . When the density is in the above range, it is easy to impart excellent impact resistance to the semiaromatic polyamide resin composition.

The melt flow rate (MFR) of the modified ethylene / α-olefin copolymer (B2) according to ASTM D 1238 at 190 ° C. and a load of 2.16 kg is 0.01 to 20 g / 10 min, preferably 0.05 to 20 g / min. 10 minutes.

Such a modified ethylene / α-olefin copolymer (B2) is obtained by graft-modifying an ethylene / α-olefin copolymer (B02) with an unsaturated carboxylic acid or a derivative thereof.

(Ethylene-α-olefin copolymer (B02))
The ethylene / α-olefin copolymer (B02) before graft modification is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms. The content of structural units derived from ethylene in the ethylene / α-olefin copolymer (B02) is 70 to 99.5 mol%, preferably 80 to 99 mol%.

As the α-olefin, the same one as described above can be used. The content of structural units derived from α-olefin in the ethylene / α-olefin copolymer (B02) is 0.5 to 30 mol%, preferably 1 to 20 mol%.

(Unsaturated carboxylic acid or its derivative)
As the unsaturated carboxylic acid, the same one as described above can be used.

The modified olein polymer (B) contains one or both of the modified ethylene / α-olefin copolymer (B1) and the modified ethylene / α-olefin copolymer (B2) as described above. When the modified olein polymer (B) contains both the modified ethylene / α-olefin copolymer (B1) and the modified ethylene / α-olefin copolymer (B2), the modified ethylene / α-olefin copolymer (B1) The content ratio of the modified ethylene / α-olefin copolymer (B2) may be (B1) :( B2) = 10: 90 to 90:10. By increasing the proportion of (B2), it is easy to increase the impact resistance of the resulting molded article, and by increasing the proportion of (B1), while improving the creep resistance and heat resistance of the resulting molded article at high temperatures, It is easy to control mold pollution.

1-3. Copper-based stabilizer (C)
The copper-based stabilizer (C) contains (i) a salt of a halogen and a metal of group 1 or 2 of the periodic table (halogen metal salt), and (ii) a copper compound, and iii) It may further contain a higher fatty acid metal salt. The copper-based stabilizer (C) can provide the semi-aromatic polyamide resin composition with heat resistance (heat aging resistance) that can withstand, for example, a high temperature of 150 ° C. or more.

Examples of (i) halogen metal salts include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride. Among them, potassium iodide and potassium bromide are preferred. The halogen metal salt may be contained alone or in combination of two or more.

(Ii) Examples of copper compounds include copper halides; copper sulfates, acetates, propionates, benzoates, adipates, terephthalates, salicylates, nicotinates and stearates. And copper chelate compounds (compounds of copper and ethylenediamine or ethylenediaminetetraacetic acid etc.) are included. Among them, copper iodide, cuprous bromide, cupric bromide, cuprous chloride and copper acetate are preferred. A copper compound may be contained only by 1 type, and 2 or more types may be contained.

From the viewpoint of easily improving the heat resistance of the molded product and the corrosion resistance at the time of production, the molar ratio of halogen to copper is 0.1 when the content mass ratio of the (i) halogen metal salt and (ii) copper compound is improved. It may be adjusted to be 1/2 to 200/1, preferably 0.5 / 1 to 100/1, more preferably 2/1 to 40/1.

(Iii) Examples of higher fatty acid metal salts include higher saturated fatty acid metal salts and higher unsaturated fatty acid metal salts.

The higher saturated fatty acid metal salt is a metal salt of a saturated fatty acid having 6 to 22 carbon atoms and a metal element (M1) such as an element of Groups 1, 2 and 3 of the Periodic Table of the Elements, zinc, and aluminum preferable. Such higher saturated fatty acid metal salt is represented by the following formula (1).

(In the formula (1), the metal element (M1) is an element of Groups 1, 2 and 3 of the Periodic Table of the Elements, zinc or aluminum, and n may be 8 to 30)

Examples of higher saturated fatty acid metal salts include capric acid, uradecyl acid, lauric acid, tridecyl acid, myristic acid, pentadecyl acid, palmitic acid, heptadecyl acid, stearic acid, nonadecanoic acid, aracic acid, behenic acid, lignoceric acid, and serotin. Included are the acids, heptacosanoic acid, montanic acid, melissic acid, lithium salts, sodium salts, magnesium salts, calcium salts, zinc salts and aluminum salts of lactose. Among them, undecylenic acid, oleic acid, elaidic acid, celylic acid, erucic acid, busic acid, sorbic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearoric acid, 2-hexadecenoic acid, 7-hexadecenoic acid, 9-hexadecenoic acid Gadeuric acid, gadoeridic acid, lithium salts, sodium salts, magnesium salts, calcium salts, zinc salts and aluminum salts of 11-eicosenoic acid are preferred.

Higher unsaturated fatty acid metal salt is a metal salt of unsaturated fatty acid having 6 to 22 carbon atoms and a metal element (M1) such as an element of Groups 1, 2 and 3 of the periodic table, zinc, and aluminum. Is preferred.

Examples of copper stabilizers (C) are mixtures of 10% by weight copper (I) iodide and 90% by weight potassium iodide or 14.3% by weight copper (I) iodide and 85.7% The mixture etc. with the potassium iodide / calcium distearate (98: 2 mass ratio) of the mass% are included.

1-4. Unmodified olefin polymer (D)
The unmodified olefin polymer (D) is an olefin polymer containing no functional structural unit containing a hetero atom. Such unmodified olefin polymer (D) can impart good melt flowability to the semiaromatic polyamide resin composition. In particular, the melt flowability of the modified ethylene / α-olefin copolymer (B2) alone tends to decrease and mold contamination is apt to occur, but the modified ethylene / α-olefin copolymer (B2) and the unmodified olefin polymer By combining with (D), the melt flowability can be enhanced, and the mold contamination thereby can be highly suppressed.

As such an unmodified olefin polymer (D), one similar to the above-mentioned ethylene / α-olefin copolymer (B01) before graft modification can be used.

1-5. Other Components The semi-aromatic polyamide resin composition of the present invention may further contain other components in addition to the components described above, as long as the effects of the present invention are not impaired. Examples of other components include semi-aromatic polyamide resin (A), modified olefin polymer (B) and heat resistant resin other than unmodified olefin polymer (D); inorganic filler, organic filler, Organic flame retardants, antioxidants (heat resistant stabilizers), heat stabilizers, weather resistant stabilizers, antistatic agents, antislip agents, anti blocking agents, antifogging agents, lubricants, pigments, dyes, natural oils, synthetic oils and Additives such as wax are included.

