JP6502755B2 - Resin composition for engine support member and engine support member - Google Patents

Description

  The present invention relates to a resin composition for an engine support member and an engine support member.

  In recent years, in order to improve the fuel efficiency of automobiles, it has been studied to reduce the weight by replacing metal members used for parts in the engine room of automobiles with resin. Among them, polyamide resins are much lighter than metals, and have excellent rigidity, heat resistance, oil resistance, and the like, and thus they are suitably used as automobile parts.

  For example, since high rigidity is required at high temperature for parts in an automobile engine room, a polyamide resin composition containing a polyamide resin and glass fibers has been proposed as a resin material for such applications (patented) Literature 1).

  On the other hand, as the resinification of metal parts and the miniaturization of parts progress, the downsizing of the engine room is rapidly expanding. Along with this, resin materials are required to have higher heat resistance than ever, and with PA 66, which is a general-purpose aliphatic polyamide resin, there are increasing situations where heat resistance requirements exceeding 100 ° C. can not be satisfied.

  For example, since high rigidity at 100 ° C. is required for the engine mount bracket, which is one of the parts supporting the engine, aliphatic polyamide and semi-aromatic compounds having a high glass transition temperature as resin materials for such applications are required. The resin composition which added group family polyamide and glass fiber is proposed (for example, patent documents 2). Further, a product shape effective for improving the strength of welds of resin engine mounts and torque rods has been proposed (for example, Patent Document 3). Further, as the polyamide resin composition, a semi-aromatic polyamide resin having a melting point of 290 ° C. or higher, a semi-aromatic polyamide resin having a heat of fusion ΔH of 5 J / g or less, an olefin polymer containing a functional group structural unit, and fibrous A resin composition containing a filler is also known (Patent Document 4).

Unexamined-Japanese-Patent No. 2-240160 Unexamined-Japanese-Patent No. 11-49950 gazette Japanese Patent Application Publication No. 2004-255971 International Publication No. 2015/011935

  By increasing the compounding ratio of the semiaromatic polyamide, the rigidity and heat resistance at high temperature of the molded product can be improved. However, since the aromatic concentration in the main chain skeleton of the polyamide resin in the resin composition increases and the molecular chain becomes rigid, for example, the weld portion of the injection-molded product (the molten resin streams merge and melt in the mold) There is a concern that the strength of the worn part) may be reduced, or the strength against impact may be reduced.

  Engine supporting members such as engine mounts not only have strength (stiffness) and heat resistance to withstand use under high temperature conditions, but also have resistance to vibration during vehicle travel (weld strength and impact resistance) Although it is required, the conventional polyamide resin composition has a problem that it is difficult to achieve both heat resistance and resistance to vibration (weld strength and impact resistance).

  Furthermore, the engine not only has a large temperature change when it is repeatedly stopped and driven, but also the engine room is made compact, so there is also a demand for higher heat aging characteristics than ever before. When the resin is deteriorated by the high temperature atmosphere, there is a concern that the rigidity of the molded product is insufficient and the long-term use becomes impossible.

  Patent Document 4 does not disclose the idea of achieving both strength (rigidity) under high temperature and vibration resistance. Moreover, in order to use the said resin composition as an engine support member, much higher heat resistance and rigidity are desired.

  The present invention has been made in view of the above problems, and an engine support member having high heat resistance and strength that can withstand use under high temperature conditions, and high vibration resistance (weld strength and impact resistance). It is an object of the present invention to provide a resin composition for use as well as an engine support member using the same.

[1] Polyamide resin (A) 29.89 to 68.9 mass having a glass transition temperature of 80 ° C. to 150 ° C. and a melting point (Tm) of 300 ° C. or higher, which is measured by a differential scanning calorimeter (DSC) %, And a polyamide resin (B) 0.1 to 20% by mass in which the melting point (Tm) measured by a differential scanning calorimeter (DSC) is not substantially observed, and a fibrous filler (C) 30 to 70% by mass; Heat-resistant stabilizer (D) in an amount of 0.01 to 3.0% by mass (provided that the total of (A), (B), (C) and (D) is 100% by mass); (A) contains 20 to 100 mol% of terephthalic acid component units, 0 to 80 mol% of aromatic dicarboxylic acid component units other than terephthalic acid and 0 to 40 mol% of aliphatic dicarboxylic acid component units having 4 to 20 carbon atoms Dicarboxylic acid containing at least one of An engine support member comprising component unit (a1) (wherein the total of dicarboxylic acid component units is 100 mol%) and diamine component unit (a2) containing aliphatic diamine component units having 4 to 20 carbon atoms Resin composition.
[2] The resin composition for an engine supporting member according to [1], wherein the aliphatic diamine component unit of the polyamide resin (A) satisfies at least one of the following 1) and 2).
1) containing 40 to 100 mol% of a linear alkylene diamine component unit having 4 to 20 carbon atoms with respect to the total number of moles of the aliphatic diamine component unit 2) a branched alkylene diamine having 4 to 20 carbon atoms The component unit is contained in an amount of 60 mol% or less based on the total number of moles of the aliphatic diamine component unit [3] The polyamide resin (B) comprises a dicarboxylic acid component unit (b1) containing an isophthalic acid component unit, and a carbon atom The resin composition for engine supporting members as described in [1] or [2] which contains the diamine component unit (b2) containing several 4-15 aliphatic diamine component unit.
[4] In the polyamide resin (B), the dicarboxylic acid component unit (b1) may further contain a terephthalic acid component unit, and the molar ratio of the isophthalic acid component unit to the terephthalic acid component unit is The resin composition for engine supporting members as described in [3], which is isophthalic acid component unit / terephthalic acid component unit = 55/45 to 100/0.
[5] The mass ratio B / (A + B) of the polyamide resin (A) to the polyamide resin (B) is in a range of 0.05 to 0.35, according to any one of [1] to [4]. Resin composition for engine supporting member.
[6] In the polyamide resin (A), the aromatic dicarboxylic acid component unit other than terephthalic acid contains an isophthalic acid component unit, and the aliphatic diamine component unit having 4 to 20 carbon atoms has 4 carbon atoms The resin composition for engine supporting members as described in [1] or [2] which contains -20 linear alkylene diamine component units.
[7] In the polyamide resin (A), the molar ratio of the terephthalic acid component unit to the isophthalic acid component unit is terephthalic acid component unit / isophthalic acid component unit = 55/45 to 80/20, [6 ] The resin composition for engine supporting members as described in-.
[8] In the polyamide resin (A), the linear alkylene diamine component unit having 4 to 20 carbon atoms is a hexamethylene diamine component unit, and the branched alkylene diamine component unit having 4 to 20 carbon atoms The resin composition for an engine supporting member according to [2], which is a 2-methyl-1,5-pentanediamine component unit.
[9] In the polyamide resin (A), the branched alkylenediamine component unit having 4 to 20 carbon atoms is 1,9-nonanediamine component unit and 2-methyl-1,8-octanediamine component unit, The resin composition for engine supporting members as described in [2].
[10] An engine support member comprising the molded product of the resin composition for an engine support member according to any one of [1] to [9].

  According to the present invention, a resin composition for an engine support member and an engine support member having high heat resistance and strength that can withstand use under high temperature conditions and high resistance to vibration (weld strength and impact resistance) Can be provided.

It is a schematic diagram which shows an example of an engine mount.

  As described above, the resin composition used for the engine support member is desired to be compatible with heat resistance and strength (rigidity) that withstands use at high temperatures and high vibration resistance (weld strength and impact resistance). .

