JP6834006B2 - Semi-aromatic polyamide resin composition and its molded product - Google Patents

Description

The present invention relates to a semi-aromatic polyamide resin composition and a molded product thereof.

Conventionally, various proposals have been made for semi-aromatic polyamides having impact resistance. For example, Patent Document 1 describes a dicarboxylic acid unit consisting of 50 to 100 mol% of terephthalic acid unit and 0 to 40 mol% of aromatic dicarboxylic acid other than terephthalic acid or linear aliphatic dicarboxylic acid unit having 6 to 18 carbon atoms. A polyamide composition comprising a), a semi-aromatic polyamide containing an alkylenediamine unit (b), and a modified elastic copolymer is disclosed. Further, it is also known that a polyamide composition composed of such a semi-aromatic polyamide and a modified elastic polymer is excellent in heat resistance and impact resistance (for example, Patent Documents 2 and 3).

In recent years, it has been studied to replace metal members used for automobile parts with resin to reduce the weight. Polyamide resins are remarkably lighter than metals and have excellent rigidity, heat resistance, oil resistance, and the like, and are therefore suitably used as resin materials constituting automobile parts.

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

Japanese Unexamined Patent Publication No. 4-108855 Japanese Unexamined Patent Publication No. 2-4-1318 Japanese Unexamined Patent Publication No. 5-98152 Japanese Unexamined Patent Publication No. 2-240160 JP-A-2010-202724

As shown in Patent Document 5, a molded product is obtained by further blending a copper compound (C) with a polyamide composition containing a semi-aromatic polyamide resin (A) and a relatively low-density modified polyolefin (B). It is possible to improve the rigidity and heat resistance (hereinafter, also referred to as heat aging resistance) at high temperatures. However, the above-mentioned polyamide composition further containing the copper compound (C) tends to generate white powder derived from a low molecular weight component such as an unreacted monomer, a low-order oligomer or a polymer decomposition product component at the time of molding, and contaminates the mold. There was a new problem that it was easy to cause. The white powder generated in the mold tends to cause the vent hole of the mold to be clogged, and if it is clogged, it is necessary to stop the molding and clean the mold. Further, when the white powder generated in the mold is used to mold an electronic component, particularly a minute component such as a connector, the appearance is likely to be impaired or the dimensional accuracy is likely to be deteriorated. Further, the molded product obtained from the above-mentioned polyamide composition also has a problem that the creep resistance at a high temperature is low.

Therefore, a semi-aromatic polyamide that can suppress mold contamination during molding and can produce a molded product having excellent heat resistance, creep resistance at high temperature, and mechanical strength (rigidity, impact resistance, bending strength, etc.). A resin composition is desired.

The present invention has been made in view of the above circumstances, and is capable of producing a molded product that is less likely to cause mold contamination during molding and has excellent 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 semi-aromatic polyamide resin compositions and molded articles thereof.
[1] A semi-aromatic polyamide resin (A) having a melting point of 280 to 330 ° C. as measured by a differential scanning calorimeter (DSC) and a modified olefin polymer (B) containing a functional group structural unit containing a heteroatom. A semi-aromatic polyamide resin composition containing a copper-based stabilizer (C) and the like.
The semi-aromatic polyamide resin (A) contains a repeating unit composed 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 contains 50 to 100 mol% of a linear alkylenediamine component unit having 4 to 18 carbon atoms and 4 to 4 carbon atoms having a side chain alkyl group with respect to the total number of moles of the diamine component unit. Contains 18 alkylenediamine component units of 0 to 50 mol%.
The semi-aromatic polyamide resin composition is a semi-aromatic polyamide resin composition that satisfies the 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 is contained.
The modified ethylene / α-olefin copolymer (B1) is
The functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or its derivative is contained in an amount of 0.01 to 5% by mass, and the following requirements (i) to (iii) are satisfied (i) The density is 0.89. The temperature (melting point; Tm) at the maximum peak position of the heat absorption curve measured by a differential scanning calorimeter (DSC) in the range of ~ 0.95 g / cm ^{3 is 90 to 127 ° C. (iii) X-ray.} The degree of crystallization measured by the 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 is contained.
The modified ethylene / α-olefin copolymer (B2) 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 a derivative thereof, meets the following requirement (iv), and has a (iv) density of 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 is an unmodified olefin polymer (D) containing no functional group structural unit, which is unmodified ethylene and has 3 to 3 carbon atoms. It further comprises a polymer with 20 α-olefins.

That is, the first aspect of the present invention relates to the following semi-aromatic polyamide resin composition and a molded product thereof.
[2] The semi-aromatic polyamide resin composition according to [1], which satisfies the above (1).
[3] The modified olefin polymer (B) is a modified ethylene / α-olefin co-weight 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) further contains a coalescence (B2), and the modified ethylene / α-olefin copolymer (B2) contains 0.01 to 5 mass of a functional group structural unit containing the hetero atom derived from the unsaturated carboxylic acid or a derivative thereof. The semi-aromatic polyamide resin composition according to [2], which contains% and satisfies the following requirement (iv).
(Iv) The density is in ^{the range of 0.80 g / cm 3} or more and less than 0.89 g / cm ³ [4] The unmodified olefin polymer (D) containing no functional group structural unit containing the hetero atom is further contained. 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 dicarboxylic acid component unit other than terephthalic acid and / or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms with respect 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 alkylenediamine 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], which comprises 1 to 50 mol% of an alkylenediamine component unit having 4 to 18 carbon atoms.
[7] The semi-aromatic polyamide resin composition according to any one of [2] to [6], wherein the linear alkylenediamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit. ..
[8] The alkylenediamine component unit having a side chain alkyl group and having 4 to 18 carbon atoms is described in any one of [2] to [7], which is a 2-methyl-1,5-diaminopentano component unit. Semi-aromatic polyamide resin composition.
[9] The semi-aromatic polyamide resin (A) has an ultimate viscosity [η] of 0.9 dl / in concentrated sulfuric acid measured at 30 ° C. with respect to 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A). Semi-aromatic polyamide resin (A1) of g or more is 35 to 100 parts by mass, and the ultimate viscosity [η] measured at 30 ° C. in concentrated sulfuric acid is 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], which comprises 0 to 65 parts by mass of the aromatic polyamide resin (A2).
[10] The semi-aromatic polyamide resin composition according to any one of [2] to [9], further containing 1 to 200 parts by mass of the inorganic filler (E) with respect to 100 parts by mass of the resin component.
[11] The semi-aromatic polyamide resin composition according to [10], wherein the inorganic filler (E) contains a fibrous inorganic filler or talc.
[12] The semi-aromatic polyamide resin (A) is 50 to 98 parts by mass, the modified olefin polymer (B) is 1 to 40 parts by mass, and the copper-based stabilizer (C) is 0.0001 to 1 part. It contains 0 to 40 parts by mass of the unmodified olefin polymer (D) containing no heteroatomic structural unit and 0 to 50 parts by mass of the inorganic filler (E) (however, 0 to 50 parts by mass). The total of the semi-aromatic polyamide resin (A), the modified olefin polymer (B), the copper-based stabilizer (C), the unmodified olefin polymer (D), and the inorganic filler (E) is 100 mass. The semi-aromatic polyamide resin composition according to any one of [2] to [11].
[13] A molded product obtained from the semi-aromatic polyamide resin composition according to any one of [2] to [12].

The second aspect of the present invention relates to the following semi-aromatic polyamide resin composition and a molded product thereof.
[14] The semi-aromatic polyamide resin composition according to [1], which satisfies the above (2).
[15] The modified olefin polymer (B) is a modified ethylene / α-olefin copolymer 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. Including coalescence (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 a derivative thereof, and has the following requirements (i). )-(Iii), the semi-aromatic polyamide resin composition according to [14].
(I) The density is in ^{the range of 0.89 to 0.95 g / cm 3.} (ii) The temperature (melting point; Tm) at the maximum peak position of the heat absorption curve measured by the differential scanning calorimeter (DSC) is 90 to 127. The degree of crystallization measured by (iii) X-ray diffractometry is 20 to 60%. [16] The dicarboxylic acid component unit is other than terephthalic acid with respect 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 an aromatic carboxylic acid component unit and / or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms in a total of 55 mol% or less.
[17] The diamine component unit has 50 to 99 mol% of the linear alkylenediamine 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], which comprises 1 to 50 mol% of an alkylenediamine component unit having 4 to 18 carbon atoms.
[18] The semi-aromatic polyamide resin composition according to any one of [14] to [17], wherein the linear alkylenediamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit. ..
[19] The alkylenediamine component unit having a side chain alkyl group and having 4 to 18 carbon atoms is described in any one of [14] to [17], which is a 2-methyl-1,5-diaminopentano component unit. Semi-aromatic polyamide resin composition.
[20] The semi-aromatic polyamide resin (A) has an ultimate viscosity [η] of 0.9 dl / in concentrated sulfuric acid measured at 30 ° C. with respect to 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A). Semi-aromatic polyamide resin (A1) of g or more is 35 to 100 parts by mass, and the ultimate viscosity [η] measured at 30 ° C. in concentrated sulfuric acid is 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], which comprises 0 to 65 parts by mass of the aromatic polyamide resin (A2).
[21] The semi-aromatic polyamide resin composition according to any one of [14] to [20], further containing 1 to 200 parts by mass of the inorganic filler (E) with respect to 100 parts by mass of the resin component.
[22] The semi-aromatic 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 semi-aromatic polyamide resin (A), 1 to 40 parts by mass of the modified olefin polymer (B), and 0.0001 to 1 parts of the copper-based stabilizer (C). The semi-aromatic polyamide resin (A) contains 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-based stabilizer (C), the unmodified olefin polymer (D), and the inorganic filler (E) is 100 parts by mass), [14] to [ 22] The semi-aromatic polyamide resin composition according to any one of.
[24] A molded product obtained from the semi-aromatic 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 product which is less likely to cause mold contamination during molding and has excellent heat resistance, creep resistance at high temperature and mechanical strength. be able to.