[Other heat resistant resin]
Examples of other heat resistant resins include PPS (polyphenylene sulfide), PPE (polyphenyl ether), PES (polyether sulfone), PEI (polyether imide), LCP (liquid crystal polymer), modified products of these resins, etc. Is included. Particularly preferred is polyphenylene sulfide.

[Inorganic filler (E)]
The inorganic filler (E) may be an inorganic filler having a fibrous, powdery, granular, plate-like, needle-like, cloth-like, or mat-like shape.

Examples of fibrous inorganic fillers include glass fibers, carbon fibers, asbestos fibers and boron fibers. Among these, glass fiber is particularly preferred. By using the glass fiber, the formability is improved, and mechanical properties such as tensile strength, flexural strength, flexural modulus and heat resistance properties such as thermal deformation temperature of the molded article containing the inorganic filler are improved.

The average length of the fibrous inorganic filler is usually in the range of 0.1 to 20 mm, preferably 0.3 to 6 mm, and the aspect ratio is usually in the range of 10 to 2000, preferably 30 to 600. It is in. It is preferred to use fibrous inorganic fillers having an average length and aspect ratio within such ranges.

In addition to fibrous inorganic fillers, other fillers having a powdery, granular, plate-like, needle-like, cloth-like, mat-like or other shape can also be used. Examples of such other fillers include silica, silica alumina, alumina, calcium carbonate, titanium dioxide, talc, wollastonite, diatomaceous earth, clay, kaolin, spherical glass, mica, gypsum, bengara, magnesium oxide and Powdered or plate-like inorganic compounds such as zinc oxide and needle-like inorganic compounds such as potassium titanate are included. These fillers can also be used in mixture of 2 or more types.

The average particle size of the other fillers is usually in the range of 0.1 to 200 μm, preferably 1 to 100 μm.

The fibrous filler and other fillers can be used after being treated with a silane coupling agent or a titanium coupling agent.

The inorganic filler (E) preferably contains at least one of a fibrous filler and another filler, and more preferably contains at least one of a fibrous filler and talc.

The content of the inorganic filler (E) may be usually 1 to 200 parts by mass, preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the resin component.

[Organic filler]
Examples of organic fillers include polyparaphenylene terephthalamide, polymetaphenylene terephthalamide, polyparaphenylene isophthalamide, polymetaphenylene isophthalamide, condensates of diaminodiphenyl ether with terephthalic acid (isophthalic acid) and para (meth) Fully aromatic polyamides such as condensates of aminobenzoic acid; wholly aromatic polyamideimides such as condensates of diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride; wholly aromatic polyesters; wholly aromatic polyimides; polybenzimidazole And heterocycle-containing compounds such as polyimidazophenanthroline; and secondary products such as powder, plate, fiber or cloth formed from polytetrafluoroethylene and the like.

[Organic flame retardant]
The organic flame retardant is to be blended with an organic flame retardant such as polybrominated styrene, a brominated form of polyethylene ether, a brominated form of polystyrene or the like having as a main component a structural unit of the following formula [IV] produced from a brominated styrenic monomer Can. In the following formula, m is a number of 1 or more and 5 or less.

The polybrominated styrene preferably contains 60% by weight or more of dibrominated styrene units, and particularly preferably 70% by weight or more. In addition to dibrominated styrene, it may be polybrominated styrene obtained by copolymerizing monobrominated styrene and / or tribrominated styrene at 40% by weight or less, preferably 30% by weight or less.

The content of the organic flame retardant is 0 to 60 parts by mass, preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the semiaromatic polyamide resin (A). Further, in order to obtain more sufficient flame retardancy, it is preferable to add about 40 to 60 parts by mass. If the amount is less than 0.5 parts by mass, the flame retardant effect is insufficient. If the amount is more than 60 parts by mass, the mechanical and thermal properties are unfavorably deteriorated.

In the semi-aromatic polyamide resin composition of the present invention, at least one flame retardant auxiliary selected from antimony oxide, sodium antimonate, tin oxide, iron oxide, zinc oxide and zinc nitrate in addition to the above organic flame retardant Can be used. In particular, sodium antimonate, particularly substantially anhydrous sodium antimonate heat-treated at a high temperature of 550 ° C. or higher is preferable. The content of the flame retardant aid may be 0 to 10 parts by mass, preferably 2 to 8 parts by mass, with respect to 100 parts by mass of the semiaromatic polyamide resin (A).

[Antioxidant]
Examples of the antioxidant include phosphorus-based antioxidants, phenol-based antioxidants, amine-based antioxidants, sulfur-based antioxidants and the like.

Examples of phosphorus antioxidants include 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, triphenyl phosphite, 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 penta Erythritol diphosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite, trioctadecyl phosphite, 1,1,3-tris (2-methyl-di-tridecyl phosphite-5-tert -Butylpheny ) Butane, 4,4'-butylidene-bis (3-methyl-6-tert-butyl) tridecylphosphite, 4,4'-butylidene-bis (3-methyl-6-tert-butyl-di-tridecyl) Phosphite, bis (2,4-di-tert-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, tridecyl phosphite, tristearyl phosphite, 2,2′-methylene bis (4, 6-di-tert-butylphenyl) octyl phosphite, Sorbit-Tris-Eo Fight - distearyl - mono -C30- diol ester and bis (2,4,6-tri -tert- butylphenyl) include pentaerythritol diphosphite or the like. Among these, bis (2,4-di-tert-butylphenyl) pentaerythritol-di-phosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-di-phosphite and the like Included are phosphorus-based antioxidants of the pentaerythritol-di-phosphite type, as well as tetrakis (2,4-di-tert-butylphenyl) 4,4′-bisphenylene diphosphite.

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-tert-butyl-p-cresol, 2,4,6-tri-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′-iso-propylidene bisphenol, 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- -(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, tris [β- (3, (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) Etc. are included.

Examples of amine antioxidants 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, Included are polymers of 2,2,4-trimethyl-1,2-dihydroquinone and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline and the like.

Examples of sulfur-based antioxidants include thiobis (β-naphthol), thiobis (N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, dodecyl mercaptan, tetramethylthiuram monosulfide, tetra-tetra Included are methyl thiuram disulfide, nickel dibutyl dithiocarbamate, nickel isopropyl xanthate, dilauryl thiodipropionate, distearyl thiodipropionate and the like.

An antioxidant can be used individually or in combination of 2 or more types. Among such antioxidants, it is particularly preferable to use phosphorus-based antioxidants alone or in combination with other antioxidants.