  A molded product containing a high melting point (high crystallinity) polyamide resin (A) is excellent in high strength (stiffness) and heat resistance at high temperatures, but has low flexibility and vibration resistance (weld part strength and impact resistance) ) Tend to be low. On the other hand, by combining the low crystalline polyamide resin (B) in a predetermined ratio, high vibration resistance can be imparted to the molded product without losing the strength and heat resistance under high temperature.

  Furthermore, by combining the polyamide resin (A) and the heat resistant stabilizer (D), the molded article can be provided with high heat resistance suitable for the engine support member. The present invention has been made based on such findings.

1. Resin composition for engine supporting member The resin composition for engine supporting member of the present invention comprises a polyamide resin (A), a polyamide resin (B), a fibrous filler (C), and a heat resistant stabilizer (D). Including.

1-1. Polyamide resin (A)
The polyamide resin (A) is a polyamide resin having a glass transition temperature (Tg) of 80 ° C. to 150 ° C. and a melting point (Tm) of 300 ° C. or higher, which is measured by a differential scanning calorimeter (DSC) preferable. Such polyamide resin (A) can impart high temperature strength (rigidity) and heat resistance to a molded article.

  The melting point (Tm) of the polyamide resin (A) measured by differential scanning calorimeter (DSC) is more preferably 300 ° C. or more and 340 ° C. or less, and still more preferably 300 ° C. or more and 330 ° C. or less. When the melting point (Tm) of the polyamide resin (A) is 300 ° C. or more, a molded product having high heat resistance and strength (rigidity) is easily obtained. When the melting point (Tm) of the polyamide resin (A) is 340 ° C. or less, it is not necessary to excessively increase the molding temperature, so it is possible to suppress the thermal decomposition of the polymer and various additives during melt polymerization or melt molding. .

  The glass transition temperature (Tg) of the polyamide resin (A) measured by differential scanning calorimetry (DSC) is preferably 80 ° C. to 150 ° C., and more preferably 90 to 135 ° C. When the glass transition temperature (Tg) of the polyamide resin (A) is 80 ° C. or higher, the molded article can maintain good heat resistance under the operating environment temperature.

  The melting point (Tm) and the glass transition temperature (Tg) of the polyamide resin (A) can be measured with a differential scanning calorimeter (for example, DSC 220 C type, manufactured by Seiko Instruments Inc.). Specifically, about 5 mg of polyamide resin is sealed in an aluminum pan for measurement, and heated from room temperature to 330 ° C. at 10 ° C./min. In order to completely melt the polyamide resin, it is held at 330 ° C. for 5 minutes, and then cooled to 30 ° C. at 10 ° C./min. After 5 minutes at 30 ° C., perform a second heating to 330 ° C. at 10 ° C./min. The peak temperature (° C.) at the second heating is taken as the melting point (Tm) of the polyamide resin, and the displacement point corresponding to the glass transition is taken as the glass transition temperature (Tg).

  The melting point and the glass transition temperature of the polyamide resin (A) can be adjusted, for example, by the composition of the dicarboxylic acid component unit and the diamine component unit. In order to increase the melting point of the polyamide resin (A), for example, the content ratio of terephthalic acid component units may be increased.

  The polyamide resin (A) is preferably a semiaromatic polyamide resin having the above-mentioned melting point and glass transition temperature. The semiaromatic polyamide resin is a polyamide resin containing an aromatic dicarboxylic acid component unit or an aromatic diamine component unit, preferably a polyamide resin containing an aromatic dicarboxylic acid component unit.

  That is, the polyamide resin (A) preferably contains a dicarboxylic acid component unit (a1) containing an aromatic dicarboxylic acid component unit and a diamine component unit (a2) containing an aliphatic diamine component unit.

(Dicarboxylic acid component unit (a1))
The dicarboxylic acid component unit (a1) preferably contains at least a terephthalic acid component unit. The polyamide resin containing a terephthalic acid component unit has high crystallinity, and can impart good heat resistance and rigidity to the resin composition.

  The dicarboxylic acid component unit (a1) comprises 20 to 100 mol% of terephthalic acid component unit, 0 to 80 mol% of aromatic dicarboxylic acid component unit other than terephthalic acid, and 0 aliphatic dicarboxylic acid component unit having 4 to 20 carbon atoms It is more preferable to contain at least one of 40 to 40 mol%; further preferably 55 to 100 mol% of terephthalic acid component unit and 0 to 45 mol% of aromatic dicarboxylic acid component unit other than terephthalic acid. However, the total (total number of moles) of dicarboxylic acid component units is 100 mol%.

  Examples of terephthalic acid include terephthalic acid and terephthalic acid ester (C1-C4 alkyl ester of terephthalic acid).

  Examples of aromatic dicarboxylic acids other than terephthalic acid include isophthalic acid, 2-methylterephthalic acid, naphthalenedicarboxylic acid and esters thereof, preferably it may be isophthalic acid.

  The aliphatic dicarboxylic acid having 4 to 20 carbon atoms is preferably an aliphatic dicarboxylic acid having 6 to 12 carbon atoms, and examples thereof include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethyl glutaric acid, 3, 3-diethyl succinic acid, azelaic acid, sebacic acid, suberic acid etc., preferably adipic acid .

  The molar ratio of the terephthalic acid component unit to the aromatic dicarboxylic acid component unit other than terephthalic acid (preferably isophthalic acid component unit) in the dicarboxylic acid component unit (a1) is: terephthalic acid component unit / aromatic compound other than terephthalic acid The dicarboxylic acid component unit (preferably isophthalic acid component unit) is preferably 20/80 to 100/0, more preferably 55/45 to 80/20, and 60/40 to 85/15. Is more preferred. When the amount of the terephthalic acid component unit is a certain amount or more, the heat resistance and the rigidity of the resulting molded product are likely to be enhanced. When the amount of the terephthalic acid component unit is less than or equal to a certain amount, the impact resistance of the resulting molded product tends to be increased.

  The dicarboxylic acid component unit (a1) may further contain an alicyclic dicarboxylic acid component unit as long as the effects of the present invention are not impaired. Examples of alicyclic dicarboxylic acids include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and the like.

(Diamine component unit (a2))
The diamine component unit (a2) contains an aliphatic diamine component unit having 4 to 20 carbon atoms. The aliphatic diamine component unit having 4 to 20 carbon atoms can impart hydrophobicity to the molded product, and can lower hygroscopicity and water absorption.

  The aliphatic diamine component unit having 4 to 20 carbon atoms has 1) a linear alkylene diamine component unit having 4 to 20 carbon atoms, and 2) a branched alkylene diamine having 4 to 20 carbon atoms (a side chain It is preferable to include at least one of alkylene diamine) component units.

  The number of carbon atoms of the linear alkylene diamine component unit is preferably 4 to 15, and more preferably 6 to 12. Examples of linear alkylene diamines include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-octanediamine, 1,9-diaminononane, 1,10-diaminodecane 1, 1, 11-diaminoundecane, 1, 12-diaminododecane and the like. Among these, 1,6-diaminohexane and 1,9-nonanediamine are preferable. The linear alkylene diamine component unit may be contained alone or in combination of two or more.

  The content of the linear alkylene diamine component unit is preferably 40 to 100 mol% with respect to the total (total number of moles) of the aliphatic diamine component unit having 4 to 20 carbon atoms. It is thought that the water resistance of the molded object obtained will be easy to increase as content of a linear alkylene diamine component unit is more than fixed.

  The number of carbon atoms of the branched alkylene diamine component unit is preferably 4 to 15, and more preferably 6 to 12. Examples of branched alkylene diamines include 2-methyl-1,5-pentanediamine, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, 2-methyl-1,8- Included are octanediamine, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 2-methyl-1,11-diaminoundecane and the like. Among these, 2-methyl-1,5-pentanediamine and 2-methyl-1,8-octanediamine are preferable. The branched alkylene diamine component unit may be contained alone or in combination of two or more.