As a result of diligent studies, the present inventors have made a semi-aromatic polyamide resin composition containing the semi-aromatic polyamide resin (A) and the copper-based stabilizer (C) as "a relatively modified olefin polymer (B)". Either a high-density modified ethylene / α-olefin copolymer (B1) is further contained (constituent (1) above), or a relatively low-density modified ethylene / α-α-as a modified olefin polymer (B). By further containing the olefin copolymer (B2) and the unmodified olefin polymer (D) (constituent (2) above), white powder is generated in the mold during molding while improving heat resistance. It was found that the polymer can be suppressed and the mold contamination can be satisfactorily suppressed.

The reason for this is not clear, but it is presumed as follows. That is, as described above, the modified ethylene / α-olefin copolymer (B1) having a relatively high density is further contained, or the modified ethylene / α-olefin copolymer (B2) having a relatively low density is further contained. By further containing the unmodified olefin polymer (D), the melt fluidity of the semi-aromatic polyamide resin composition during molding is improved to the extent that the creep resistance of the molded product at high temperature is not impaired, and molding is performed. It is possible to reduce the shear insulation at the time. As a result, the amount of low molecular weight components such as unreacted monomers, low-order oligomers, and polymer decomposition products components produced or scattered is reduced without impairing the creep resistance of the obtained molded product at high temperatures, and white powder is produced. Is suppressed (mold depot is reduced). That is, it is considered that the heat resistance can be improved and the mold contamination during molding can be suppressed without impairing the creep resistance of the molded product at a high temperature.

Further, as the semi-aromatic polyamide resin (A), the semi-aromatic polyamide resin (A1) having a relatively high ultimate viscosity and the semi-aromatic polyamide resin (A2) having a relatively low ultimate viscosity are combined to contaminate the mold. Was found to be able to be suppressed to a higher degree. The present invention has been made based on these findings.

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

The modified olefin polymer (B) includes 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), the unmodified olefin polymer (D) is further combined in order to suppress mold contamination. Is preferable.

That is, the first semi-aromatic polyamide resin composition of the present invention comprises a semi-aromatic polyamide resin (A) and a modified ethylene / α-olefin copolymer (B) having a relatively high density as a modified olefin polymer (B). B1) and a copper-based stabilizer (C) are included. The second semi-aromatic polyamide resin composition of the present invention comprises the semi-aromatic polyamide resin (A) and the modified ethylene / α-olefin copolymer (B2) having a relatively low density as the modified olefin polymer (B). , A copper-based 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 whose main structural unit is 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 mol of the terephthalic acid component unit (a-1) when the total number of moles of the dicarboxylic acid component unit contained in the semi-aromatic polyamide resin (A) is 100 mol%. It is contained in an amount of%, and may be contained in an amount of 50 to 90 mol%, preferably 55 to 80 mol%, if necessary.
Further, the dicarboxylic acid component unit [a] is a dicarboxylic acid component unit other than terephthalic acid, that is, an aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid and / or an aliphatic dicarboxylic having 4 to 20 carbon atoms. The acid component unit (a-3) is contained in an amount of 0 to 55 mol% in total, and may be contained in an amount of 10 to 50 mol%, preferably 20 to 45 mol%, if necessary. 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 semi-aromatic polyamide resin (A) can be further improved. If the content of the aliphatic dicarboxylic acid component unit is 55 mol% or less, the content of the terephthalic acid component unit inevitably exceeds 45 mol%, and the obtained semi-aromatic polyamide resin (A) Has a low water absorption rate and tends to have a melting point of 280 ° C. or higher. Therefore, the molded product formed of such a semi-aromatic polyamide resin (A) has little dimensional change due to water absorption and may have sufficient heat resistance.

Examples of the aromatic dicarboxylic acid component unit (a-2) other than terephthalic acid include component units derived from isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid and the like. Among these, the 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 having 4 to 20 carbon atoms, preferably 6 to 12 carbon atoms. Examples of such an aliphatic dicarboxylic acid component unit (a-3) include component units derived from succinic acid, adipic acid, azelaic acid and sebacic acid. Among these, adipic acid component unit and sebacic acid component unit are preferable.

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

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

The diamine component unit [b] is a linear alkylenediamine component unit (b-) having 4 to 18 carbon atoms, where the total number of moles of the diamine component units contained in the semi-aromatic polyamide resin (A) is 100 mol%. 1) is contained in an amount of 50 to 100 mol%, and if necessary, 50 to 99 mol%, preferably 50 to 98 mol%, more preferably 50 to 95 mol%, still more preferably 50 to 93 mol. May be contained in an amount of%.
The diamine component unit [b] contains an alkylene diamine component unit (b-2) having a side chain alkyl group and having 4 to 18 carbon atoms in an amount of 0 to 50 mol%, if 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%.
As described above, the diamine component unit [b] contains two types of specific alkylenediamine component units in the above amounts, whereby the melting point of the semi-aromatic polyamide resin (A) is set to semi-aromatic at the time of molding. The polyamide resin composition can be reduced to the extent that it does not cause gas burning. Further, the melt fluidity of the semi-aromatic polyamide resin composition during molding can be increased, and the creep resistance of the molded product at a high temperature can be enhanced.

The diamine component unit [b] is a linear alkylenediamine component unit (b-1) having 4 to 18 carbon atoms and an alkylenediamine component unit (b-2) having 4 to 18 carbon atoms having a side chain alkyl group. When both are included, if the content of the linear alkylenediamine component unit (b-1) having 4 to 18 carbon atoms is 99 mol% or less, the melt fluidity during molding is unlikely to be significantly reduced. Further, when the content of the alkylenediamine component unit (b-2) having a side chain alkyl group and having 4 to 18 carbon atoms is 50 mol% or less, the crystallization rate of the semi-aromatic polyamide resin (A) is slow. It is hard to become, and the heat resistance tends to be sufficient.

Examples of the linear alkylenediamine component unit (b-1) include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, Includes component units derived from 1,10-diaminodecane, 1,11-diaminoundecane and 1,12-diaminododecane. Among these, component units derived from 1,6-diaminohexane, 1,8-diaminooctane, 1,10-diaminodecane and 1,12-diaminododecane are preferable, and they are derived from 1,6-diaminohexane. The component unit is more preferable. A plurality of these component units may be contained in the semi-aromatic polyamide resin (A).

Examples of the alkylenediamine component unit (b-2) having a side chain alkyl group having 4 to 18 carbon atoms include 1-butyl-1,2-diamino-ethane and 1,1-dimethyl-1,4-diamino. -Butane, 1-ethyl-1,4-diamino-butane, 1,2-dimethyl-1,4-diamino-butane, 1,3-dimethyl-1,4-diamino-butane, 1,4-dimethyl-1 , 4-Diamino-butane, 2,3-dimethyl-1,4-diamino-butane, 2-methyl-1,5-diaminopentane, 2,5-dimethyl-1,6-diamino-hexane, 2,4- Dimethyl-1,6-diamino-hexane, 3,3-dimethyl-1,6-diamino-hexane, 2,2-dimethyl-1,6-diamino-hexane, 2,2,4-trimethyl-1,6- Diamino-hexane, 2,4,4-trimethyl-1,6-diamino-hexane, 2,4-diethyl-1,6-diamino-hexane, 2,3-dimethyl-1,7-diamino-heptane, 2, 4-Dimethyl-1,7-diamino-heptane, 2,5-dimethyl-1,7-diamino-heptane, 2,2-dimethyl-1,7-diamino-heptane, 2-methyl-4-ethyl-1, 7-Diamino-heptane, 2-ethyl-4-methyl-1,7-diamino-heptane, 2,2,5,5-tetramethyl-1,7-diamino-heptane, 3-isopropyl-1,7-diamino -Heptane, 3-isooctyl-1,7-diamino-heptane, 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- Includes component units derived from diamino-octane, 2,4-diethyl-1,8-diamino-octane, and 5-methyl-1,9-diamino-nonane. Among these, a component unit derived from a side chain alkyldiamine 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 is preferable, and 2- Component units derived from methyl-1,5-diaminopentane are more preferred. A plurality of these component units may be contained in the semi-aromatic polyamide resin (A).

In the present invention, the number of carbon atoms in the alkylenediamine 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 unless otherwise specified.

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

Not all of the repeating units constituting the semi-aromatic polyamide resin (A) need to be the repeating units represented by the above [Ia], but a part of the terephthalic acid component unit (a-1) as described above. May further include repeating units in which is replaced by another dicarboxylic acid component.

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

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 formula below, R ¹ is an alkylene group having 4 to 18 carbon atoms, which may have a side chain.

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

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

The ultimate viscosity [η] of the semi-aromatic 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 in the range of 0.6 to 2.5 dl / g.