The content of the antioxidant is 0.05 to 2 parts by mass, preferably 0.1 to 1.5 parts by mass, and more preferably 0.2 to 1.0 parts by mass with respect to 100 parts by mass of the resin component. sell.

1-6. Composition of Semi-Aromatic Polyamide Resin Composition The first semi-aromatic polyamide resin composition of the present invention comprises 50 to 98 parts by mass of the semi-aromatic polyamide resin (A) and 1 to 6 parts of the modified olefin polymer (B). 40 parts by mass, 0.0001 to 1 parts by mass of a copper stabilizer (C), 0 to 40 parts by mass of an unmodified olefin polymer (D), and 0 to 50 parts by mass of an inorganic filler (E) And preferably. However, the total of the semi-aromatic polyamide resin (A), modified olefin polymer (B), copper stabilizer (C), unmodified olefin polymer (D), and inorganic filler (E) is 100 parts by mass. .

The second semi-aromatic polyamide resin composition of the present invention comprises 50 to 97 parts by mass of the semi-aromatic polyamide resin (A), 1 to 40 parts by mass of the modified olefin polymer (B), and a copper stabilizer. It is preferable to contain 0.0001 to 1 part by mass of (C), 1 to 40 parts by mass of the unmodified olefin polymer (D), and 0 to 50 parts by mass of the inorganic filler (E). However, the total of the semi-aromatic polyamide resin (A), modified olefin polymer (B), copper stabilizer (C), unmodified olefin polymer (D), and inorganic filler (E) is 100 parts by mass. .

In the first and second semi-aromatic polyamide resin compositions of the present invention, the content of the semi-aromatic polyamide resin (A) is (A) component, (B) component, (C) component, (D) component The amount is preferably 60 to 97 parts by mass, more preferably 70 to 88 parts by mass, based on 100 parts by mass of the component (E). When the content of the semi-aromatic polyamide resin (A) is a certain amount or more, the mechanical strength and the heat resistance of the resulting molded article can be easily enhanced, and when the content is a certain degree or less, the creep resistance of the resulting molded body under high temperature It is hard to be lost.

In the first semi-aromatic polyamide resin composition of the present invention, the content of the modified olefin polymer (B) is (A) component, (B) component, (C) component, (D) component and (E) The amount is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass in total of the components. If the content of the modified olefin polymer (B) is a certain amount or more, the impact resistance of the resulting molded article can be easily enhanced, and if it is a certain amount or less, the melt flowability of the semiaromatic polyamide resin composition is impaired. Hateful.

In the first and second semi-aromatic polyamide resin compositions of the present invention, the content of the copper stabilizer (C) is as follows: (A) component, (B) component, (C) component, (D) component and The amount is preferably 0.001 to 1 part by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the component (E). If the content of the copper-based stabilizer (C) is a certain amount or more, the heat resistance (heat aging resistance) of the resulting molded article can be easily enhanced, and if it is a certain amount or less, mold contamination can be easily suppressed.

In the first and second semi-aromatic polyamide resin compositions of the present invention, the content of the unmodified olefin polymer (D) is the component (A), the component (B), the component (C), the component (D) The amount is preferably 1 to 30 parts by mass, more preferably 5 to 20 parts by mass with respect to 100 parts by mass in total of the component (E). When the content of the unmodified olefin polymer (D) is a certain amount or more, the melt flowability of the semi-aromatic polyamide resin composition can be easily improved, and the mold contamination can be easily suppressed. When the content of the unmodified olefin polymer (D) is at or below a certain level, the impact resistance and heat resistance of the resulting molded article are less likely to be impaired.

The total content of the components (B) and (D) is preferably based on 100 parts by mass of the components (A), (B), (C), (D) and (E). The amount is 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and still more preferably 10 to 20 parts by mass. Among them, the content of the component (D) is preferably 1 to 75% by mass, more preferably the sum of the components (B) and (D), from the viewpoint of enhancing the impact resistance of the molded body. It is 10 to 70% by mass, more preferably 20 to 60% by mass. From the viewpoint of facilitating suppression of mold contamination, the content of the component (D) is preferably 30 to 80% by mass, more preferably 50 to 80, based on the total of the components (B) and (D). It is mass%. By enhancing the proportion of (B), the impact resistance and heat resistance of the resulting molded article can be easily enhanced, and by enhancing the proportion of (D), the melt flowability of the semi-aromatic polyamide resin composition can be enhanced, and gold It is easy to control mold pollution.

In the first and second semi-aromatic polyamide resin compositions of the present invention, the content of the inorganic filler (E) is (A) component, (B) component, (C) component, (D) component and ( The amount is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass in total of the component E). When the content of the inorganic filler (E) is a certain amount or more, the mechanical strength of the resulting molded article can be easily enhanced. When the content is a certain amount or less, the melt flowability of the semiaromatic polyamide resin composition is less likely to be impaired.

The first semiaromatic polyamide resin composition of the present invention comprises a modified ethylene / α-olefin copolymer (B1) and a copper stabilizer (C); the second semiaromatic polyamide resin of the present invention Since the composition contains the modified ethylene / α-olefin copolymer (B2), the unmodified olefin polymer (D) and the copper stabilizer (C), the heat aging resistance of the molded article is enhanced, and at the time of molding Can suppress the formation of white powder in the mold and can highly suppress mold contamination.

2. Process for Producing Semi-Aromatic Polyamide Resin Composition The semi-aromatic polyamide resin composition of the present invention comprises the semi-aromatic polyamide resin (A), the modified olefin polymer (B) and the copper stabilizer (C) in the above ratio. , Unmodified olefin polymer (D), inorganic filler (E), and, if necessary, other components, a known method such as a method of mixing with a Henschel mixer, V blender, ribbon blender or tumbler blender, or It can manufacture by the method of melt-kneading with a single screw extruder, a multi-screw extruder, a kneader, a Banbury mixer etc. after mixing, and then granulating or grinding.

3. Molded Body of Semi-Aromatic Polyamide Resin Composition Using the semi-aromatic polyamide resin composition prepared as described above, a conventional melt molding method, for example, a compression molding method, an injection molding method or an extrusion molding method is used. As a result, a molded product having a desired shape can be produced.

For example, by introducing the semiaromatic polyamide resin composition of the present invention into an injection molding machine in which the cylinder temperature is adjusted to about 350 to 300 ° C. to bring it into a molten state, it is introduced into a mold of a predetermined shape. Moldings can be produced.