  The content of the branched alkylene diamine component unit is preferably 60 mol% or less with respect to the total (total number of moles) of the aliphatic diamine component unit having 4 to 20 carbon atoms. If the content of the branched alkylene diamine component unit is 60 mol% or less, there is little possibility that the strength of the molded product may be reduced or defects at the time of molding may be caused due to the excessive decrease in crystallinity.

  When the aliphatic diamine component unit having 4 to 20 carbon atoms contains both a linear alkylene diamine component unit and a branched alkylene diamine component unit, examples of preferable combinations thereof include 1,6-diaminohexane component A combination of units and 2-methyl-1,5-pentanediamine component units is included. The content of 1,6-diaminohexane component units is more than 45 mol% and less than 55 mol% based on the total number of moles of aliphatic diamine component units, and the content of 2-methyl-1,5-pentanediamine Is preferably more than 45 mol% and less than 55 mol%. Other examples of preferred combinations include combinations of 1,9-nonane diamine component units and 2-methyl-1,8-octane diamine component units. The content of 1,9-nonane diamine component units is more than 45 mol% and less than 85 mol% based on the total number of moles of aliphatic diamine component units, and containing 2-methyl-1,8-octane diamine component units The amount is preferably more than 15 mol% and less than 55 mol%.

  The content of the aliphatic diamine component unit is preferably 50 to 100 mol%, and more preferably 60 to 100 mol% with respect to the total (total number of moles) of diamine component units.

  The diamine component unit (a2) may further contain other diamine component units other than aliphatic diamine component units having 4 to 20 carbon atoms, as long as the effects of the present invention are not impaired. Examples of other diamine component units include alicyclic diamine component units and aromatic diamine component units. Examples of alicyclic diamines include 1,4-cyclohexanediamine, 1,3-cyclohexanediamine and the like. Examples of aromatic diamines include metaxylylene diamine and the like. The content of other diamine component units may be 50 mol% or less, preferably 40 mol% or less.

  In a specific example of the polyamide resin (A), a resin in which the dicarboxylic acid component unit is terephthalic acid component unit, and the aliphatic diamine component unit is 1,6-diaminohexane and 2-methyl-1,5-pentanediamine A resin wherein the dicarboxylic acid component unit is terephthalic acid component unit and the aliphatic diamine component unit is 1,9-nonanediamine and 2-methyl-1,8-pentanediamine; the dicarboxylic acid component unit is terephthalic acid component unit, A resin which is an isophthalic acid component unit and the aliphatic diamine component unit is 1,6-diaminohexane; and a dicarboxylic acid component unit is a terephthalic acid component unit and an adipic acid component unit, and the aliphatic diamine component unit is 1 , 6-diaminohexane and the like. The polyamide resin (A) may be contained alone or in combination of two or more.

  The intrinsic viscosity [η] of the polyamide resin (A) measured in a 96.5% sulfuric acid at a temperature of 25 ° C. is preferably 0.7 to 1.6 dl / g, and 0.8 to 1.2 dl. It is more preferable that it is / g. When the intrinsic viscosity [η] of the polyamide resin (A) is a certain value or more, the strength of the molded product tends to be sufficiently increased. The flowability at the time of shaping | molding of a resin composition is hard to be impaired as an intrinsic viscosity [eta] is below fixed. The intrinsic viscosity [η] is adjusted by the molecular weight of the polyamide resin (A).

The intrinsic viscosity is obtained by dissolving about 0.5 g of polyamide resin (A) in 50 ml of 96.5% concentrated sulfuric acid, and the resulting solution is allowed to flow seconds under 25 ° ± 0.05 ° C. It measures using a viscometer and is calculated based on the following formula.
[Η] = ηSP / (C (1 + 0.205ηSP))
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
t: Seconds of flow of sample solution (seconds)
t0: Blank sulfuric acid flow down seconds (seconds)
ηSP = (t−t0) / t0

  The polyamide resin (A) can be produced by the same method as a known polyamide resin, and can be produced, for example, by polycondensation of dicarboxylic acid and diamine in a uniform solution. Specifically, a lower condensate is obtained by heating a dicarboxylic acid and a diamine in the presence of a catalyst as described in WO 03/085029, and then the lower condensate is It can be produced by applying shear stress to the melt to cause polycondensation.

  When adjusting the intrinsic viscosity of a polyamide resin (A), it is preferable to mix | blend a molecular weight modifier (for example, terminal blocker) with a reaction system. The molecular weight modifier can be, for example, a monocarboxylic acid or a monoamine. Examples of monocarboxylic acids include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, aromatic monocarboxylic acids and alicyclic monocarboxylic acids. These molecular weight modifiers can adjust the amount of terminal amino groups of the polyamide resin (A) as well as adjusting the molecular weight of the polyamide resin (A). The aromatic monocarboxylic acid and alicyclic monocarboxylic acid may have a substituent at the cyclic structure part.

  Examples of aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid, myristic acid, palmitic acid, stearic acid, stearic acid, oleic acid and linoleic acid etc. included. Examples of aromatic monocarboxylic acids include benzoic acid, toluic acid, naphthalene carboxylic acid, methyl naphthalene carboxylic acid, phenylacetic acid and the like. Examples of alicyclic monocarboxylic acids include cyclohexanecarboxylic acid and the like.

  A molecular weight modifier is added to the reaction system of dicarboxylic acid and diamine. The addition amount is preferably 0.07 mol or less, more preferably 0.05 mol or less, per 1 mol of the total amount of the dicarboxylic acid. By using a molecular weight modifier in such an amount, at least a portion thereof is incorporated into the polyamide, whereby the molecular weight of the polyamide, that is, the intrinsic viscosity [η] is adjusted within the desired range.

  The content of the polyamide resin (A) is preferably 29.89 to 68.9 mass% with respect to the total of the components (A), (B), (C) and (D), and 35 It is more preferable that it is -65 mass%. When the content of the polyamide resin (A) is 30% by mass or more, high strength (rigidity) and heat resistance can be imparted to the resin composition. When the content of the polyamide resin (A) is 68.9% by mass or less, the impact resistance of the resin composition and the remarkable decrease in weld strength hardly occur.

1-2. Polyamide resin (B)
The polyamide resin (B) is preferably a polyamide resin whose melting point (Tm) which is measured by a differential scanning calorimeter (DSC) can not be substantially measured. Such a polyamide resin (B) has low crystallinity, and can impart good impact resistance and weld strength to the resin composition.

  “The melting point (Tm) is not substantially measured” means an endothermic peak based on crystal melting in the second heating (from room temperature to 330 ° C.) in the measurement of the above-mentioned melting point using a differential scanning calorimeter (DSC) Is not observed substantially.

  The heat of fusion (ΔH) of the polyamide resin (B) in the heating process (heating rate: 10 ° C./min) obtained by differential scanning calorimetry (DSC) is 0 J / g to 5 J / g. Preferably, it is 0 J / g. The heat of fusion is an index of the crystallinity of the resin, and the smaller the heat of fusion, the lower the crystallinity. When the heat of fusion (ΔH) of the polyamide resin (B) is 5 J / g or less and the crystallinity is low, the compatibility with the polyamide resin (A) is excellent and the appearance of the molded article of the resin composition is excellent. preferable. The polyamide resin (B) is preferably an amorphous resin.

  The heat of fusion (ΔH) is a value determined according to JIS K 7122. That is, in the differential scanning calorimetry chart obtained when scanning at a temperature rising rate of 10 ° C./min, from the area of the exothermic peak associated with crystallization It is a value to be obtained. The heat of fusion (ΔH) is a value at the first temperature rise that does not erase the history.