The semi-aromatic polyamide resin (A) may be a combination of two or more semi-aromatic polyamide resins having different extreme viscosities. For example, the semi-aromatic polyamide resin (A) has a semi-aromatic polyamide resin (A1) having an ultimate viscosity [η] of 0.9 dl / g or more and a semi-aromatic polyamide resin (A1) having an ultimate viscosity [η] of 0.7 dl / g or more. It may be a mixture with a semi-aromatic polyamide resin (A2) having a pressure of less than 9 dl / g. That is, the semi-aromatic polyamide resin composition contains 35 to 100 parts by mass of the semi-aromatic polyamide resin (A1) and the semi-aromatic polyamide resin (A2) with respect to 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A). It is preferable to contain 0 to 65 parts by mass; it is preferable to contain 45 to 100 parts by mass of the semi-aromatic polyamide resin (A1) and 0 to 55 parts by mass of the semi-aromatic polyamide resin (A2). When the content ratio of the semi-aromatic polyamide resin (A1) and the semi-aromatic polyamide resin (A2) is within the above range, the semi-aromatic polyamide resin composition melts and flows without impairing the mechanical strength and heat aging property. Since the property can be enhanced, it is easy to suppress mold contamination to a higher degree. The ultimate viscosity [η] of the semi-aromatic polyamide resin (A) is adjusted by the molecular weight; the molecular weight can be adjusted by the amount of the molecular weight adjusting agent compounded during the synthesis of the semi-aromatic polyamide resin.

The ultimate viscosity [η] of the semi-aromatic polyamide resin (A) can be measured as follows. 0.5 g of the semi-aromatic 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 obtained solution under the condition of 25 ° C. ± 0.05 ° C. is measured using an Ubbelohde viscometer and calculated based on the following formula.
[Η] = ηSP / (C * (1 + 0.205ηSP))
[Η]: Extreme viscosity (dl / g)
ηSP: Specific viscosity C: Sample concentration (g / dl)
t: Number of seconds (seconds) of flow of the sample solution
t ₀ : Number of seconds (seconds) of blank sulfuric acid flowing down
ηSP = (t−t ₀ ) / t ₀

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

The glass transition temperature of the semi-aromatic 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 exemplified as typical examples of the semi-aromatic polyamide resin (A).

(PA-i): Polyamide consisting of repeating units of formula [Ia] and 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 [Ia] 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 in the range of 70-30 mol%, most preferably in the range of 60-40 mol%.

(PA-ii): Polyamide composed of repeating units of the formula [Ia], the formula [Ib] and the formula [III].
^{However, R 1} in the formula [Ia] and the formula [Ib] are both linear alkylene groups (C number: 4 to 18), and R ² in the formula [III] is p-. Use as a phenylene group. In this case, the repeating unit of the formula [Ia] is 25 to 65 mol%, preferably 30 to 50 mol%, and the repeating unit of the formula [Ib] is 5 to 30 mol%, preferably 10 to 20 mol%. , The repeating unit of formula [III] is in the range of 30-70 mol%, preferably 40-60 mol%.

Further, the semi-aromatic polyamide resin (A) contained in the semi-aromatic polyamide resin composition may be of one kind or two or more kinds. For example, as the dicarboxylic acid component unit [a], a semi-aromatic polyamide containing only the terephthalic acid component unit (a-1), the terephthalic acid component unit (a-1) and other component units (a-2), or A semi-aromatic polyamide resin containing (a-3) may be combined; as the diamine component unit [b], a semi-aromatic polyamide containing only a linear alkylenediamine component unit (b-1) and a direct diamine component unit (b-1) are used. A semi-aromatic polyamide resin containing a chain alkylenediamine component unit (b-1) and a side chain alkylenediamine component unit (b-2) may be combined.
For example, the dicarboxylic acid component unit [a] contains only the terephthalic acid component unit (a-1), and the diamine component unit [b] includes the linear alkylene diamine component unit (b-1) and the side chain alkylene diamine component unit. A semi-aromatic polyamide resin containing (b-2) and a terephthalic acid component unit (a-1) and other component units (a-2) or (a-3) as the dicarboxylic acid component unit [a]. And, as the diamine component unit [b], a semi-aromatic polyamide resin containing only the linear alkylenediamine component unit (b-1) may be combined.

The semi-aromatic polyamide resin (A) can be produced by polycondensation of a dicarboxylic acid component and a diamine component. Specifically, the semi-aromatic polyamide resin (A) contains terephthalic acid, an aromatic dicarboxylic acid other than (arbitrary) terephthalic acid and / or an aliphatic dicarboxylic acid, a linear dialkylenediamine and a side chain alkyl. An alkylenediamine having a group is blended in an aqueous medium in the above amount and heated while pressurizing in the presence of a catalyst such as sodium hypophosphate to produce a polyamide precursor; then this polyamide precursor. Can be produced by melt-kneading. When producing the polyamide precursor, a molecular weight modifier such as benzoic acid can be added.

Further, the semi-aromatic polyamide resin (A) is produced by individually producing a polyamide having a side chain alkyl group and a polyamide having no side chain, and subjecting them to a amide exchange reaction by melt-kneading them. You can also.

Further, in the semi-aromatic polyamide resin (A), the blending amount of at least two kinds of polyamides having different compositions is adjusted so that the dicarboxylic acid component unit [a] and the diamine component unit [b] are within the above ranges. , This can also be produced by melt-kneading.

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 (both modified ethylene and α-olefin) containing a functional group structural unit containing a hetero atom. Polymer). Since the modified olefin polymer (B) has higher dispersibility in the semi-aromatic polyamide resin (A) than the unmodified olefin polymer (D), it is excellent in mechanical strength such as impact strength and is a copper-based stabilizer. By combining with (C), a molded product having high high temperature resistance can be imparted.

The modified olefin polymer (B) contains 0.1 to 1.5 parts by mass, preferably 0.1 to 3 parts by mass of a functional group structural unit containing a heteroatom with respect to 100 parts by mass of the modified olefin polymer (B). Including part. 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 an anhydrous carboxylic acid group), an ester group, an ether group, an aldehyde group and a ketone group. included. Of these, 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 semi-aromatic polyamide resin composition, the functional group reacts with or interacts with the terminal group of the semi-aromatic polyamide resin (A). At this time, if the amount of the functional group structural unit of the modified olefin polymer (B) is within the above range, the semi-aromatic polyamide resin (A) and the modified olefin polymer (B) may bond or interact with each other. As a result, the impact resistance of the obtained molded product is enhanced. If the amount of the functional group structural unit is excessive, the bond or interaction may become too strong and the melt fluidity of the semi-aromatic polyamide resin composition may decrease, but the amount of the functional group structural unit may increase. When it is 1.5 parts by mass or less, the melt fluidity of the semi-aromatic polyamide resin composition is sufficiently maintained.

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

Specifically, the following conditions can be exemplified as examples of conditions for specifying the amount of functional group structural units.
^{1 In} the case of 1 H-NMR measurement, an ECX400 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. is used, and the solvent is deuterated orthodichlorobenzene. The sample concentration is 20 mg / 0.6 mL, the measurement temperature is 120 ° C, the observation nucleus is ¹ H (400 MHz), the sequence is a single pulse, the pulse width is 5.12 μsec (45 ° pulse), and the repetition time is 7.0. The number of seconds and the number of integrations shall be 500 or more. In the standard chemical shift, the hydrogen content of tetramethylsilane is set to 0 ppm, but the same result can be obtained by setting the peak derived from residual hydrogen of deuterated orthodichlorobenzene to 7.10 ppm and using it as the reference value for the chemical shift. Can be obtained. Peak of the ^{1 H} or the like from functional group-containing compound may assign a conventional manner.

^{13 In} the case of C-NMR measurement, the measuring device is an ECP500 type nuclear magnetic resonance device manufactured by JEOL Ltd., and the solvent is an orthodichlorobenzene / heavy benzene (80/20% by volume) mixed solvent. In addition, the measurement temperature is 120 ° C, the observation nucleus is ¹³ C (125 MHz), single pulse proton decoupling, 45 ° pulse, repetition time is 5.5 seconds, the number of integrations is 10,000 times or more, and 27.50 ppm is a chemical shift. Use as a reference value. The assignment of various signals can be performed based on the conventional method, and the quantification can be performed based on the integrated value of the signal intensity.

Examples of such a modified olefin polymer (B) include a relatively high-density modified ethylene / α-olefin copolymer (B1) and a 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 a high elastic modulus to the semi-aromatic polyamide resin composition, and can enhance creep resistance at high temperatures. Further, since the decrease in melt fluidity during molding is smaller than that 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) easily enhances the creep resistance of the obtained molded product at high temperature and is less likely to cause decomposition during molding, so that white powder is less likely to be generated during molding. Can be done.

(I) The density of the modified ethylene / α-olefin copolymer (B1) measured by 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, polymerization temperature, hydrogen concentration, etc. of ethylene and α-olefin during the synthesis of the ethylene / α-olefin copolymer (B01) before graft modification. Can be adjusted.

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

The crystallinity of the modified ethylene / α-olefin copolymer (B1) measured by the 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 adjusting the composition of ethylene or α-olefin during the 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 Examples described later.

The melt flow rate (MFR) of the modified ethylene / α-olefin copolymer (B1) according to ASTM D1238 at 190 ° C. and a load of 2.16 kg is usually 0.01 to 100 g / 10 minutes, preferably 0.1 to 1. It is 50 g / 10 minutes, more preferably 0.2 to 20 g / 10 minutes.