The shape of the molded article produced using the semiaromatic polyamide resin composition of the present invention is not particularly limited, and may take various shapes depending on the application.

The polyamide resin composition of the present invention is also suitable as a resin for forming various molded articles, preferably automobile interior and exterior parts, engine room interior parts, automobile electrical parts and the like. Examples of moldings obtained from the semi-aromatic polyamide resin composition of the present invention include radiator grille, rear spoiler, wheel cover, wheel cap, cowl vent grille, air outlet louver, air scoop, hood bulge, fender and back. Exterior parts such as doors; cylinder head cover, engine mount, air intake manifold, throttle body, air intake pipe, radiator tank, radiator support, water pump inlet, water pump outlet, thermostat housing, cooling fan , Fan shroud, oil pan, oil filter housing, oil filler cap, oil level gauge, timing belt, timing belt cover And car engine compartment parts such as engine covers; fuel caps, fuel filler tubes, fuel tanks for vehicles, fuel sender modules, fuel cut-off valves, quick connectors, canisters, fuel delivery pipes and fuel filler necks Fuel system parts such as automobile; Drive system parts such as shift lever, housing and propeller shaft; Chassis parts such as stabilizer bar, linkage rod etc. Window regulator, door lock, door handle, outside door mirror, Functional parts for automobiles such as stays, accelerator pedals, pedal modules, seal rings, bearings, bearing retainers, gears and actuators; Wire harness / connector Automotive electronic components such as relay blocks, sensor housings, encapsulations, ignition coils and distributor caps; Fuel components for general-purpose devices such as fuel tanks for general-purpose devices (mowing machines, lawn mowers and chain saws, etc.) And electric and electronic parts such as connectors and LED reflectors, electric and electronic parts, building materials parts, various casings, exterior parts and the like.

The semi-aromatic polyamide resin composition of the present invention is less likely to cause mold contamination during molding, and the appearance and dimensional accuracy of the resulting molded article are excellent. Moreover, the said molded object is simultaneously excellent in mechanical characteristics, such as the creep characteristic under high temperature, heat resistance, and impact resistance. Therefore, it is suitable for automobile fuel tanks, quick connectors, bearing retainers, fuel tanks for general-purpose devices, fuel caps, fuel filler necks, fuel sender modules, wheel caps, fenders or back doors, various housings, exterior parts, etc. .
As various housings and exterior parts, small-sized housings, exterior molded articles, and mobile phone housings can be mentioned, and in particular, they can be preferably used as mobile phone housings.

Furthermore, the semi-aromatic polyamide resin composition of the present invention is also preferably used as a resin for producing a connector for interconnecting electronic circuits. That is, the connector produced from the above semi-aromatic polyamide resin composition has excellent heat resistance, as well as the connector has little deformation under stress under high temperature and high humidity.

Hereinafter, the present invention will be more specifically described with reference to examples, but the scope of the present invention is not limited to the description of the examples.

1. Preparation of Semi-Aromatic Polyamide Resin (A) <Preparation of Semi-Aromatic Polyamide (PA-1)>
139.3 g (1.20 moles) of 1,6-diaminohexane, 139.3 g (1.20 moles) of 2-methyl-1,5-diaminopentane, 365.5 g (2.2 moles) of terephthalic acid, as a catalyst 0.55 g (5.2 × 10 ^-3 mol) of sodium hypophosphite and 64 ml of ion-exchanged water are charged in a 1-liter reactor, and after nitrogen substitution, react for 1 hour under conditions of 250 ° C. and 35 kg / cm ² Did. After one hour, the reaction product formed in the reactor is extracted into a receiver connected to the reactor and set at a pressure lower by about 10 kg / cm ² , and the intrinsic viscosity [η] is 0.15 dl / g. The obtained polyamide precursor was 561 g.
Next, this polyamide precursor was dried and melt-polymerized using a twin-screw extruder at a cylinder setting temperature of 330 ° C. to obtain a semiaromatic polyamide (PA-1).

In the composition of the obtained semi-aromatic polyamide (PA-1), the terephthalic acid component unit content in the dicarboxylic acid component unit is 100 mol%, and the 1,6-diaminohexane component unit content in the diamine component unit The content of 2-methyl-1,5-diaminopentane component unit was 50 mol%. The semi-aromatic polyamide (PA-1) had an intrinsic viscosity of 1.0 dl / g and a melting point Tm of 300.degree.

<Preparation of Semi-Aromatic Polyamide (PA-2)>
269.3 g (2.32 mol) of 1,6-diaminohexane, 205.6 g (1.24 mol) of terephthalic acid, 148.0 g (1.01 mol) of adipic acid, 0.48 g of sodium hypophosphite as a catalyst (4.50 × 10 ^-3 mol), 3.43 g (2.81 × 10 ^-2 mol) of benzoic acid as a molecular weight modifier, and 62 ml of ion exchanged water are charged in a 1 liter reactor and purged with nitrogen, 250 The reaction was performed under the conditions of 35 ° C. and 35 kg / cm ² for 1 hour. After one hour, the reaction product formed in the reactor is extracted into a receiver connected to the reactor and set at a pressure lower by about 10 kg / cm ² , and the intrinsic viscosity [η] is 0.15 dl / g. 559 g of a polyamide precursor of
Next, this polyamide precursor was dried and melt-polymerized using a twin-screw extruder at a cylinder setting temperature of 330 ° C. to obtain a semiaromatic polyamide (PA-2).

In the composition of the obtained semi-aromatic polyamide (PA-2), the content of terephthalic acid component unit in the dicarboxylic acid component unit is 55 mol%, the content ratio of adipic acid component unit is 45 mol%, and The content ratio of 1,6-diaminohexane component unit was 100 mol%. The semi-aromatic polyamide (PA-2) had an intrinsic viscosity of 1.0 dl / g and a melting point Tm of 310 ° C.

<Preparation of Semi-Aromatic Polyamide (PA-3)>
269.3 g (2.32 mol) of 1,6-diaminohexane, 198.3 g (1.19 mol) of terephthalic acid, 142.8 g (0.98 mol) of adipic acid, 0.48 g of sodium hypophosphite as a catalyst (4.50 × 10 ^-3 mol), 7.44 g (6.10 × 10 ^-2 mol) of benzoic acid as a molecular weight modifier, and 62 ml of ion exchanged water are charged in a 1-liter reactor and purged with nitrogen, 250 The reaction was performed under the conditions of 35 ° C. and 35 kg / cm ² for 1 hour. After one hour, the reaction product formed in the reactor is extracted into a receiver connected to the reactor and set at a pressure lower by about 10 kg / cm ² , and the intrinsic viscosity [η] is 0.15 dl / g. The polyamide precursor of 525 g was obtained.
Next, this polyamide precursor was dried and melt-polymerized using a twin-screw extruder at a cylinder setting temperature of 330 ° C. to obtain a semiaromatic polyamide (PA-3).