  The polyamide resin (B) is preferably a semiaromatic polyamide resin satisfying the above-mentioned melting point or heat of fusion (ΔH). The semiaromatic polyamide resin is a polyamide resin containing an aromatic dicarboxylic acid component unit or an aromatic diamine component unit, preferably a polyamide resin containing an aromatic dicarboxylic acid component unit.

  That is, the polyamide resin (B) preferably contains a dicarboxylic acid component unit (b1) containing an aromatic dicarboxylic acid component unit and a diamine component unit (b2) containing an aliphatic diamine component unit.

(Dicarboxylic acid component unit (b1))
The dicarboxylic acid component unit (b1) preferably contains at least an isophthalic acid component unit. The isophthalic acid component unit can lower the crystallinity of the polyamide resin, and can impart good impact resistance and weld strength to a molded article containing the polyamide resin.

  The content of the isophthalic acid component unit is preferably 40 mol% or more, more preferably 50 mol% or more based on the total (total number of moles) of the dicarboxylic acid component in the polyamide resin (B). When the content of the isophthalic acid component unit is 40 mol% or more, it is easy to impart impact resistance and weld strength to the molded product.

  The dicarboxylic acid component unit (b1) may further contain other dicarboxylic acid component units other than the isophthalic acid component unit, as long as the effects of the present invention are not impaired. Examples of other dicarboxylic acids include aromatic dicarboxylic acids other than isophthalic acid such as terephthalic acid, 2-methylterephthalic acid and naphthalene dicarboxylic acid, aliphatic dicarboxylic acids, and alicyclic dicarboxylic acids. The aliphatic dicarboxylic acid and the alicyclic dicarboxylic acid may be similar to the above-mentioned aliphatic dicarboxylic acid and alicyclic dicarboxylic acid, respectively. Among these, aromatic dicarboxylic acids other than isophthalic acid are preferable, and terephthalic acid is more preferable.

  The molar ratio of an isophthalic acid component unit to an aromatic dicarboxylic acid (preferably terephthalic acid) component unit other than isophthalic acid in the dicarboxylic acid component unit (b1) is an aromatic dicarboxylic acid other than isophthalic acid component unit / isophthalic acid ( Preferably, the component unit of terephthalic acid is 55/45 to 100/0, and more preferably 60/40 to 90/10. When the molar ratio of isophthalic acid component unit / aromatic dicarboxylic acid (preferably terephthalic acid) component unit other than isophthalic acid is within the above range, the polyamide resin (B) becomes amorphous and at the same time as the polyamide resin (A) Since the compatibility is also good, it is easy to increase the impact resistance and weld strength of the resin composition.

(Diamine component unit (b2))
The diamine component unit (b2) contains an aliphatic diamine component unit having 4 to 15 carbon atoms.

  It is more preferable that the carbon atom number of aliphatic diamine is 4-9. Examples of aliphatic diamines include those similar to the above-mentioned linear alkylene diamines and branched alkylene diamines, preferably 1,6-hexane diamine.

  The content of the aliphatic diamine component unit is preferably 50 to 100 mol%, and more preferably 60 to 100 mol% with respect to the total (total number of moles) of the diamine component unit (b2).

  The diamine component unit (b2) may further contain other diamine component units other than the aliphatic diamine component units, as long as the effects of the present invention are not impaired. Examples of other diamine components include alicyclic diamines and aromatic diamines. Alicyclic diamines and aromatic diamines may be similar to the aforementioned alicyclic diamines and aromatic diamines, respectively. The content of other diamine component units may be 50 mol% or less, preferably 40 mol% or less.

  Specific examples of the polyamide resin (B) include a polycondensate of isophthalic acid / terephthalic acid / 1,6-hexanediamine / bis (3-methyl-4-aminocyclohexyl) methane, isophthalic acid / bis (3-methyl- 4-aminocyclohexyl) methane / ω-laurolactam polycondensate, isophthalic acid / terephthalic acid / 1,6-hexanediamine polycondensate, isophthalic acid / 2,2,4-trimethyl-1,6-hexanediamine Polycondensate of / 2,4,4-trimethyl-1,6-hexanediamine, isophthalic acid / terephthalic acid / 2,2,4-trimethyl-1,6-hexanediamine / 2,4,4-trimethyl-1 , A polycondensate of 6-hexanediamine, a polycondensate of isophthalic acid / bis (3-methyl-4-aminocyclohexyl) methane / ω-laurolactam, And polycondensates of isophthalic acid / terephthalic acid / other diamine components and the like. Among them, a polycondensate of isophthalic acid / terephthalic acid / 1,6-hexanediamine is preferable. The polyamide resin (B) may be contained alone or in combination of two or more.

  The intrinsic viscosity [η] of the polyamide resin (B) measured in a 96.5% sulfuric acid at a temperature of 25 ° C. is preferably 0.6 to 1.6 dl / g, and 0.65 to 1.2 dl. It is more preferable that it is / g.

  The polyamide resin (B) can be produced by the same method as described above.

  The content of the polyamide resin (B) is preferably 0.1 to 20% by mass with respect to the total of the components (A), (B), (C) and (D). It is more preferable that it is -15 mass%. When the content of the polyamide resin (B) is 0.1% by mass or more, high impact resistance and weld strength can be imparted to the molded product. When the content of the polyamide resin (B) is 20% by mass or less, a remarkable decrease in the strength (rigidity) of the molded product hardly occurs.

  The content mass ratio B / (A + B) of the polyamide resin (A) to the polyamide resin (B) is preferably 0.05 to 0.35, and more preferably 0.07 to 0.2. When B / (A + B) is 0.05 or more, it is easy to impart sufficient impact resistance and weld strength to the resin composition. When B / (A + B) is 0.35 or less, it is easy to impart sufficient heat resistance and rigidity to the molded product.

1-3. Fibrous filler (C)
The fibrous filler (C) can impart strength (rigidity) to the molded product. Examples of fibrous fillers (C) include glass fibers, wollastonite, potassium titanate whiskers, calcium carbonate whiskers, aluminum borate whiskers, magnesium sulfate whiskers, sepiolite, sonotolite, zinc oxide whiskers, milled fibers, cut fibers And wholly aromatic polyamide fibers (eg, polyparaphenylene terephthalamide fibers, polymetaphenylene terephthalamide fibers, polyparaphenylene isophthalamide fibers, polymetaphenylene isophthalamide fibers and condensation products of diaminodiphenyl ether and terephthalic acid or isophthalic acid) The resulting fibers, etc.), boron fibers, liquid crystal polyester fibers, carbon fibers and the like are included. Among these, glass fiber, wollastonite and carbon fiber are preferable because the strength (rigidity) and heat resistance of the molded product can be easily improved. The fibrous filler (C) may be contained alone or in combination of two or more.

  The average fiber length of the fibrous filler (C) is preferably 1 μm to 20 mm, more preferably 5 μm to 10 mm, from the viewpoint of obtaining a molded product with sufficient strength without impairing moldability. More preferably, it is 10 μm to 7 mm. The aspect ratio of the fibrous filler (C) is preferably 5 to 2000, and more preferably 30 to 1000.