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 the structural unit 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 the structural unit derived from the α-olefin in the ethylene / α-olefin copolymer (B01) is 0.5 to 30 mol%, preferably 2 to 20 mol%.

(I) The density of the ethylene / α-olefin copolymer (B01) measured by JIS K7112 is 0.89 to 0.95 g / cm ³ , preferably 0.99 to 0.94 g / cm ³ , and more. It is preferably in the range of 0.91 to 0.93 g / cm ^3. The density of the ethylene / α-olefin copolymer (B01) can be adjusted in the same manner as described above.

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

The crystallinity of the ethylene / α-olefin copolymer (B01) measured by the X-ray diffraction method is 20 to 60%, preferably 25 to 55%, and 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-mentioned physical properties is produced by a conventionally known method using a catalyst such as titanium (Ti) -based, vanadium (V) -based, or zirconium (Zr) -based catalyst. 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 and the like, and specifically include maleic anhydride, itaconic anhydride, citraconic anhydride, methyl acrylate, and methacryl. Methyl acid, ethyl acrylate, ethyl methacrylate, glycidyl acrylate, monoethyl maleic acid ester, diethyl maleic acid ester, monomethyl fumarate ester, dimethyl fumarate, monomethyl itaconic acid ester, diethyl itaconic acid ester, acrylamide, methacrylic amide , Maleic acid monoamide, maleic acid diamide, maleic acid-N-monoethylamide, maleic acid-N, N-diethylamide, maleic acid-N-monobutylamide, maleic acid-N, N-dibutylamide, fumaric acid monoamide, Fumaric acid diamide, fumaric acid-N-monobutylamide, fumaric acid-N, N-dibutylamide, maleimide, N-butylmaleimide, N-phenylmaleimide, sodium acrylate, sodium methacrylate, potassium acrylate, potassium methacrylate Etc. are included. Of these, maleic anhydride is most preferred.

Graft modification to an ethylene / α-olefin copolymer using an unsaturated carboxylic acid or a derivative thereof (graft monomer) can be carried out by various conventionally known methods. 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 to carry out a graft copolymerization, or an ethylene / α-olefin copolymer (B01) is used as a solvent. There is a solution modification method in which the mixture is dissolved in ethylene and a graft monomer is added to carry out graft copolymerization. In either case, it is preferable to initiate the reaction in the presence of a radical initiator in order to efficiently carry out the graft copolymerization of the graft monomer.

Examples of radical initiators include organic peroxides, organic peroxides and the like, specifically benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2. , 5-Di (peroxide benzoate) hexin-3,1,4-bis (tert-butylperoxyisopropyl) benzene, organic peroxides such as lauroyl peroxide; tert-butylperacetate, 2,5-dimethyl-2,5-di (Tert-butylperoxy) hexin-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, tert-butylperbenzoate, tert-butylperphenylacetate, tert-butylperisobutyrate, Organic peroxides such as tert-butylper-sec-octate, tert-butylperpivalate, cumilpervivalate, and tert-butylperdiethyl acetate; azo compounds such as azoisobutyronitrile and dimethylazoisobutyrate included. Among these, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (peroxybenzoate) hexin-3, 2,5-dimethyl-2,5-di (tert-butyl) Dialkyl peroxides such as peroxy) hexane and 1,4-bis (tert-butylperoxyisopropyl) benzene are preferred. The radical initiator is usually 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 lower density than the modified ethylene / α-olefin copolymer (B1). The modified ethylene / α-olefin copolymer (B2) can impart good impact resistance to the semi-aromatic 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 the molded product.

The density of the (iv) modified ethylene / α-olefin copolymer (B2) measured by 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 within the above range, it is easy to impart excellent impact resistance to the semi-aromatic polyamide resin composition.

The melt flow rate (MFR) of the modified ethylene / α-olefin copolymer (B2) according to ASTM D1238 at 190 ° C. and a load of 2.16 kg is 0.01 to 20 g / 10 minutes, preferably 0.05 to 20 g /. It is 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 the structural unit 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 the structural unit derived from the 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 as described above can be used.

As described above, 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). 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) ) And the modified ethylene / α-olefin copolymer (B2) can be (B1) :( B2) = 10: 90 to 90:10. By increasing the ratio of (B2), it is easy to increase the impact resistance of the obtained molded product, and by increasing the ratio of (B1), while increasing the creep resistance and heat resistance of the obtained molded product at high temperatures, Mold contamination is also easy to control.

1-3. Copper-based stabilizer (C)
The copper-based stabilizer (C) contains (i) a salt of a halogen and a Group 1 or Group 2 metal element of the Periodic Table of the Elements (halogen metal salt), and (ii) a copper compound, if necessary ( iii) Higher fatty acid metal salts may be further included. The copper-based stabilizer (C) can impart heat resistance (heat aging property) to the semi-aromatic polyamide resin composition even at a high temperature of, for example, 150 ° C. or higher.

Examples of (i) halide metal salts include potassium iodide, potassium bromide, potassium chloride, sodium iodide and sodium chloride. Of these, potassium iodide and potassium bromide are preferable. Only one type of halogen metal salt may be contained, or two or more types may be contained.

(Ii) Examples of copper compounds include copper halides; copper sulfates, acetates, propionates, benzoates, adipates, terephthalates, sartylates, nicotinates, stearate. Includes copper chelate compounds (compounds of copper with ethylenediamine or ethylenediaminetetraacetic acid). Of these, copper iodide, cupric bromide, cupric bromide, cupric chloride, and copper acetate are preferred. Only one type of copper compound may be contained, or two or more types may be contained.

The content mass ratio of (i) halogen metal salt and (ii) copper compound is such that the molar ratio of halogen to copper is 0.1 from the viewpoint of facilitating improvement of heat resistance of the molded product and corrosiveness during production. It can be adjusted to be / 1 to 200/1, preferably 0.5 / 1 to 100/1, and 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.

（式（１）中、金属元素（Ｍ１）は、元素周期律表の１、２、３族元素、亜鉛又はアルミニウムであり、ｎは、８〜３０でありうる）The higher saturated fatty acid metal salt may be a metal salt of a saturated fatty acid having 6 to 22 carbon atoms and a metal element (M1) such as group 1, 2 and 3 elements of the Periodic Table of the Elements, zinc, and aluminum. preferable. Such a higher saturated fatty acid metal salt is represented by the following formula (1).

(In the formula (1), the metal element (M1) is a group 1, 2 or 3 element, zinc or aluminum in the periodic table of elements, and n can be 8 to 30).

Examples of higher saturated fatty acid metal salts include capric acid, uradecic acid, lauric acid, tridecic acid, myristic acid, pentadecic acid, palmitic acid, heptadecic acid, stearic acid, nonadecanic acid, araquinic acid, bechenic acid, lignoseric acid, cellotin. Includes acids, heptacosanoic acid, montanic acid, melisic acid, lithium and sodium salts of laxelic acid, magnesium salts, calcium salts, zinc salts and aluminum salts. Among them, undecylene acid, oleic acid, ellaic acid, setreic acid, erucic acid, brassic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, stearolic acid, 2-hexadecenoic acid, 7-hexadecenoic acid, 9-hexadecenoic acid , Gadrain acid, gadoellaic acid, lithium salt of 11-eicosenoic acid, sodium salt, magnesium salt, calcium salt, zinc salt and aluminum salt are preferable.

The higher unsaturated fatty acid metal salt is a metal salt of an unsaturated fatty acid having 6 to 22 carbon atoms and a metal element (M1) such as group 1, 2 and 3 elements of the Periodic Table of the Elements, zinc, and aluminum. Is preferable.

Examples of copper-based stabilizers (C) include a mixture of 10% by weight copper (I) iodide and 90% by weight potassium iodide; 14.3% by weight copper (I) iodide and 85.7. A mixture with% by mass of potassium iodide / calcium distearate (98: 2 mass ratio) and the like are included.

1-4. Unmodified olefin polymer (D)
The unmodified olefin polymer (D) is an olefin polymer containing no functional group structural unit containing a hetero atom. Such an unmodified olefin polymer (D) can impart good melt fluidity to the semi-aromatic polyamide resin composition. In particular, the modified ethylene / α-olefin copolymer (B2) alone tends to reduce the melt fluidity and cause mold contamination, but the modified ethylene / α-olefin copolymer (B2) and the unmodified olefin polymer are likely to occur. By combining with (D), the melt fluidity can be enhanced, and the mold contamination due to this can be highly suppressed.

As such an unmodified olefin polymer (D), the same one as 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 components other than the above-mentioned components as long as the effects of the present invention are not impaired. Examples of other components include heat-resistant resins other than semi-aromatic polyamide resins (A), modified olefin polymers (B) and unmodified olefin polymers (D); inorganic fillers, organic fillers, etc. Organic flame retardants, antioxidants (heat-resistant stabilizers), heat stabilizers, weather-resistant stabilizers, antistatic agents, anti-slip agents, anti-blocking agents, antifogging agents, lubricants, pigments, dyes, natural oils, synthetic oils and Contains additives such as wax.

[Other heat resistant resins]
Examples of other heat-resistant resins include PPS (polyphenylene sulfide), PPE (polyphenyl ether), PES (polyether sulphon), PEI (polyetherimide), LCP (liquid crystal polymer) and modified products of these resins. Is included. Particularly, polyphenylene sulfide is preferable.