In the composition of the obtained semi-aromatic polyamide (PA-3), the content of terephthalic acid component unit in the dicarboxylic acid component unit is 55 mol%, the content of adipic acid component unit is 45 mol%, and The content ratio of 1,6-diaminohexane component unit was 100 mol%. The semi-aromatic polyamide (PA-3) had an intrinsic viscosity of 0.8 dl / g and a melting point Tm of 310 ° C.

<Preparation of Semi-Aromatic Polyamide (PA-4)>
303.9 g (1.92 mol) of 1,9-diaminononane, 44.3 g (0.28 mol) of 2-methyl-1,8-diaminooctane, 365.5 g (2.2 mol) of terephthalic acid Charge 0.55 g (5.2 × 10 ^-3 mol) of sodium phosphite and 64 ml of ion-exchanged water to a 1-liter reactor, replace with nitrogen, and react for 1 hour under conditions of 250 ° C. and 35 kg / cm ² went. After one hour, the reaction product formed in the reactor is extracted to a receiver connected to the reactor and set at a pressure lower by about 10 kg / cm ² , and the intrinsic viscosity [η] is 0.16 dl / g. 622 g of a polyamide precursor of
Next, this polyamide precursor was dried and melt-polymerized using a twin-screw extruder at a cylinder setting temperature of 330 ° C. to obtain a semiaromatic polyamide (PA-4).

In the composition of the obtained semi-aromatic polyamide (PA-4), the content of terephthalic acid component unit in the dicarboxylic acid component unit is 100 mol%, and the content ratio of 1,9-diaminononane component unit in the diamine component unit is 87. The content was 3 mol%, and the content ratio of 2-methyl-1,8-diaminooctane component unit was 12.7 mol%. The semi-aromatic polyamide (PA-4) had an intrinsic viscosity of 0.99 dl / g and a melting point Tm of 303.degree.

The intrinsic viscosity and the melting point Tm of the semiaromatic polyamide resins (PA-1) to (PA-4) were measured by the following methods, respectively.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the obtained semiaromatic polyamide resin was measured as follows. 0.5 g of semiaromatic polyamide resin was dissolved in 50 ml of 96.5% sulfuric acid solution. The number of seconds of flow of the resulting solution under 25 ° C. ± 0.05 ° C. is measured using a Ubbelohde viscometer, “formula: [η] = ηSP / (C (1 + 0.205ηSP)) Calculated based on
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
t: Seconds of flow of sample solution (seconds)
t ₀ : Blank sulfuric acid flow down seconds (seconds)
ηSP = (t−t ₀ ) / t ₀

[Melting point Tm]
The melting point Tm of the semiaromatic polyamide resin was measured according to JIS K7121. Specifically, the temperature is raised at a rate of 10 ° C./min using a PerkinElemer DSC 7 to obtain an endothermic curve of DSC, and the temperature at the maximum peak position is taken as the melting point Tm.

2. Preparation of Modified Olefin Polymer (B) / Unmodified Olefin Polymer (D) 2-1. Unmodified olefin polymer (D)
<Preparation of ethylene / 1-butene copolymer (PE-1)>
An ethylene / 1-butene copolymer (PE-1) was prepared using a Ti-based catalyst.
The ethylene content of the ethylene / 1-butene copolymer (PE-1) was 96 mol%. Further, the density was 0.920 g / cm ³ , MFR (ASTM D 1238, 190 ° C., 2.16 kg load) was 1.0 g / 10 min, and the melting point was 124 ° C.

2-2. Modified olefin polymer (B)
<Preparation of Modified Ethylene / 1-butene Copolymer (MAH-PE-1)>
The ethylene / 1-butene copolymer (PE-1) prepared above (density = 0.920 g / cm ³ , melting point Tm = 124 ° C, crystallinity = 48%, MFR (ASTM D 1238, 190 ° C, 2. 16 kg load) = 1.0 g / 10 min, ethylene content = 96 mol%) 100 parts by mass, maleic anhydride 0.8 parts by mass, and peroxide [trade name Perhexin-25B, manufactured by Nippon Oil & Fats Co., Ltd.] 0.07 parts by mass is mixed with a hexshell mixer, and the obtained mixture is melt graft modified with a 65 mmφ single screw extruder set at 230 ° C. to obtain a modified ethylene / 1-butene copolymer (MAH-PE-1) Got).

The amount of maleic anhydride grafted of the modified ethylene / 1-butene copolymer (MAH-PE-1) was measured by IR analysis to be 0.8% by mass. The density is 0.916 g / cm ³ , MFR (ASTM D 1238, 190 ° C., 2.16 kg load) is 0.27 g / 10 min, the melting point is 121 ° C., and the crystallinity is 43%. The

<Preparation of Modified Ethylene / 1-butene Copolymer (MAH-PE-2)>
An ethylene / 1-butene copolymer (PE-2) was prepared using a Ti-based catalyst.
The ethylene content of the ethylene / 1-butene copolymer (PE-2) was 81 mol%. Moreover, the density was 0.865 g / cm ³ , and the MFR (ASTM D 1238, 190 ° C., 2.16 kg load) was 0.5 g / 10 min.
100 parts by mass of the ethylene / 1-butene copolymer (PE-2) prepared above, 1.2 parts by mass of maleic anhydride, and peroxides (trade name: Perhexin-25B, manufactured by Nippon Oil & Fats Co., Ltd.) 0.06 Parts by mass were mixed with a hexshell mixer, and the obtained mixture was melt graft modified with a 65 mmφ single screw extruder set at 230 ° C. to obtain a modified ethylene / 1-butene copolymer (MAH-PE-2) The
The amount of maleic anhydride grafted of the modified ethylene / 1-butene copolymer (MAH-PE-2) was measured by IR analysis to be 1.0% by mass. Moreover, the density was 0.866 g / cm ³ , and the MFR (ASTM D 1238, 190 ° C., 2.16 kg load) was 0.6 g / 10 min.

The composition, density and melt flow rate of the modified olefin polymer (B) and the unmodified olefin polymer (D) were determined by the following methods.