The average fiber length and the average fiber diameter of the fibrous reinforcing material (C) can be measured by the following method.
1) The resin composition or the molded product is dissolved in a hexafluoroisopropanol / chloroform solution (0.1 / 0.9% by volume) and then filtered to collect a filtrate obtained.
2) The filtrate obtained in the above 1) is dispersed in water, and the fiber length (Li) and the fiber diameter (Di) of each 300 arbitrary fibers are measured with an optical microscope (magnification: 50 times). Assuming that the number of fibers whose fiber length is Li is qi, the weight average length (Lw) is calculated based on the following equation, and this is used as the average fiber length of the fibrous reinforcement.
Weight average length (Lw) = (Σqi × Li ² ) / (Σqi × Li)
Similarly, assuming the number of fibers having a fiber diameter Di as ri, the weight average diameter (Dw) is calculated based on the following equation, and this is used as the average fiber diameter of the fibrous reinforcing material.
Weight average diameter (Dw) = (Σri × Di ² ) / (Σri × Di)

  The average fiber length and the average fiber diameter of the fibrous reinforcement (C) in the resin composition or in the molded product are generally substantially the same as the average fiber length and the average fiber diameter of the fibrous reinforcement (C) before melt-kneading It is an extent.

  The fibrous filler (C) is preferably surface-treated because the adhesion with the polyamide resin is improved and the mechanical properties of the resulting polyamide resin composition are significantly improved. Examples of surface treatment agents in the surface treatment include coupling agents such as silane coupling agents, titanium coupling agents and aluminate coupling agents, and sizing agents.

  Examples of coupling agents include aminosilanes, epoxysilanes, methyltrimethoxysilane, methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriacetoxysilane and vinyltrimethoxysilane. Examples of the sizing agent include epoxy compounds, urethane compounds, carboxylic acid compounds, urethane / maleic acid modified compounds, urethane / amine modified compounds and the like. One of these surface treatment agents may be used alone, or two or more thereof may be used in combination. In particular, when the coupling agent and the sizing agent are used in combination, the adhesion between the fibrous filler (C) and the polyamide resin is further improved, and the mechanical properties of the resulting resin composition are further improved.

  The content of the fibrous filler (C) is preferably 30 to 70% by mass with respect to the total of the components (A), (B), (C) and (D), and 35 to 60. It is more preferable that it is mass%, and it is still more preferable that it is 40-60 mass%. When the content of the fibrous filler (C) is 30% by mass or more, high rigidity can be easily imparted to the resin composition. When the content of the fibrous filler (C) is 70% by mass or less, it is difficult to cause an excessive increase in viscosity at the time of molding, a remarkable decrease in the impact resistance of the molded product and the weld strength.

1-4. Heat-resistant stabilizer (D)
The heat resistant stabilizer (D) preferably contains at least one of a copper stabilizer (D-1) and an organic heat stabilizer (D-2).

1-4-1. Copper-based stabilizer (D-1)
The copper-based stabilizer (D-1) is a salt of (i) a halogen and a metal of Group 1 or 2 of the periodic table (halogen metal salt), (ii) a copper compound, and (iii) a higher fatty acid metal Contains a mixture of salts.

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

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

  From the viewpoint of easily improving the heat resistance of the molded product and the corrosion resistance at the time of production, the molar ratio of halogen to copper is 0.1 It may be adjusted to be 1/1 to 200/1, preferably 0.5 / 1 to 100/1, more preferably 2/1 to 40/1.

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

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

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

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

  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 an element of Groups 1, 2 and 3 of the Periodic Table of the Elements, zinc, and aluminum Is preferred.

  The content of the copper stabilizer (D-1) is preferably 0.01 to 3 parts by mass with respect to 100 parts by mass in total of the polyamide resin (A) and the polyamide resin (B), and 0.01 The amount is more preferably about 2.0 parts by mass, further preferably 0.025 to 1.5 parts by mass, and most preferably 0.05 to 1.0 parts by mass.

1-4-2. Organic heat stabilizer (D-2)
The organic heat stabilizer (D-2) is preferably at least one selected from hindered phenol compounds, hindered amine compounds, phosphites, organic phosphorus compounds, and bisphenol type epoxy resins.

  Examples of hindered phenol compounds include N, N'-hexamethylenebis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide, bis (3,3-bis (4'-) Hydroxy-3'-tert-butylphenyl) butanoic acid) glycol ester, 2,1'-thioethyl bis- (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-butylidene bis (3-methyl-6-tert-butylphenol), and triethylene glycol-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate and the like.

  Examples of hindered amine compounds include acetone adduct of phenylenediamine (Naugard A), linolenic adduct of phenylenediamine, Naugard 445, N, N'-dinaphthyl-p-phenylenediamine, N-phenyl-N'-cyclohexyl-p Phenylenediamine, and Nylostab S-EED [N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,3-benzenedicarboxamide] manufactured by Clariant Co., etc. are included.

  Examples of phosphites and organophosphorus compounds include triphenyl phosphite, diphenyl alkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, and distearyl pentaerythritol dichloride. Phosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6 -Di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4 6-tris (tert-butylphenyl)) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, 6-isooctyl Oxy-2,4,8,10-tetra-tert-butyl-12H-dibenz- [d, g] -1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra -tert-Butyl-12-methyldibenz [d, g] -1,3,2-dioxaphosphocin, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite and bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite and the like are preferably included, preferably tris [2-tert-butyl-4-thio- (2′-methyl-4′-hydroxy-5′-tert] Butyl) phenyl-5-methyl] phenyl phosphite and tris (2,4- -tert- butylphenyl) phosphite (Basel, Clariant Corporation of commercial products, Hostanox (TM) is a PAR 24).

  Examples of the bisphenol type epoxy resin include EPIKOTE manufactured by Yuka Shell Epoxy Co., Ltd., and the like.

  As described above, the organic heat stabilizer (D-2) may be a mixture of two or more types selected from hindered phenol compounds, hindered amine compounds, phosphites, organic phosphorus compounds, and bisphenol-type epoxy resins. Examples of such mixtures include BASF's Irgatec NC66 etc.

  The content of the organic heat stabilizer (D-2) can be adjusted from the viewpoint of mold staining, formation of silver on the surface of molded articles, and toughness. For example, the total of polyamide resin (A) and polyamide resin (B) It is preferable that it is 0.01-3 mass parts with respect to 100 mass parts, It is more preferable that it is 0.01-2 mass parts, It is still more preferable that it is 0.025-2 mass parts, 0. Most preferably, it is from 0.5 to 1.5 parts by mass.

  The content of the heat resistant stabilizer (D) is preferably 0.01 to 3.0% by mass with respect to the total of the components (A), (B), (C) and (D). It is more preferable that it is 0.1-2.0 mass%. It is easy to provide high heat resistance to a molded article as content of a heat-resistant stabilizer (D) is 0.01 mass% or more. The intensity | strength (rigidity) of a molded article is hard to be impaired as content of a heat-resistant stabilizer (D) is 3.0 mass% or less.

  The mass ratio of the copper stabilizer (D-1) to the organic heat stabilizer (D-2) is, for example, 10/90 to 100/0, and preferably 50/50 to 90/10. When the proportion of the copper-based stabilizer (D-1) is large, it tends to exhibit good heat aging resistance in a temperature range exceeding 150 ° C .; when the proportion of the organic heat stabilizer (D-2) is large, 100 to 150 ° C. Tends to show good heat aging resistance in the temperature range of

1-5. Other Components The resin composition for an engine support member of the present invention may further contain other components as long as the effects of the present invention are not impaired. Examples of other components include antioxidants (phenols, amines, sulfurs and phosphoruss, etc.), non-fibrous inorganic fillers (clay, silica, alumina, talc, kaolin, quartz, mica, graphite, etc. ), Photostabilizers (benzotriazoles, triazines, benzophenones, benzoates, hindered amines and olgenanilides, etc.), other polymers (polyolefins, ethylene / propylene copolymer, ethylene / 1-butene copolymer) And olefin copolymers such as propylene / 1-butene copolymer, polystyrene, polyamide, polycarbonate, polyacetal, polysulfone, polysulfone, polyphenylene oxide, fluorocarbon resin, silicone resin and LCP etc., flame retardant (bromine) , Chlorine, Phosphorus, Antimony and Inorganic And the like), mold release agents, fluidity improvers, hydrolysis inhibitors, optical brighteners, plasticizers, thickeners, antistatic agents, pigments, nucleating agents, and the like. Among them, inorganic fillers other than fibrous, flowability improvers, hydrolysis inhibitors and the like are preferable.