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

Examples of fibrous inorganic fillers include glass fibers, carbon fibers, asbestos fibers and boron fibers. Among these, glass fiber is particularly preferable. By using glass fiber, the moldability is improved, and the mechanical properties such as tensile strength, bending strength and flexural modulus of the molded product containing the inorganic filler and the heat resistance characteristics such as thermal deformation temperature 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 preferable to use a fibrous inorganic filler having an average length and aspect ratio within such a range.

In addition to the fibrous inorganic filler, other fillers having a shape such as powder, granular, plate, needle, cloth, mat, etc. can also be used. Examples of such other fillers include silica, silica-alumina, alumina, calcium carbonate, titanium dioxide, talc, wallastnite, caestic soil, clay, kaolin, spherical glass, mica, sequel, red iron oxide, magnesium oxide and It includes powdery or plate-shaped inorganic compounds such as zinc oxide and needle-shaped inorganic compounds such as potassium titanate. Two or more kinds of these fillers can be mixed and used.

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

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

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) can 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 and terephthalic acid (isophthalic acid) and para (meth). Total aromatic polyamide such as a condensate of aminobenzoic acid; Total aromatic polyamideimide such as a condensate of diaminodiphenyl ether and trimellitic anhydride or pyromellitic anhydride; Total aromatic polyester; Total aromatic polyimide; Polybenzimidazole And heterocyclic compounds such as polyimidazole phenanthroline; and secondary processed products such as powdery, plate-like, fibrous or cloth-like products formed from polytetrafluoroethylene and the like.

[Organic flame retardant]
The organic flame retardant shall contain an organic flame retardant such as polybromineed styrene, polyethylene ether bromide, polystyrene bromide, etc., whose main constituent is the structural unit of the following formula [IV] produced from brominated styrene monomer. Can be done. 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 the dibrominated styrene unit, and particularly preferably contains 70% by weight or more. In addition to dibrominated styrene, monobrominated styrene and / or tribrominated styrene may be copolymerized in an amount of 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, and more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the semi-aromatic 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 it is less than 0.5 parts by mass, the flame retardant effect is insufficient, and if it is more than 60 parts by mass, the mechanical and thermal characteristics are deteriorated, which is not preferable.

In the semi-aromatic polyamide resin composition of the present invention, at least one flame retardant aid selected from antimony oxide, sodium antimonate, tin oxide, iron oxide, zinc oxide, and zinc nitrate in addition to the above organic flame retardants. 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 semi-aromatic polyamide resin (A).

[Antioxidant]
Examples of antioxidants 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, triphenylphosphite, 2-ethylhexyl acid phosphate, dilaurylphosphite, tri-iso-. Octylphosphite, tris (2,4-di-tert-butylphenyl) phosphite, trilaurylphosphite, trilauryl-di-thiophosphite, trilauryl-tri-thiophosphite, trisnonylphenylphosphite, distearylpenta Ellisritol diphosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) phosphite, trioctadecylphosphite, 1,1,3-tris (2-methyl-di-tridecylphosphite-5-tert -Butylphenyl) butane, 4,4'-butylidene-bis (3-methyl-6-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-phos Fight, tetrakis (2,4-di-tert-butylphenyl) 4,4'-bisphenylenediphosphite, distearylpentaerythritol diphosphite, tridecylphosphite, tristearylphosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, sorbit-tris-phosphite-distearyl-mono-C30-diol ester and bis (2,4,6-tri-tert-butylphenyl) pentaerythritol Includes diphosphite and 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, etc. Includes pentaerythritol-di-phosphite-based phosphorus antioxidants and tetrakis (2,4-di-tert-butylphenyl) 4,4'-bisphenylenediphosphite.

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, stylated phenol, 4-hydroxy-methyl-2,6-di-tert-butylphenol, 2,5-di-tert-butyl-hydroquinone, Cyclohexylphenol, butylhydroxyanisol, 2,2'-methylene-bis- (4-methyl-6-tert-butylphenol), 2,2'-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4'-Iso-propylidenebisphenol, 4,4'-butylidene-bis (3-methyl-6-tert-butylphenol), 1,1-bis- (4-hydrooxy-phenyl) cyclohexane, 4,4' -Methylene-bis- (2,6-di-tert-butylphenol), 2,6-bis (2'-hydrooxy-3'-tert-butyl-5'-methylmethylbenzyl) 4-methyl-phenol, 1, 1,3-Tris (2-methyl-4-hydrooxy-5-tert-butyl-phenyl) butane, 1,3,5-Tris-methyl-2,4,6-tris (3,5-di-tert-) Butyl-4-hydrooxy-benzyl) benzene, tetrakis [methylene-3- (3,5-di-tert-butyl-4-hydrooxyphenyl) propionate] methane, tris (3,5-di-tert-butyl-4) -Hydrooxyphenyl) isocyanurate, tris [β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl-oxyethyl] isocyanate, 4,4'-thiobis (3-methyl-6-tert-butylphenol) ), 2,2'-thiobis (4-methyl-6-tert-butylphenol), 4,4'-thiobis (2-methyl-6-tert-butylphenol), and N, N'-hexamethylenebis (3, 5-Di-tert-butylphenol-4-hydroxycinnamamide) and the like are included.

Examples of amine-based 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, Polymers of 2,2,4-trimethyl-1,2-dihydroquinone and 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline are included.

Examples of sulfur-based antioxidants include thiobis (β-naphthol), thiobis (N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, dodecyl mercaptan, tetramethylthiuram monosulfide, tetra. Includes methylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthate, dilaurylthiodipropionate, distearylthiodipropionate and the like.

The antioxidants can be used alone or in combination of two or more. Among such antioxidants, it is particularly preferable to use a phosphorus-based antioxidant 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 contains 50 to 98 parts by mass of the semi-aromatic polyamide resin (A) and 1 to 1 to 98 parts by mass of the modified olefin polymer (B). 40 parts by mass, 0.0001 to 1 part by mass of copper-based stabilizer (C), 0 to 40 parts by mass of unmodified olefin polymer (D), and 0 to 50 parts by mass of inorganic filler (E). And are preferably included. However, the total of the semi-aromatic polyamide resin (A), the modified olefin polymer (B), the copper-based stabilizer (C), the unmodified olefin polymer (D), and the inorganic filler (E) is 100 parts by mass. ..

The second semi-aromatic polyamide resin composition of the present invention contains 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-based 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), the modified olefin polymer (B), the copper-based stabilizer (C), the unmodified olefin polymer (D), and the 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 the component (A), the component (B), the component (C), and the component (D). It is preferably 60 to 97 parts by mass, and more preferably 70 to 88 parts by mass with respect to 100 parts by mass of the total of the components (E). When the content of the semi-aromatic polyamide resin (A) is above a certain level, the mechanical strength and heat resistance of the obtained molded product can be easily increased, and when it is below a certain level, the obtained molded product has creep resistance at high temperatures. Etc. are not easily damaged.

In the first semi-aromatic polyamide resin composition of the present invention, the content of the modified olefin polymer (B) is the component (A), the component (B), the component (C), the component (D) and the component (E). It is preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total components. When the content of the modified olefin polymer (B) is more than a certain level, the impact resistance of the obtained molded product is likely to be enhanced, and when it is less than a certain level, the melt fluidity of the semi-aromatic 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-based stabilizer (C) is the component (A), the component (B), the component (C), the component (D) and The amount is preferably 0.001 to 1 part by mass, and more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total component (E). When the content of the copper-based stabilizer (C) is above a certain level, the heat resistance (heat aging property) of the obtained molded product is likely to be increased, and when it is below a certain level, mold contamination is likely to be 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), and the component (D). It is preferably 1 to 30 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the total of the components (E). When the content of the unmodified olefin polymer (D) is at least a certain level, the melt fluidity of the semi-aromatic polyamide resin composition can be easily increased, and mold contamination can be easily suppressed. When the content of the unmodified olefin polymer (D) is not more than a certain level, the impact resistance and heat resistance of the obtained molded product are not easily impaired.

The total content of the component (B) and the component (D) is preferably based on 100 parts by mass of the total of the component (A), the component (B), the component (C), the component (D) and the component (E). It is 1 to 30 parts by mass, more preferably 5 to 25 parts by mass, and further preferably 10 to 20 parts by mass. Of these, from the viewpoint of further enhancing the impact resistance of the molded product, the content of the component (D) is preferably 1 to 75% by mass, more preferably 1 to 75% by mass, based on the total of the components (B) and (D). It is 10 to 70% by mass, more preferably 20 to 60% by mass. From the viewpoint of making it easier to suppress mold contamination, the content of the component (D) is preferably 30 to 80% by mass, more preferably 50 to 80% of the total of the components (B) and (D). It is mass%. By increasing the ratio of (B), it is easy to increase the impact resistance and heat resistance of the obtained molded product, and by increasing the ratio of (D), the melt fluidity of the semi-aromatic polyamide resin composition is increased, and gold is used. Easy to control mold contamination.

In the first and second semi-aromatic polyamide resin compositions of the present invention, the content of the inorganic filler (E) is the component (A), the component (B), the component (C), the component (D) and ( E) It is preferably 0.5 to 30 parts by mass, and more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the total components. When the content of the inorganic filler (E) is at least a certain level, the mechanical strength of the obtained molded product is likely to be increased, and when it is at least a certain level, the melt fluidity of the semi-aromatic polyamide resin composition is not easily impaired.