[composition]
The composition of the modified olefin polymer, for example, the content (mol%) of ethylene and α-olefin having 3 or more carbon atoms and the content (% by mass) of functional group structural units were measured by ¹³ C-NMR. The measurement conditions are as follows.
Measurement device: Nuclear magnetic resonance device (ECP 500 type, manufactured by Nippon Denshi Co., Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse proton decoupling Pulse width: 4.7 μs (45 ° pulse)
Repeating time: 5.5 seconds Number of integrations: 10,000 or more Solvent: ortho-dichlorobenzene / deuterated benzene (volume ratio: 80/20) mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Reference value for chemical shift: 27.50 ppm

[density]
The density was measured at a temperature of 23 ° C. using a density gradient tube in accordance with JIS K7112.

[Melt flow rate (MFR)]
Melt flow rate (MFR: Melt Flow Rate) was measured at 190 ° C. and a load of 2.16 kg in accordance with ASTM D1238. The unit is g / 10 min.

[Degree of crystallinity]
A test piece of 3 mm in thickness of ASTM-1 (dumbbell piece) was prepared, and a section was cut out from the central part in the longitudinal direction and the central part in the thickness direction. The obtained sample was fixed to a sample holder, and was measured by wide-angle X-ray diffraction while rotating the sample holder using RINT 2550 manufactured by Rigaku Corporation.

3. Other materials <Copper-based stabilizer (C)>
Copper-based stabilizer (C-1): A mixture of 10% by mass of copper (I) iodide and 90% by mass of potassium iodide

<Inorganic filler (E)>
Talc (average particle size 1.6 μm)

4. Preparation of First Semi-Aromatic Polyamide Resin Composition (Examples 1 to 13 and Comparative Examples 1 to 5)
Semiaromatic polyamide resin (A), modified olefin polymer (B), copper stabilizer (C), unmodified olefin polymer (D), and inorganic filler (E) at the composition ratio shown in Table 1 or 2 ) Were mixed in a tumbler blender, and melt-kneaded using a 30 mmφ vented twin screw extruder at a cylinder temperature of 300 to 335 ° C. Then, the kneaded material was extruded in a strand and cooled in a water tank. Thereafter, the strand was taken up with a pelletizer and cut to obtain a pellet-like semi-aromatic polyamide resin composition.

The flexural strength and elastic modulus, Charpy impact strength, creep deformation, bend closure and heat aging resistance of the obtained semi-aromatic polyamide resin composition were evaluated by the following methods.

[Bending strength, bending elastic modulus]
The obtained semi-aromatic polyamide resin composition was injection-molded under the following molding conditions to prepare a test piece having a length of 64 mm, a width of 6 mm and a thickness of 0.8 mm.
Molding machine: Sodick Plastic Co., Ltd., Tupearl TR40S3A
Molding machine cylinder temperature: (Tm + 15) ° C, mold temperature: 120 ° C
The obtained test piece was left to stand at a temperature of 23 ° C. under a nitrogen atmosphere for 24 hours. Next, a bending test was performed under the atmosphere of temperature 23 ° C. and relative humidity 50%: bending test made by NTESCO AB5, span 26 mm, bending speed 5 mm / min, and measuring bending strength (MPa) and elastic modulus (MPa) did.

[Charpy impact strength]
Using the resulting semi-aromatic polyamide resin composition, notched multipurpose test pieces were produced according to ISO-179, and Charpy impact strength (J / m) was measured.

[Creep deformation]
The obtained semi-aromatic polyamide resin composition was injection molded under the following molding conditions to prepare a test piece having a length of 125 mm, a width of 13 mm and a thickness of 1.6 mm.
Molding machine: Sodick Plastic Tupearl TR40S3A
Molding machine cylinder temperature: (melting point Tm + 15 ° C of semi-aromatic polyamide resin (A),
Mold temperature: Tg + 20 ° C of semi-aromatic polyamide resin (A)
A load of 1.6 MPa is applied to the obtained test piece under a condition of 80 ° C. × 95% RH using a creep tester (model number: CP6-L-250 manufactured by A & D Co., Ltd.), The amount of creep deformation after 24 hours was determined.
○: creep deformation is 0.8 mm or less Δ: creep deformation is more than 0.8 mm and 1.6 mm or less ×: creep deformation is more than 1.6 mm Δ was determined to be good.

[Bent occlusion]
The obtained semi-aromatic polyamide resin composition was injection-molded for 400 shots under the following molding conditions. Thereafter, the area of the mold deposit attached to the mold nest was measured.
Molding machine: Sumitomo Heavy Industries, Ltd. SG50-MIII
Cylinder set temperature: 340 ° C
Mold temperature: 40 ° C
Injection speed: 150 mm / sec
As the area of the mold deposit is larger, the amount of the mold deposit is larger, the vent is easily blocked, and the continuous formability is inferior. Specifically, it was determined that the area of the mold depot was 3.5 cm ² or less, which is good, and less than 3.0 cm ² .

[Heat resistant aging resistance]
The following dumbbell test pieces were produced using the obtained semi-aromatic polyamide resin composition.
(Dumbbell test strip)
Thickness: 3.2 mm
Parallel part length: 16.5 mm, parallel part width: 3 mm
Test piece length: 64 mm, chuck width: 12 mm
After storing the obtained test piece in an air circulating furnace for 200 hours or 300 hours under the condition of a temperature of 160 ° C., the test piece was removed from the furnace and cooled to 23 ° C. Using this test piece, a tensile test was performed under an atmosphere of temperature 23 ° C. and relative humidity 50%. Then, after storing for 200 hours and after storing for 300 hours, it was judged whether or not the yield point was confirmed.
:: Yield point after 300 hours storage △: Yield point after 200 hours storage but no yield point after 300 hours storage ×: No yield point after 200 hours storage

The evaluation results of Examples 1 to 9 are shown in Table 1, and the evaluation results of Examples 10 to 13 and Comparative Examples 1 to 5 are shown in Table 2.

As shown in Tables 1 and 2, all of the semiaromatic polyamide resin compositions of Examples 1 to 13 containing the modified ethylene / α-olefin copolymer (B1) and the copper stabilizer (C) It can be seen that the heat aging resistance is high, the bend blockage is also small, and mold contamination can be suppressed.

In addition, it is understood that the impact strength is enhanced by further including the modified ethylene / α-olefin copolymer (B2) (comparison of Examples 4 and 8).

Furthermore, it is understood that the vent blockage can be further reduced by further including the unmodified olefin polymer (D) (comparison of Examples 1 and 2; Comparison of Examples 4 and 6, etc.).