  A flowability improver may be added for the purpose of enhancing the flowability of the resin composition at the time of molding. In the present invention, in particular, a fibrous filler (C) may be contained in a relatively large amount in order to enhance the rigidity and the heat resistance. Even in such a case, an excessive increase in viscosity of the resin composition at the time of molding can be suppressed, and a decrease in moldability and releasability can be suppressed. Examples of such flow improvers include aliphatic metal salts.

  The fatty acid metal salt may be a known compound. Examples of fatty acids constituting fatty acid metal salts include montanic acid, behenic acid, and stearic acid. Examples of metal salts constituting fatty acid metal salts include lithium salts, calcium salts, barium salts, zinc salts, aluminum salts and the like. Preferred examples of fatty acid metal salts include lithium salts, calcium salts, barium salts, zinc salts, and aluminum salts of montanic acid or behenic acid from the viewpoint of enhancing fluidity during molding, and more preferably montanic acid. Contains calcium.

  The hydrolysis inhibitor can be added, for example, for the purpose of suppressing the hydrolysis of the polyamide resin in the resin composition and suppressing the decrease in the activity of the copper stabilizer (D-1). Examples of such hydrolysis inhibitors include compounds having one or more functional groups selected from the group consisting of carbodiimide groups, imino groups and amino groups.

The compound having a carbodiimide group (carbodiimide group-containing compound) is more preferably a compound having a structure represented by the following formula (2).

  R1 of Formula (2) shows a divalent organic group. The divalent organic group is an aliphatic group (preferably an alkylene group) or an aromatic group (preferably an arylene group), preferably an aliphatic group (preferably an alkylene group).

  N of Formula (2) is an integer greater than or equal to 1, Preferably it is an integer of 2-15, More preferably, it is an integer of 3-13, More preferably, it is an integer of 3-11.

  The polystyrene equivalent number average molecular weight (Mn) determined by gel permeation chromatography (GPC) of the carbodiimide group-containing compound is usually preferably 400 to 500,000, and 1,000 to 10,000. Is more preferable, and 2,000 to 4,000 is more preferable. When the number average molecular weight (Mn) is in this range, the hydrolysis resistance and the activity of the copper-based stabilizer can be preferably improved.

  A carbodiimide group containing compound may be used individually by 1 type, and may be used in combination of multiple types.

  The carbodiimide group-containing compound may be a synthetic product or a commercially available product. Although the synthesis method of the carbodiimide group-containing compound is not particularly limited, it can be synthesized, for example, by reacting an organic polyisocyanate in the presence of a catalyst which promotes the carbodiimidization reaction of an isocyanate group. Examples of commercially available carbodiimide group-containing compounds include Carbodilite HMV-8CA and LA1 (all trade names) manufactured by Nisshinbo Co., Ltd., and the like.

  The compound containing an imino group or an amino group is preferably an aliphatic hydrocarbon compound having two or more imino groups or amino groups in one molecule. Examples of compounds containing an imino group or an amino group include linear polyamines such as 1,4-diaminobutane and diethylenetriamine; 1,4,8,11-tetraazacyclotetradecane, 1,4,7,10,13 And cyclic polyamines such as 16-hexaazacyclooctadecane; poly (lower alkylenimine); polyallylamine and the like. Among these, poly (lower alkylene imine) and poly (allylamine) are preferable. Lower alkylene means alkylene groups having 2 to 4 carbon atoms.

（式（３）中、ｎは、２以上の整数である） The poly (lower alkyleneimine) is preferably a polyethyleneimine having a structure represented by the following formula (3).

(In the formula (3), n is an integer of 2 or more)

  The number average molecular weight of the poly (lower alkylene) imine is not particularly limited, but is preferably 200 to 80,000. The poly (lower alkylene) imine may be branched or linear. Polyethyleneimine may be a commercially available product, and examples thereof include “Epomin SP-018”, “Epomin SP-200” and the like manufactured by Nippon Shokubai Co., Ltd.

  Although content of each other component in a resin composition is based also on the kind, 0-10 mass% is each with respect to the sum total of (A) component, (B) component, (C) component, and (D) component. It is preferable that it is, 0-5 mass% is more preferable, and 0-1 mass% is more preferable.

2. A method of producing a resin composition for an engine support member The resin composition for an engine support member of the present invention comprises a polyamide resin (A), a polyamide resin (B), a fibrous filler (C) and a heat resistant stabilizer at least in the above ratio. (D) may be mixed by a known method, such as a Henschel mixer, V blender, ribbon blender or tumbler blender, or after mixing and further melt kneading by a single screw extruder, multi-screw extruder, kneader or Banbury mixer, etc. , Granulation or grinding method.

3. Engine support member The engine support member of the present invention includes a molded product of the resin composition for an engine support member of the present invention on at least a part of its component parts. The molded product of the resin composition for an engine support member of the present invention can be obtained, for example, by injection molding the resin composition for an engine support member.

  Examples of the engine support member of the present invention include an engine mount, an engine mount bracket, an oil pan upper, an engine torque rod and the like. Among them, the engine mount is preferable.

  FIG. 1 is a schematic view showing an example of an engine mount. As shown in FIG. 1, the engine mount 1 includes an inner cylinder 2 made of metal, a resin bracket 3 surrounding the inner cylinder 2 coaxially and concentrically, and a space between the inner cylinder 2 and the resin bracket 3 And a rubber bush 4 which interposes and elastically connects the two. The inner cylinder 2 is connected to a bracket (not shown) on the engine side, and the resin bracket 3 is fixed to the vehicle body side.

  The resin bracket 3 has left and right leg portions 5 for fixing to the vehicle body, and a metal nut 6 is embedded in the leg portions 5. The resin bracket 3 may be a molded product of the resin composition for an engine support member of the present invention.

  Such an engine mount 1 is set, for example, in a mold for resin molding, with the rubber bush 4 set together with a core (not shown), and after the metal nut 6 is further set, it is melted in the cavity in the mold It is manufactured by injection injection of resin to form a resin bracket. In this injection molding, a weld portion (fused portion) having low resin strength is formed at the peripheral edge of the opening of the resin bracket 3 or the peripheral edge of the bolt hole of the metal nut 6.

  The resin bracket 3 which comprises the engine mount 1 consists of a molding of the resin composition for engine supporting members of this invention. The molded product of the resin composition for an engine support member of the present invention has high strength and heat resistance, and has high vibration resistance. Therefore, since the resin bracket 3 has high strength and heat resistance, high weld strength and impact resistance, it can well withstand vibration of an engine or the like.

  The invention will be described in more detail below with reference to examples. The scope of the present invention is not interpreted as being limited by these examples.