The first semi-aromatic polyamide resin composition of the present invention contains a modified ethylene / α-olefin copolymer (B1) and a copper-based stabilizer (C); the second semi-aromatic polyamide resin of the present invention. Since the composition contains a modified ethylene / α-olefin copolymer (B2), an unmodified olefin polymer (D), and a copper-based stabilizer (C), the heat-resistant aging property of the molded product is enhanced during molding. It is possible to suppress the formation of white powder in the mold and highly suppress mold contamination.

2. 2. Method for Producing Semi-Aromatic Polyamide Resin Composition The semi-aromatic polyamide resin composition of the present invention has the above ratio of semi-aromatic polyamide resin (A), modified olefin polymer (B), and copper-based stabilizer (C). , The unmodified olefin polymer (D), the inorganic filler (E), and if necessary, other components are mixed by a known method, for example, a Henschel mixer, a V blender, a ribbon blender, a tumbler blender, or the like. After mixing, it can be further melt-kneaded with a uniaxial extruder, a multi-screw extruder, a kneader, a Banbury mixer, or the like, and then granulated or pulverized.

3. 3. Molded product of semi-aromatic polyamide resin composition Using the semi-aromatic polyamide resin composition prepared as described above, a usual melt molding method, for example, a compression molding method, an injection molding method, an extrusion molding method, or the like is used. This makes it possible to produce a molded product having a desired shape.

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

The shape of the molded product produced by using the semi-aromatic polyamide resin composition of the present invention is not particularly limited and may take various shapes depending on the intended use.

The polyamide resin composition of the present invention is also suitable as a resin for forming various molded bodies, preferably automobile interior / exterior parts, engine room interior parts, automobile electrical components, and the like. Examples of moldings obtained from the semi-aromatic polyamide resin compositions of the present invention include radiator grills, rear spoilers, wheel covers, wheel caps, cowl vent grills, air outlet louvers, air scoops, hood bulges, fenders and backs. Automotive 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 engine cover and other parts in the automobile engine room; fuel cap, fuel filler tube , Automotive fuel tanks, fuel sender modules, fuel cut-off valves, quick connectors, canisters, fuel delivery pipes, fuel filler necks, and other automotive fuel system components; shift lever housings, propeller shafts, and other automotive drives. System parts; Automotive chassis parts such as stabilizer bars and linkage rods; Window regulators, door locks, door handles, outside door mirror stays, accelerator pedals, pedal modules, seal rings, bearings, bearing retainers, gears and actuators. Automotive functional parts such as wire harnesses / connectors, relay blocks, sensor housings, encapsulations, ignition coils and distributor caps and other automotive electronics components; general-purpose equipment (cutting machines, lawn mowers and chainsaws, etc.) ) Fuel system parts for general-purpose equipment such as fuel tanks; and electrical and electronic parts such as connectors and LED reflectors, electrical and electronic parts, building material parts, various housings, 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 is excellent in appearance and dimensional accuracy of the obtained molded product. In addition, the molded product is simultaneously excellent in mechanical properties such as creep characteristics at high temperatures, heat resistance, and impact resistance. Therefore, it is suitable for automobile fuel tanks, quick connectors, bearing retainers, general-purpose equipment fuel tanks, fuel caps, fuel filler necks, fuel sender modules, hubcaps, fenders or back doors, various housings, exterior parts, etc. ..
Examples of various housings and exterior parts include small housings, exterior molded products, and mobile phone housings, which can be particularly preferably used as mobile phone housings.

Further, the semi-aromatic polyamide resin composition of the present invention is preferably used as a resin for manufacturing a connector for connecting electronic circuits to each other. That is, the connector manufactured from the semi-aromatic polyamide resin composition as described above has excellent heat resistance, and of course, this connector is less deformed under stress under high temperature and high humidity.

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

1. 1. Preparation of semi-aromatic polyamide resin (A) <Preparation of semi-aromatic polyamide (PA-1)>
13,6-diaminohexane 139.3 g (1.20 mol), 2-methyl-1,5-diaminopentano 139.3 g (1.20 mol), terephthalic acid 365.5 g (2.2 mol), as a catalyst 0.55 g (5.2 × 10 ^-3 mol) of sodium hypophosphite and 64 ml of ion-exchanged water were charged into a 1 liter reactor, and after nitrogen substitution, the reaction was carried out at 250 ° C. and 35 kg / cm ² for 1 hour. Was done. After 1 hour, the reaction product produced in the reactor ^{was withdrawn into a receiver connected to the reactor and the pressure was set to be about 10 kg / cm 2} lower, and the ultimate viscosity [η] was 0.15 dl / g. 561 g of the polyamide precursor of the above was obtained.
Next, this polyamide precursor was dried and melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain a semi-aromatic polyamide (PA-1).

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

<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 benzoic acid as a molecular weight regulator (2.81 × ^{10 -2} mol), and g of ion-exchanged water 62ml to 1 liter reactor, after nitrogen substitution, 250 The reaction was carried out at ° C. and 35 kg / cm ^{2 for 1 hour.} After 1 hour, the reaction product produced in the reactor ^{was withdrawn into a receiver connected to the reactor and the pressure was set to be about 10 kg / cm 2} lower, and the ultimate viscosity [η] was 0.15 dl / g. 559 g of the polyamide precursor of the above was obtained.
Next, this polyamide precursor was dried and melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain a semi-aromatic polyamide (PA-2).

The composition of the obtained semi-aromatic polyamide (PA-2) is such that the terephthalic acid component unit content in the dicarboxylic acid component unit is 55 mol% and the adipic acid component unit content is 45 mol%, and the diamine component unit contains. The content of 1,6-diaminohexane component unit was 100 mol%. The ultimate viscosity of the semi-aromatic polyamide (PA-2) was 1.0 dl / g, and the melting point Tm was 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 benzoic acid as a molecular weight regulator (6.10 × ^{10 -2} mol), and g of ion-exchanged water 62ml to 1 liter reactor, after nitrogen substitution, 250 The reaction was carried out at ° C. and 35 kg / cm ^{2 for 1 hour.} After 1 hour, the reaction product produced in the reactor ^{was withdrawn into a receiver connected to the reactor and the pressure was set to be about 10 kg / cm 2} lower, and the ultimate viscosity [η] was 0.15 dl / g. 525 g of the polyamide precursor of the above was obtained.
Next, this polyamide precursor was dried and melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain a semi-aromatic polyamide (PA-3).

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

<Preparation of semi-aromatic polyamide (PA-4)>
1,9-diaminononane 303.9 g (1.92 mol), 2-methyl-1,8-diaminooctane 44.3 g (0.28 mol), terephthalic acid 365.5 g (2.2 mol), as a catalyst 0.55 g (5.2 × 10 ^-3 mol) of sodium phosphite and 64 ml of ion-exchanged water were charged in a 1 liter reactor, and after nitrogen substitution, the reaction was carried out at 250 ° C. and 35 kg / cm ² for 1 hour. went. After 1 hour, the reaction product produced in the reactor ^{was withdrawn into a receiver connected to the reactor and the pressure was set to be about 10 kg / cm 2} lower, and the ultimate viscosity [η] was 0.16 dl / g. 622 g of the polyamide precursor of the above was obtained.
Next, this polyamide precursor was dried and melt-polymerized at a cylinder set temperature of 330 ° C. using a twin-screw extruder to obtain a semi-aromatic polyamide (PA-4).

The composition of the obtained semi-aromatic polyamide (PA-4) was such that the terephthalic acid component unit content in the dicarboxylic acid component unit was 100 mol%, and the 1,9-diaminononane component unit content in the diamine component unit was 87. It was 3 mol%, and the 2-methyl-1,8-diaminooctane component unit content was 12.7 mol%. The ultimate viscosity of the semi-aromatic polyamide (PA-4) was 0.99 dl / g, and the melting point Tm was 303 ° C.

The ultimate viscosities and melting points Tm of the semi-aromatic polyamide resins (PA-1) to (PA-4) were measured by the following methods, respectively.

[Ultimate viscosity [η]]
The ultimate viscosity [η] of the obtained semi-aromatic polyamide resin was measured as follows. 0.5 g of a semi-aromatic polyamide resin was dissolved in 50 ml of a 96.5% sulfuric acid solution. The number of seconds of flow of the obtained solution under the condition of 25 ° C. ± 0.05 ° C. was measured using an Ubbelohde viscometer, and "Formula: [η] = ηSP / (C (1 + 0.205ηSP)). It was calculated based on.
[Η]: Extreme viscosity (dl / g)
ηSP: Specific viscosity C: Sample concentration (g / dl)
t: Number of seconds (seconds) of flow of the sample solution
t ₀ : Number of seconds (seconds) of blank sulfuric acid flowing down
ηSP = (t−t ₀ ) / t ₀

[Melting point Tm]
The melting point Tm of the semi-aromatic polyamide resin was measured according to JIS K7121. Specifically, using DSC7 manufactured by Perkin Elemer, the temperature was raised at a rate of 10 ° C./min to obtain the endothermic curve of DSC, and the temperature at the maximum peak position was defined as the melting point Tm.

2. 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%. The density was 0.920 g / cm ³ , the MFR (ASTM D 1238, 190 ° C., 2.16 kg load) was 1.0 g / 10 minutes, and the melting point was 124 ° C.