Furthermore, by combining the semi-aromatic polyamide (PA-1) or (PA-2) having a high intrinsic viscosity with the semi-aromatic polyamide (PA-3) having a low intrinsic viscosity, the mechanical strength is not reduced. It can be seen that the bend closure can be further improved (compare the examples 2 and 4 and the examples 1, 10 and 14).

Furthermore, the ratio ((PA-1 + PA-2) / PA-3) of the semi-aromatic polyamide (PA-1) and (PA-2) having a high intrinsic viscosity to the semi-aromatic polyamide (PA-3) having a low intrinsic viscosity It can be seen that the heat aging resistance and the bending strength are less likely to be impaired as the higher the)) (compare with Examples 3, 10 and 12).

Furthermore, it turns out that the bending strength of the molded object obtained can be raised more by adding further the talc which is an inorganic filler (D) (comparison of Example 1 and 16).

On the other hand, it is understood that the semi-aromatic polyamide resin compositions of Comparative Examples 1, 4 and 5 which do not contain the copper stabilizer (C) have low heat aging resistance. In addition, the semi-aromatic polyamide resin composition of Comparative Example 2 containing the unmodified olefin polymer (D) instead of the modified ethylene / α-olefin copolymer (B1) not only does not improve the heat aging resistance. , It can be seen that the Charpy impact strength is low. In addition, the semi-aromatic polyamide resin composition of Comparative Example 3 containing the modified ethylene / α-olefin copolymer (B2) instead of the modified ethylene / α-olefin copolymer (B1) has a large amount of creep deformation. Also, it can be seen that the bend closure is high and mold contamination is likely to occur.

5. Preparation of Second Semi-Aromatic Polyamide Resin Composition (Examples 14 to 16)
With the composition ratio shown in Table 3, semi-aromatic polyamide resin (A), modified olefin polymer (B), copper stabilizer (C), unmodified olefin polymer (D) and inorganic filler (E) The mixture was mixed in a tumbler blender, and melt-kneaded under a cylinder temperature condition of 300 to 335 ° C. using a vented twin screw extruder of 30 mmφ. Then, the kneaded material was extruded in a strand and cooled in a water tank. Thereafter, the strand was taken up with a pelletizer and cut to obtain a pellet-like semi-aromatic polyamide resin composition.

The flexural strength and elastic modulus, Charpy impact strength, creep deformation, bend closure and heat aging resistance of the obtained semi-aromatic polyamide resin composition were evaluated in the same manner as described above.

The evaluation results of Examples 14 to 16 are shown in Table 3. Table 3 also shows the results of Comparative Examples 1 to 5.

As shown in Table 3, the semiaromatic polyamides of Examples 14 to 16 containing modified ethylene / α-olefin copolymer (B2), unmodified olefin polymer (D) and copper stabilizer (C) It is found that all resin compositions have high heat aging resistance, less bend clogging, and can suppress mold contamination.

On the other hand, it is understood that the semi-aromatic polyamide resin compositions of Comparative Examples 1, 4 and 5 which do not contain the copper stabilizer (C) have low heat aging resistance. Further, it can be seen that the semi-aromatic polyamide resin composition of Comparative Example 2 not containing the modified ethylene / α-olefin copolymer (B2) not only does not improve the heat aging resistance but also has a low Charpy impact strength. In addition, the semi-aromatic polyamide resin composition of Comparative Example 3 which does not contain the unmodified ethylene / α-olefin copolymer (D) has a large amount of creep deformation, high bend closure property, and mold contamination occurs. I understand that it is easy.

This application claims the priority based on Japanese Patent Application No. 2017-158130 filed on Aug. 18, 2017. The contents described in the application specification are all incorporated herein by reference.

The semi-aromatic polyamide resin composition of the present invention is less likely to cause mold contamination during molding and can produce molded articles excellent in heat resistance, creep resistance at high temperatures and mechanical strength, for example. It is particularly suitably used for forming automotive parts.