<Preparation of Polyamide Resin (A)>
Synthesis Example 1 Preparation of Polyamide Resin (A-1) 2800 g (24.1 mol) of 1,6-diaminohexane, 2774 g (16.7 mol) of terephthalic acid, 1196 g (7.2 mol) of isophthalic acid, benzoic acid 36.6 g (0.30 mol), 5.7 g of sodium hypophosphite monohydrate and 545 g of distilled water were charged in an 13.6 L autoclave and purged with nitrogen. Stirring was started from 190 ° C., and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was raised to 3.03 MPa. It was continued in this state for 1 hour the reaction, from spray nozzles installed in the autoclave lower withdrawn by atmospheric discharge low-order condensate. Then, after cooling to room temperature, the low-order condensate was ground to a particle size of 1.5 mm or less by a grinder and dried at 110 ° C. for 24 hours. The water content of the lower condensate obtained was 4100 ppm, and the intrinsic viscosity [粘度] was 0.15 dl / g.
Next, this lower condensate was placed in a tray type solid phase polymerization apparatus, and after nitrogen substitution, the temperature was raised to 180 ° C. over about 1 hour and 30 minutes. Then, it reacted for 1 hour and 30 minutes, and was made to cool to room temperature. The intrinsic viscosity [η] of the obtained compound was 0.20 dl / g.
Thereafter, this compound is melt-polymerized in a twin screw extruder with a screw diameter of 30 mm and L / D = 36 at a barrel setting temperature of 330 ° C. and a screw rotation speed of 200 rpm and a resin feed rate of 6 kg / h. (A-1) was obtained.

Synthesis Example 2 Preparation of Polyamide Resin (A-2) 1312 g (11.1 mol) of 1,6-diaminohexane, 1312 g (11.1 mol) of 2-methyl-1,5-diaminopentane, 3655 g of terephthalic acid 22.0 mol), 34.2 g (0.28 mol) of benzoic acid, 5.5 g (5.2 × 10 ^-2 mol) of sodium hypophosphite as a catalyst, and 640 ml of distilled water in a 1-liter reactor After charging and nitrogen substitution, the reaction was performed at 250 ° C. and 35 kg / cm ² for 1 hour. The molar ratio of 1,6-diaminohexane to 2-methyl-1,5-diaminopentane was 50:50. After one hour, the reaction product formed in the reactor is withdrawn into a receiver connected to the reactor and set to a pressure lower by about 10 kg / cm ² , and the intrinsic viscosity [η] is 0.15 dl //. The lower condensate which is g was obtained.
Next, the low-order condensate was dried and then melt polymerized at a cylinder setting temperature of 330 ° C. using a twin-screw extruder to obtain a polyamide resin (A-2).

Synthesis Example 3 Preparation of Polyamide Resin (A-3) 4537.7 g (27.3 mol) of terephthalic acid, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine [1,9- Nonane diamine / 2-methyl-1, 8-octane diamine = 80/20 (molar ratio) 4385 g (27.5 mol), benzoic acid 41.5 g (0.34 mol), sodium hypophosphite monohydrate 9.12 g (0.1% by mass based on the total mass of the raw materials) and 2.5 liters of distilled water were placed in an autoclave having an inner volume of 20 liters and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the temperature inside the autoclave was raised to 220 ° C. over 2 hours. At this time, the pressure inside the autoclave was increased to 2 MPa. The reaction was continued as it was for 2 hours, and the temperature was raised to 230 ° C. Then, the temperature was kept at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing steam to keep the pressure at 2 MPa. Next, the pressure was lowered to 1 MPa over 30 minutes, and reaction was further performed for 1 hour to obtain a low-order condensate having an intrinsic viscosity [η] of 0.15 dl / g. The lower condensate was dried at 100 ° C. under reduced pressure for 12 hours and ground to a particle size of 2 mm or less.
The lower condensate obtained was subjected to solid phase polymerization at 230 ° C. and 13 Pa (0.1 mmHg) for 10 hours to obtain a polyamide resin (A-3).

<Polyamide resin for comparison>
(A-1): Toray Industries nylon resin, Amilan CM3001-N (66 nylon)

<Preparation of Polyamide Resin (B)>
Synthesis Example 4 Preparation of Polyamide Resin (B-1) 1390 g (8.4 mol) of terephthalic acid, 2800 g (24.1 mol) of 1,6-hexanediamine, 2581 g (15.5 mol) of isophthalic acid, benzoic acid 109.5 g (0.9 mol), 5.7 g of sodium hypophosphite monohydrate and 545 g of distilled water were charged in an 13.6 L autoclave and purged with nitrogen. Stirring was started from 190 ° C., and the internal temperature was raised to 250 ° C. over 3 hours. At this time, the internal pressure of the autoclave was increased to 3.02 MPa. After continuing the reaction as it was for 1 hour, air was released to the atmosphere from a spray nozzle installed at the lower part of the autoclave to extract a lower condensate. Thereafter, the low-order condensate was cooled to room temperature, pulverized to a particle size of 1.5 mm or less by a pulverizer, and dried at 110 ° C. for 24 hours. The water content of the lower condensate obtained was 3000 ppm, and the intrinsic viscosity [粘度] was 0.14 dl / g.
Next, this low-order condensate is melt polymerized at a resin setting rate of 6 kg / h at a barrel setting temperature of 330 ° C. and a screw rotation speed of 200 rpm by a twin screw extruder with a screw diameter of 30 mm and L / D = 36. And a polyamide resin (B-1) were obtained.

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the obtained polyamide resins (A) and (B) was measured as follows. 0.5 g of polyamide resin was dissolved in 50 ml of 96.5% sulfuric acid solution. The number of seconds of flow of the resulting solution under 25 ° C. ± 0.05 ° C. is measured using a Ubbelohde viscometer, “formula: [η] = ηSP / (C (1 + 0.205ηSP)) Calculated based on
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
t: Seconds of flow of sample solution (seconds)
t0: Blank sulfuric acid flow down seconds (seconds)
ηSP = (t−t0) / t0

[Melting point (Tm), glass transition temperature (Tg), and heat of fusion ΔH]
The melting point (Tm) of the polyamide resin was measured using a differential scanning calorimeter (DSC 220C, manufactured by Seiko Instruments Inc.) as a measurement device. Specifically, about 5 mg of polyamide resin was sealed in an aluminum pan for measurement, and heated to 330 ° C. at room temperature to 10 ° C./min. In order to completely melt the polyamide resin, it was maintained at 330 ° C. for 5 minutes and then cooled to 30 ° C. at 10 ° C./min. After 5 minutes at 30 ° C., a second heating to 330 ° C. was performed at 10 ° C./min. The peak temperature (° C.) at this second heating was taken as the melting point (Tm) of the polyamide resin, and the displacement point corresponding to the glass transition was taken as the glass transition temperature (Tg). The heat of fusion ΔH was determined from the area of the exothermic peak of crystallization in accordance with JIS K7122.

The obtained measurement results are shown in Table 1.

<Fibrous filler (C)>
(C-1): Glass fiber (manufactured by Owens Corning, FT756D, glass fiber length 3 mm, aspect ratio 300)

<Heat resistant stabilizer (D)>
(D-1): Copper stabilizer (mixture of 14.3% by mass of copper (I) iodide and 85.7% by mass of potassium iodide / calcium distearate (98: 2))
(D-2): BASF Corporation Irgatec NC 66 (organic heat stabilizer mixture)

<Other ingredients>
Additive (E): Carbodilite HMV-8 CA (aliphatic polycarbodiimide) manufactured by Nisshinbo Co., Ltd.
Talc (F): other inorganic filler, average particle size 1.6 μm
Calcium montanate (G) (removal improver / flow improver)

Example 1
Polyamide resin (A-1), polyamide resin (B-1), fibrous filler (C-1), heat resistant stabilizer (D-1), talc (F) and montanic acid in amounts shown in Table 2 Calcium (G) was mixed using a tumbler blender, and the raw materials were melt-kneaded at a cylinder temperature (Tm1 + 15) ° C. by a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.). Thereafter, the melt-kneaded product was extruded into strands and cooled in a water tank. Thereafter, the strand was taken up with a pelletizer and cut to obtain a pellet-like resin composition.

Examples 2 to 7 and Comparative Examples 1 to 5
A pellet-like resin composition was obtained in the same manner as in Example 1 except that the composition was changed as shown in Table 2 or 3.