2-2. Modified olefin polymer (B)
<Preparation of modified ethylene / 1-butene copolymer (MAH-PE-1)>
The above-prepared ethylene / 1-butene copolymer (PE-1) (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 minutes, ethylene content = 96 mol%) 100 parts by mass, 0.8 parts by mass of maleic anhydride, and peroxide [trade name Perhexin-25B, manufactured by Nippon Oil & Fats Co., Ltd.] 0.07 parts by mass were mixed with a hex shell mixer, and the obtained mixture was melt-grafted and modified with a 65 mmφ uniaxial extruder set at 230 ° C. to obtain a modified ethylene / 1-butene copolymer (MAH-PE-1). ) Was obtained.

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

<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%. 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 minutes.
100 parts by mass of the above-prepared ethylene / 1-butene copolymer (PE-2), 1.2 parts by mass of maleic anhydride, and peroxide [trade name: Perhexin-25B, manufactured by Nippon Oil & Fats Co., Ltd.] 0.06 The parts by mass were mixed with a hexshell mixer, and the obtained mixture was melt-grafted with a 65 mmφ uniaxial extruder set at 230 ° C. to obtain a modified ethylene / 1-butene copolymer (MAH-PE-2). It was.
The amount of maleic anhydride graft of the modified ethylene / 1-butene copolymer (MAH-PE-2) was measured by IR analysis and found to be 1.0% by mass. 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 minutes.

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, respectively.

[composition]
The composition of the modified olefin polymer, for example, the content of ethylene and α-olefin having 3 or more carbon atoms (mol%) and the content of functional group structural units (mass%) were ^{measured by 13} C-NMR. The measurement conditions are as follows.
Measuring device: Nuclear magnetic resonance device (ECP500 type, manufactured by JEOL Ltd.)
Observation nucleus: ¹³ C (125 MHz)
Sequence: Single pulse Proton decoupling Pulse width: 4.7 μsec (45 ° pulse)
Repeat time: 5.5 seconds Number of integrations: 10,000 times or more Solvent: Ortodichlorobenzene / Deuterated benzene (volume ratio: 80/20) Mixed solvent Sample concentration: 55 mg / 0.6 mL
Measurement temperature: 120 ° C
Standard value of chemical shift: 27.50ppm

[density]
The density was measured at a temperature of 23 ° C. using a density gradient tube according to JIS K7112.

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

[Crystallinity]
A test piece of ASTM-1 (dumbbell piece) having a thickness of 3 mm was prepared, and a section was cut out from the central part in the length direction and the central part in the thickness direction. The obtained sample was fixed to a sample holder and measured by a wide-angle X-ray diffraction method while rotating the sample holder using RINT2550 manufactured by Rigaku Corporation.

3. 3. Other materials <Copper stabilizer (C)>
Copper-based stabilizer (C-1): Mixture of 10% by mass copper (I) iodide and 90% by mass 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)
Semi-aromatic polyamide resin (A), modified olefin polymer (B), copper-based stabilizer (C), unmodified olefin polymer (D) and inorganic filler (E) at the composition ratios shown in Table 1 or 2. ) Was mixed with a tumbler blender and melt-kneaded at a cylinder temperature condition of 300 to 335 ° C. using a 30 mmφ vent type twin-screw extruder. Then, the kneaded product was extruded into a strand shape and cooled in a water tank. Then, the strands were taken up with a pelletizer and cut to obtain a pellet-shaped semi-aromatic polyamide resin composition.

The bending strength / elastic modulus, Charpy impact strength, creep deformation amount, bend occlusion property, and heat aging property of the obtained semi-aromatic polyamide resin composition were evaluated by the following methods.

[Bending strength / flexural 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 at a temperature of 23 ° C. in a nitrogen atmosphere for 24 hours. Next, a bending test was performed under an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% at an AB5 manufactured by NTESCO, a span of 26 mm, and a bending speed of 5 mm / min, and the bending strength (MPa) and elastic modulus (MPa) were measured. did.

[Charpy impact strength]
Using the obtained semi-aromatic polyamide resin composition, a notched multipurpose test piece was prepared in accordance with ISO-179, and the Charpy impact strength (J / m) was measured.

[Creep deformation amount]
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)
The obtained test piece was loaded with a load of 1.6 MPa using a creep tester (manufactured by A & D Co., Ltd., model number; CP6-L-250) under 80 ° C. × 95% RH conditions. The amount of creep deformation after 24 hours was determined.
◯: Creep deformation amount of 0.8 mm or less Δ: Creep deformation amount of more than 0.8 mm and 1.6 mm or less ×: Creep deformation amount of more than 1.6 mm Δ or more was judged to be good.

[Vent obstructive]
The obtained semi-aromatic polyamide resin composition was injection molded by 400 shots under the following molding conditions. After that, the area of the mold depot attached to the mold nest was measured.
Molding machine: SG50-MIII manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder set temperature: 340 ° C
Mold temperature: 40 ° C
Injection speed: 150 mm / sec
The larger the area of the mold depot, the larger the amount of the mold depot, the easier it is to block the vent, and the poorer the continuous moldability. Specifically, it was judged that the area of the mold depot was good if it ^{was 3.5 cm 2} or less, and further good if it was less than ^{3.0 cm 2.}

[Heat-resistant aging]
The following dumbbell test pieces were prepared using the obtained semi-aromatic polyamide resin composition.
(Dumbbell test piece)
Thickness: 3.2 mm
Length of parallel part: 16.5 mm, width of parallel part: 3 mm
Specimen length: 64 mm, chuck width: 12 mm
The obtained test piece was stored in an air circulation furnace under the condition of a temperature of 160 ° C. for 200 hours or 300 hours, and then the test piece was taken out from the furnace and cooled to 23 ° C. Using this test piece, a tensile test was conducted in an atmosphere having a temperature of 23 ° C. and a relative humidity of 50%. Then, it was determined whether or not the yield point was confirmed after the storage for 200 hours and the storage for 300 hours, respectively.
〇: There is a yield point after storage for 300 hours Δ: There is a yield point after storage for 200 hours, but there is no yield point after storage for 300 hours ×: No yield point after storage for 200 hours

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, the semi-aromatic polyamide resin compositions of Examples 1 to 13 containing the modified ethylene / α-olefin copolymer (B1) and the copper-based stabilizer (C) are all included. It can be seen that the heat-resistant aging property is high, the bend blockage is small, and mold contamination can be suppressed.

Further, it can be seen that the impact strength is enhanced by further containing the modified ethylene / α-olefin copolymer (B2) (comparison between Examples 4 and 8).

Further, it can be seen that the vent clogging can be further reduced by further containing the unmodified olefin polymer (D) (contrast 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 ultimate viscosity and the semi-aromatic polyamide (PA-3) having a low ultimate viscosity, the mechanical strength is not lowered. , It can be seen that the bend obstruction can be further improved (comparison between Examples 2 and 4, comparison between Examples 1, 10 and 14).

Furthermore, the ratio of semi-aromatic polyamides (PA-1) and (PA-2) with high extreme viscosities to semi-aromatic polyamides (PA-3) with low extreme viscosities ((PA-1 + PA-2) / PA-3). ) Is higher, the heat aging resistance and bending strength are less likely to be impaired (comparison with Examples 3, 10 and 12).

Further, it can be seen that the bending strength of the obtained molded product can be further increased by further adding talc, which is the inorganic filler (D) (comparison between Examples 1 and 16).

On the other hand, it can be seen that the semi-aromatic polyamide resin compositions of Comparative Examples 1, 4 and 5 which do not contain the copper-based stabilizer (C) have low heat aging resistance. Further, 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 property. , It can be seen that the impact strength of Charpy is low. Further, 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. It can be seen that the bend obstruction is high and mold contamination is likely to occur.

5. Preparation of Second Semi-Aromatic Polyamide Resin Composition (Examples 14-16)
Semi-aromatic polyamide resin (A), modified olefin polymer (B), copper-based stabilizer (C), unmodified olefin polymer (D) and inorganic filler (E) at the composition ratios shown in Table 3. The mixture was mixed with a tumbler blender, and melt-kneaded using a vent-type twin-screw extruder having a diameter of 30 mm under a cylinder temperature condition of 300 to 335 ° C. Then, the kneaded product was extruded into a strand shape and cooled in a water tank. Then, the strands were taken up with a pelletizer and cut to obtain a pellet-shaped semi-aromatic polyamide resin composition.

The bending strength / elastic modulus, Charpy impact strength, creep deformation amount, bend occlusion property, and heat aging property of the obtained semi-aromatic polyamide resin composition were evaluated by the same methods 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 semi-aromatic polyamides of Examples 14 to 16 containing the modified ethylene / α-olefin copolymer (B2), the unmodified olefin polymer (D), and the copper-based stabilizer (C). It can be seen that all of the resin compositions have high heat aging resistance and less bend clogging, and can suppress mold contamination.

On the other hand, it can be seen that the semi-aromatic polyamide resin compositions of Comparative Examples 1, 4 and 5 which do not contain the copper-based stabilizer (C) have low heat aging resistance. Further, it can be seen that the semi-aromatic polyamide resin composition of Comparative Example 2 containing no modified ethylene / α-olefin copolymer (B2) not only does not improve the heat aging property but also has a low Charpy impact strength. Further, the semi-aromatic polyamide resin composition of Comparative Example 3 containing no unmodified ethylene / α-olefin copolymer (D) has a large amount of creep deformation, high bend clogging, and mold contamination. It turns out to be easy.

This application claims priority under Japanese Patent Application No. 2017-158130 filed on August 18, 2017. All the contents described in the application specification are incorporated in the application specification.