Claims

A semi-aromatic polyamide resin (A) having a melting point of 280 to 330 ° C. as measured by differential scanning calorimetry (DSC);
A modified olefin polymer (B) containing a functional group structural unit containing a hetero atom,
A semi-aromatic polyamide resin composition comprising a copper-based stabilizer (C),
The semi-aromatic polyamide resin (A) contains a repeating unit consisting of a dicarboxylic acid component unit and a diamine component unit, and the dicarboxylic acid component unit is a terephthalic acid component with respect to the total number of moles of the dicarboxylic acid component unit. Contains 45 mol% or more of units,
The diamine component unit has 50 to 100% by mole of a linear alkylene diamine component unit having 4 to 18 carbon atoms and 4 to carbon atoms having a side chain alkyl group based on the total number of moles of the diamine component unit. Containing 18 to 50 mol% of alkylene diamine component units,
The semi-aromatic polyamide resin composition satisfies the following (1) or (2):
Semi-aromatic polyamide resin composition.
(1): The modified olefin polymer (B) is
A modified ethylene / α-olefin copolymer (B1) obtained by modifying a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms with an unsaturated carboxylic acid or a derivative thereof,
The modified ethylene / α-olefin copolymer (B1) is
It contains 0.01 to 5% by mass of a functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or its derivative, and satisfies the following requirements (i) to (iii): (i) density is 0.89 in the range of ~ 0.95g / cm 3 (ii) the temperature of the maximum peak position of an endothermic curve measured by a differential scanning calorimeter (DSC) (melting point; Tm) is 90 ~ 127 ℃ (iii) X-ray The degree of crystallinity measured by diffraction method is 20 to 60% (2): The modified olefin polymer (B) is
A modified ethylene / α-olefin copolymer (B2) obtained by modifying a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms with an unsaturated carboxylic acid or a derivative thereof,
The modified ethylene / α-olefin copolymer (B2) is
It contains 0.01 to 5% by mass of the functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or its derivative, and satisfies the following requirement (iv), and (iv) the density is 0.80 g / cm The semi-aromatic polyamide resin composition in the range of 3 or more and less than 0.89 g / cm 3 contains unmodified ethylene and 3 to 7 carbon atoms as the unmodified olefin polymer (D) not containing the functional group structural unit. Further included are copolymers with 20 alpha-olefins.
The semi-aromatic polyamide resin composition according to claim 1, which satisfies the above (1).
The modified olefin polymer (B) is
A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, further comprising a modified ethylene / α-olefin copolymer (B2) modified with an unsaturated carboxylic acid or a derivative thereof,
The modified ethylene / α-olefin copolymer (B2) is
The semiaromatic polyamide resin according to claim 2, comprising 0.01 to 5% by mass of a functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or a derivative thereof and satisfying the following requirement (iv) Composition.
(Iv) The density is in the range of 0.80 g / cm 3 to 0.89 g / cm 3
It further includes an unmodified olefin polymer (D) not containing a functional group structural unit containing the hetero atom,
The semi-aromatic polyamide resin composition according to claim 2, wherein the unmodified olefin polymer (D) is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.
The total number of moles of dicarboxylic acid component units is, in total 55, aromatic carboxylic acid component units other than terephthalic acid and / or aliphatic dicarboxylic acid component units having 4 to 20 carbon atoms, relative to the total number of moles of the dicarboxylic acid component units. The semi-aromatic polyamide resin composition according to claim 2, further comprising mol% or less.
The diamine component unit has 50 to 99 mol% of the linear alkylene diamine component unit having 4 to 18 carbon atoms and the carbon atom number having the side chain alkyl group with respect to the total number of moles of the diamine component unit. The semi-aromatic polyamide resin composition according to claim 2, comprising 1 to 50 mol% of 4 to 18 alkylene diamine component units.
The semi-aromatic polyamide resin composition according to claim 2, wherein the linear alkylene diamine component unit having 4 to 18 carbon atoms is 1,6-diaminohexane component unit.
The semi-aromatic polyamide resin composition according to claim 2, wherein the alkylene diamine component unit having 4 to 18 carbon atoms having a side chain alkyl group is a 2-methyl-1,5-diaminopentane component unit.
The semiaromatic polyamide resin (A) is
With respect to 100 parts by mass of the total amount of the semiaromatic polyamide resin (A),
35 to 100 parts by mass of a semi-aromatic polyamide resin (A1) having an intrinsic viscosity [η] of 0.9 dl / g or more measured in concentrated sulfuric acid at 30 ° C.,
Containing 0 to 65 parts by mass of a semiaromatic polyamide resin (A2) having an intrinsic viscosity [[] measured at 30 ° C. in concentrated sulfuric acid of 0.7 dl / g or more and less than 0.9 dl / g;
The semi-aromatic polyamide resin composition according to claim 2.
The inorganic filler (E) is further contained in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the resin component.
The semi-aromatic polyamide resin composition according to claim 2.
The inorganic filler (E) contains a fibrous inorganic filler or talc.
The semi-aromatic polyamide resin composition according to claim 10.
50 to 98 parts by mass of the semiaromatic polyamide resin (A),
1 to 40 parts by mass of the modified olefin polymer (B),
0.0001 to 1 part by mass of the copper-based stabilizer (C),
0 to 40 parts by mass of an unmodified olefin polymer (D) containing no functional group structural unit containing a hetero atom,
And 0 to 50 parts by mass of the inorganic filler (E) (provided that the semi-aromatic polyamide resin (A), the modified olefin polymer (B), the copper stabilizer (C), the unmodified) The total of the olefin polymer (D) and the inorganic filler (E) is 100 parts by mass),
The semi-aromatic polyamide resin composition according to claim 2.
The molded object obtained from the semi-aromatic polyamide resin composition of Claim 2.
The semi-aromatic polyamide resin composition according to claim 1, which satisfies the above (2).
The modified olefin polymer (B) is
A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, further comprising a modified ethylene / α-olefin copolymer (B1) modified with an unsaturated carboxylic acid or a derivative thereof,
The modified ethylene / α-olefin copolymer (B1) is
15. The half according to claim 14, containing 0.01 to 5% by mass of a functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or a derivative thereof and satisfying the following requirements (i) to (iii): Aromatic polyamide resin composition.
(I) the density is in the range of 0.89 to 0.95 g / cm 3 (ii) the temperature (melting point; Tm) of the maximum peak position of the endothermic curve measured by differential scanning calorimetry (DSC) is 90 to 127 ° C (iii) The crystallinity is 20 to 60% as measured by X-ray diffraction
The total number of moles of dicarboxylic acid component units is, in total 55, aromatic carboxylic acid component units other than terephthalic acid and / or aliphatic dicarboxylic acid component units having 4 to 20 carbon atoms, relative to the total number of moles of the dicarboxylic acid component units. Furthermore, below mol%,
The semi-aromatic polyamide resin composition according to claim 14.
The diamine component unit has 50 to 99 mol% of the linear alkylene diamine component unit having 4 to 18 carbon atoms and the carbon atom number having the side chain alkyl group with respect to the total number of moles of the diamine component unit. Containing 1 to 50 mol% of 4 to 18 alkylene diamine component units,
The semi-aromatic polyamide resin composition according to claim 14.
The linear alkylene diamine component unit having 4 to 18 carbon atoms is 1,6-diaminohexane component unit,
The semi-aromatic polyamide resin composition according to claim 14.
The C4-C18 alkylenediamine component unit having a side chain alkyl group is a 2-methyl-1,5-diaminopentane component unit.
The semi-aromatic polyamide resin composition according to claim 14.
The semiaromatic polyamide resin (A) is
With respect to 100 parts by mass of the total amount of the semiaromatic polyamide resin (A),
35 to 100 parts by mass of a semi-aromatic polyamide resin (A1) having an intrinsic viscosity [η] of 0.9 dl / g or more measured in concentrated sulfuric acid at 30 ° C.,
Containing 0 to 65 parts by mass of a semiaromatic polyamide resin (A2) having an intrinsic viscosity [[] measured at 30 ° C. in concentrated sulfuric acid of 0.7 dl / g or more and less than 0.9 dl / g;
The semi-aromatic polyamide resin composition according to claim 14.
The inorganic filler (E) is further contained in an amount of 1 to 200 parts by mass with respect to 100 parts by mass of the resin component.
The semi-aromatic polyamide resin composition according to claim 14.
The inorganic filler (E) contains a fibrous inorganic filler or talc.
The semi-aromatic polyamide resin composition according to claim 21.
50 to 97 parts by mass of the semiaromatic polyamide resin (A),
1 to 40 parts by mass of the modified olefin polymer (B),
0.0001 to 1 part by mass of the copper-based stabilizer (C),
1 to 40 parts by mass of the unmodified olefin polymer (D),
And 0 to 50 parts by mass of the inorganic filler (E) (provided that the semi-aromatic polyamide resin (A), the modified olefin polymer (B), the copper stabilizer (C), the unmodified) The total of the olefin polymer (D) and the inorganic filler (E) is 100 parts by mass),
The semi-aromatic polyamide resin composition according to claim 14.
The molded object obtained from the semi-aromatic polyamide resin composition of Claim 14.