  The resulting resin composition was evaluated for tensile strength, weld tensile strength, flexural modulus (25 ° C., 100 ° C.) and heat aging resistance by the following method.

(Tensile strength)
The obtained resin composition was used for the following injection molding machine, and the test piece of ASTM-1 (the dumbbell piece) of thickness 3 mm was produced on the following molding conditions.
Molding machine: Sodick Plastic Co., Ltd., Tupearl TR40S3A
Molding machine cylinder temperature: melting point (Tm) of polyamide resin (A) + 15 ° C
Mold temperature: Tg of polyamide resin (A) + 20 ° C
The prepared test piece was left to stand at a temperature of 23 ° C. under a nitrogen atmosphere for 24 hours. Subsequently, a tensile test was conducted under an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% to measure the tensile strength.

(Weld tensile strength)
Test pieces for evaluation having a weld part of ASTM type 1 were prepared, and the tensile strength was measured in the same manner as the above-mentioned tensile strength test. The tensile strength of the test piece for evaluation which has the said weld part was made into weld part strength.

(Weld part strength retention rate)
The ratio (%) of weld portion strength to tensile strength was calculated by applying the tensile strength measured in the above (tensile strength of a specimen having no weld) and the weld tensile strength to the following equations.
Weld area strength retention rate (%) = (weld area tensile strength / tensile strength) × 100

(Flexural modulus)
The obtained resin composition was injection molded under the following conditions to prepare a 1/8 inch thick strip.
Molding machine: Sodick Plastech Co., Ltd. Tupearl TR40S3A
Molding machine cylinder temperature: melting point + 10 ° C of polyamide resin (A)
Mold temperature: Tg of polyamide resin (A) + 20 ° C
The prepared test piece was left to stand at a temperature of 23 ° C. under a nitrogen atmosphere for 24 hours. Next, a bending test was performed under an atmosphere of temperature 25 ° C., 100 ° C., relative humidity 50%, bending tester: AB5 manufactured by NTESCO, span 51 mm, bending speed 12.7 mm / min, and elastic modulus was measured.

(Heat resistant aging resistance)
After a 3 mm thick test piece of ASTM-1 (dumbbell piece) was treated in an air circulating furnace for 3000 hours at a temperature of 200 ° C., the test piece was removed from the furnace and cooled to 23 ° C. Subsequently, a tensile test was conducted under an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% to measure the tensile strength. The strength retention was calculated by the following equation.
Thermal aging resistance (strength retention) (%) = (tensile strength after heat treatment / tensile strength) × 100

(IZOD impact strength)
A test piece with a thickness of 3.2 mm is prepared using the following injection molding machine and adjusted under the following molding conditions, and in accordance with ASTM D 256, in an atmosphere with a temperature of 23 ° C. and a relative humidity of 50%. It measured by IZOD impact strength.
Molding machine: SE50DU, manufactured by Sumitomo Heavy Industries, Ltd.
Molding machine cylinder temperature: (Tm + 15) ° C
Mold temperature: 120 ° C
Tm indicates the melting point of the polyamide resin (A).

The evaluation results of Examples 1 to 7 are shown in Table 2; the evaluation results of Comparative Examples 1 to 5 are shown in Table 3.

  The resin compositions of Examples 1 to 7 are all shown to have high weld tensile strength and impact strength, and high heat aging resistance and tensile strength.

  On the other hand, it is shown that the resin composition of Comparative Examples 1 to 5 is low in at least one of weld tensile strength and impact strength, heat aging resistance, and tensile strength. Since the resin composition of Comparative Example 1 does not contain the polyamide resin (B), it is shown that the weld strength and the impact strength are low. Since the resin composition of Comparative Example 2 contains too much polyamide resin (B), it is shown that the tensile strength and the heat aging resistance decrease. Since Comparative Examples 3 and 4 do not contain the heat stabilizers (D-1) and (D-2), they are shown to have low heat aging resistance. Comparative Example 5 includes the polyamide resin (a-1) having a heat resistance lower than that of the polyamide resin (A), so that it is shown that the heat aging resistance is low and the rigidity (flexural modulus) at high temperature is also low. .

  The present invention provides a resin composition for an engine support member having excellent vibration resistance (weld strength and impact resistance) and long-term heat resistance and strength in an excellent high temperature environment, and an engine support member using the same. Can be provided.

1 engine mount 2 inner cylinder 3 resin bracket 4 rubber bush 5 leg 6 nut

Claims (10)

Polyamide resin (A) 29.89-68.9 mass% which has a glass transition temperature of 80 ° C. to 150 ° C. and a melting point (Tm) of 300 ° C. or higher, which is measured by a differential scanning calorimeter (DSC),
0.1 to 20% by mass of a polyamide resin (B) having substantially no melting point (Tm) measured by a differential scanning calorimeter (DSC),
30 to 70% by mass of fibrous filler (C),
A heat-resistant stabilizer (D) containing 0.01 to 3.0% by mass of a copper-based stabilizer (D-1) (provided that the total of (A), (B), (C) and (D) Is 100% by mass),
The polyamide resin (A) is
Look including terephthalic acid component unit and isophthalic acid component unit, and the content ratio of terephthalic acid component unit / isophthalic acid component units is 55 / 45-85 / 15 (molar ratio) in which the dicarboxylic acid component unit (a1),
The resin composition for engine supporting members containing the diamine component unit (a2) containing a C4-C20 aliphatic diamine component unit. The resin composition for engine supporting members according to claim 1, wherein the aliphatic diamine component unit of the polyamide resin (A) satisfies at least one of the following 1) and 2).
1) containing 40 to 100 mol% of a linear alkylene diamine component unit having 4 to 20 carbon atoms with respect to the total number of moles of the aliphatic diamine component unit 2) a branched alkylene diamine having 4 to 20 carbon atoms 60 mol% or less of component units with respect to the total number of moles of the aliphatic diamine component units The polyamide resin (B) is
A dicarboxylic acid component unit (b1) containing an isophthalic acid component unit,
The resin composition for engine supporting members according to claim 1 or 2, comprising a diamine component unit (b2) containing an aliphatic diamine component unit having 4 to 15 carbon atoms. In the polyamide resin (B),
The dicarboxylic acid component unit (b1) may further contain a terephthalic acid component unit,
The resin composition for an engine supporting member according to claim 3, wherein a molar ratio of the isophthalic acid component unit to the terephthalic acid component unit is isophthalic acid component unit / terephthalic acid component unit = 55/45 to 100/0. .   The engine support member according to any one of claims 1 to 4, wherein a content mass ratio B / (A + B) of the polyamide resin (A) and the polyamide resin (B) is 0.05 to 0.35. Resin composition. In the polyamide resin (A) ,
The resin composition for an engine supporting member according to claim 1 or 2, wherein the aliphatic diamine component unit having 4 to 20 carbon atoms contains a linear alkylene diamine component unit having 4 to 20 carbon atoms. In the polyamide resin (A),
The linear alkylene diamine component unit having 4 to 20 carbon atoms is a hexamethylene diamine component unit,
The resin composition for an engine supporting member according to claim 2, wherein the branched alkylene diamine component unit having 4 to 20 carbon atoms is a 2-methyl-1,5-pentadiamine component unit. In the polyamide resin (A),
The resin for an engine supporting member according to claim 2, wherein the branched alkylene diamine component unit having 4 to 20 carbon atoms is 1,9-nonane diamine component unit and 2-methyl-1,8-octane diamine component unit. Composition. The content of the heat resistant stabilizer (D) is 0.1 to 3.0% by mass,
The resin composition for engine supporting members as described in any one of Claims 1-8 .   An engine support member comprising the molding of the resin composition for an engine support member according to any one of claims 1 to 9.

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