The semi-aromatic polyamide resin composition of the present invention is less likely to cause mold contamination during molding, and can produce a molded product having excellent heat resistance, creep resistance at high temperature, and mechanical strength, for example. It is particularly preferably used for molding automobile parts.

Claims (22)

A semi-aromatic polyamide resin (A) having a melting point of 280 to 330 ° C. as measured by a differential scanning calorimeter (DSC) and
A modified olefin polymer (B) containing a functional group structural unit containing a hetero atom, and
Copper-based stabilizer (C) and
A semi-aromatic polyamide resin composition containing
The semi-aromatic polyamide resin (A) contains a repeating unit composed 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 contains 50 to 100 mol% of a linear alkylenediamine component unit having 4 to 18 carbon atoms and 4 to 4 carbon atoms having a side chain alkyl group with respect to the total number of moles of the diamine component unit. 18 alkylenediamine component unit saw including a 0-50 mol%,
Before SL modified olefin polymer (B),
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 ,
A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms containing a modified ethylene / α-olefin copolymer (B2) modified with an unsaturated carboxylic acid or a derivative thereof, and containing the same.
The modified ethylene / α-olefin copolymer (B1) is
Wherein the functional group structure unit including the hetero atom derived from an unsaturated carboxylic acid or its derivative comprises 0.01 to 5 wt%, and meets the following requirements (i) ~ (iii),
(I) The density is in ^{the range of 0.89 to 0.95 g / cm 3.} (ii) The temperature (melting point; Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 90 to 127. ℃ is (iii) a crystallinity, as measured by X-ray diffractometry Ru 20% to 60% der
The modified ethylene / α-olefin copolymer (B2) is
It contains 0.01 to 5% by mass of a functional group structural unit containing the heteroatom derived from the unsaturated carboxylic acid or a derivative thereof, and satisfies the following requirement (iv).
(Iv) The density is in the range of ^{0.80 g / cm 3} or more and less than 0.89 g / cm ^3.
Semi-aromatic polyamide resin composition . The unmodified olefin polymer (D) containing no functional group structural unit containing the hetero atom is further contained.
The unmodified olefin polymer (D) is a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms.
The semi-aromatic polyamide resin composition according to claim 1. The dicarboxylic acid component unit is a total of 55 aromatic carboxylic acid component units other than terephthalic acid and / or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms with respect to the total number of moles of the dicarboxylic acid component unit. Including more than mol%,
The semi-aromatic polyamide resin composition according to claim 1 or 2. The diamine component unit has 50 to 99 mol% of the linear alkylenediamine component unit having 4 to 18 carbon atoms and the number of carbon atoms having the side chain alkyl group with respect to the total number of moles of the diamine component unit. Containing 4-18 alkylenediamine component units to 1-50 mol%,
The semi-aromatic polyamide resin composition according to any one of claims 1 to 3. The linear alkylenediamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit.
The semi-aromatic polyamide resin composition according to any one of claims 1 to 4. The alkylenediamine component unit having a side chain alkyl group and having 4 to 18 carbon atoms is a 2-methyl-1,5-diaminopentane component unit.
The semi-aromatic polyamide resin composition according to any one of claims 1 to 5. The semi-aromatic polyamide resin (A) is
With respect to 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A)
A semi-aromatic polyamide resin (A1) having an intrinsic viscosity [η] of 0.9 dl / g or more measured at 30 ° C. in concentrated sulfuric acid was added to 35 to 100 parts by mass.
A semi-aromatic polyamide resin (A2) having an ultimate viscosity [η] measured at 30 ° C. in concentrated sulfuric acid of 0.7 dl / g or more and less than 0.9 dl / g is contained in an amount of 0 to 65 parts by mass.
The semi-aromatic polyamide resin composition according to any one of claims 1 to 6. Inorganic filler (E), further comprising 1 to 200 parts by weight per 100 parts by weight wood fat component,
The semi-aromatic polyamide resin composition according to any one of claims 1 to 7. The inorganic filler (E) contains a fibrous inorganic filler or talc.
The semi-aromatic polyamide resin composition according to claim 8. 50 to 98 parts by mass of the semi-aromatic polyamide resin (A)
The modified olefin polymer (B) was added to 1 to 40 parts by mass.
The copper-based stabilizer (C) was added to 0.0001 to 1 part by mass.
The amount of the unmodified olefin polymer (D) containing no functional group structural unit containing a hetero atom was 0 to 40 parts by mass.
Inorganic filler (E) with 0 to 50 parts by mass,
(However, the semi-aromatic polyamide resin (A), the modified olefin polymer (B), the copper-based stabilizer (C), the unmodified olefin polymer (D), the inorganic filler (E). The total is 100 parts by mass),
The semi-aromatic polyamide resin composition according to any one of claims 1 to 9. The semi-aromatic polyamide resin composition according to any one of claims 1 to 10.
Molded body. A semi-aromatic polyamide resin (A) having a melting point of 280 to 330 ° C. as measured by a differential scanning calorimeter (DSC) and
A modified olefin polymer (B) containing a functional group structural unit containing a hetero atom, and
Copper-based stabilizer (C) and
A semi-aromatic polyamide resin composition containing
The semi-aromatic polyamide resin (A) contains a repeating unit composed of a dicarboxylic acid component unit and a diamine component unit, and
The dicarboxylic acid component unit contains 45 mol% or more of the terephthalic acid component unit with respect to the total number of moles of the dicarboxylic acid component unit.
The diamine component unit contains 50 to 100 mol% of a linear alkylenediamine component unit having 4 to 18 carbon atoms and 4 to 4 carbon atoms having a side chain alkyl group with respect to the total number of moles of the diamine component unit. Contains 18 alkylenediamine component units of 0 to 50 mol%.
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 is contained.
The modified ethylene / α-olefin copolymer (B2) 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 a derivative thereof, meets the following requirement (iv), and has a (iv) density of 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 is an unmodified olefin polymer (D) containing no functional group structural unit, which is unmodified ethylene and has 3 to 3 carbon atoms. Further comprising a polymer with 20 α-olefins,
Semi- aromatic polyamide resin composition. The modified olefin polymer (B) is
A copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms is further contained, and 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
It contains 0.01 to 5% by mass of a functional group structural unit containing the heteroatom derived from the unsaturated carboxylic acid or a derivative thereof, and satisfies the following requirements (i) to (iii).
The semi-aromatic polyamide resin composition according to claim 12.
(I) The density is in ^{the range of 0.89 to 0.95 g / cm 3.} (ii) The temperature (melting point; Tm) at the maximum peak position of the endothermic curve measured by a differential scanning calorimeter (DSC) is 90 to 127. The degree of crystallinity measured by (iii) X-ray diffractometry is 20 to 60%. The dicarboxylic acid component unit is a total of 55 aromatic carboxylic acid component units other than terephthalic acid and / or an aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms with respect to the total number of moles of the dicarboxylic acid component unit. Including more than mol%,
The semi-aromatic polyamide resin composition according to claim 12 or 13. The diamine component unit has 50 to 99 mol% of the linear alkylenediamine component unit having 4 to 18 carbon atoms and the number of carbon atoms having the side chain alkyl group with respect to the total number of moles of the diamine component unit. Containing 4-18 alkylenediamine component units to 1-50 mol%,
The semi-aromatic polyamide resin composition according to any one of claims 12 to 14. The linear alkylenediamine component unit having 4 to 18 carbon atoms is a 1,6-diaminohexane component unit.
The semi-aromatic polyamide resin composition according to any one of claims 12 to 15. The alkylenediamine component unit having a side chain alkyl group and having 4 to 18 carbon atoms is a 2-methyl-1,5-diaminopentane component unit.
The semi-aromatic polyamide resin composition according to any one of claims 12 to 16. The semi-aromatic polyamide resin (A) is
With respect to 100 parts by mass of the total amount of the semi-aromatic polyamide resin (A)
A semi-aromatic polyamide resin (A1) having an intrinsic viscosity [η] of 0.9 dl / g or more measured at 30 ° C. in concentrated sulfuric acid was added to 35 to 100 parts by mass.
A semi-aromatic polyamide resin (A2) having an ultimate viscosity [η] measured at 30 ° C. in concentrated sulfuric acid of 0.7 dl / g or more and less than 0.9 dl / g is contained in an amount of 0 to 65 parts by mass.
The semi-aromatic polyamide resin composition according to any one of claims 12 to 17. Inorganic filler (E), further comprising 1 to 200 parts by weight per 100 parts by weight wood fat component,
The semi-aromatic polyamide resin composition according to any one of claims 12 to 18. The inorganic filler (E) contains a fibrous inorganic filler or talc.
The semi-aromatic polyamide resin composition according to claim 19. 50 to 97 parts by mass of the semi-aromatic polyamide resin (A)
The modified olefin polymer (B) was added to 1 to 40 parts by mass.
The copper-based stabilizer (C) was added to 0.0001 to 1 part by mass.
The unmodified olefin polymer (D) was added to 1 to 40 parts by mass.
Inorganic filler (E) with 0 to 50 parts by mass,
(However, the semi-aromatic polyamide resin (A), the modified olefin polymer (B), the copper-based stabilizer (C), the unmodified olefin polymer (D), the inorganic filler (E). The total is 100 parts by mass),
The semi-aromatic polyamide resin composition according to any one of claims 12 to 20. Obtained from the semi-aromatic polyamide resin composition according to any one of claims 12 to 21.
Molded body.