JP2016169290A - Polyamide resin composition for aiming nut of vehicle lighting fixture, and aiming nut containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition for an aiming nut that has excellent heat resistance and impact resistance, has little change in dimension over a long period of time, and can be stably used; and an aiming nut using the same.SOLUTION: A polyamide resin composition for an aiming nut for a vehicle lighting fixture contains a semi-aromatic polyamide resin (A) and a modified olefin polymer (B) containing a functional group structural unit containing a hetero atom. The semi-aromatic polyamide resin (A) contains 50 mol% or more of a terephthalic acid component unit with respect to the total molar number of a dicarboxylic acid component unit. A glass transition temperature of the semi-aromatic polyamide resin (A) measured by DSC is set at 90-180°C. The modified olefin polymer (B) contains 0.03-2.0 mass% of a functional group structural unit with respect to the total mass of the modified olefin polymer (B).SELECTED DRAWING: None

Description

  The present invention relates to a polyamide resin composition for an aiming nut of a vehicle lamp, and an aiming nut including the same.

  Generally, a vehicle is provided with various lamps such as a headlamp, a high-mount stop lamp, a stop-and-tail lamp, and a direction indicator lamp. Various light sources are used for these lamps, and an LED light source is an example (for example, Patent Document 1).

  Here, the vehicular lamp is provided with not only the light source but also a reflector for condensing light from the light source in a certain direction and an aiming mechanism for adjusting the light irradiation direction (optical axis). (For example, Patent Document 2). The aiming mechanism includes an aiming screw and an aiming nut as main components. The aiming screw is arranged to be operable from the outside of the vehicular lamp; the aiming nut is arranged in connection with the aiming screw and the reflector. In such a vehicle lamp, the aiming screw and the aiming nut are interlocked to tilt the reflector vertically and horizontally by operating the aiming screw with a jig from the outside of the vehicle lamp. That is, by operating the aiming screw, the optical axis of the vehicle lamp can be adjusted in a desired direction.

  Here, crystalline polyamides represented by nylon 6, nylon 66, and the like are widely used as various members for vehicles because of their excellent characteristics and ease of melt molding. Recently, resins containing these polyamides are used. Application of the composition to a member for a vehicle lamp (for example, an aiming nut) has been studied.

JP 2007-258034 A JP 2013-69492 A

  However, since the aiming nut is disposed in the vicinity of the light source, the temperature is likely to increase due to heat from the light source. Therefore, when the polyamide resin is applied to the aiming nut, there is a problem that the aiming nut is likely to be thermally deformed and the optical axis cannot be adjusted in a desired direction.

  Furthermore, the aiming nut is also required to have resistance to vibration (impact resistance) when the vehicle is running. However, with the conventional polyamide resin composition, there is a problem that it is difficult to achieve both heat resistance and impact resistance. .

  The present invention has been made in view of the above problems, and has a polyamide resin composition for aiming nuts that has excellent heat resistance and impact resistance, has little dimensional change over a long period of time, and can be used stably. It is an object to provide an object and an aiming nut using the same.

That is, this invention relates to the polyamide resin composition for aiming nuts for vehicle lamps shown below, and the aiming nut using the same.
[1] A polyamide comprising a semi-aromatic polyamide resin (A) comprising a dicarboxylic acid component unit and an aliphatic diamine component unit, and a modified olefin polymer (B) comprising a functional group structural unit containing a hetero atom. In the resin composition, the semi-aromatic polyamide resin (A) includes 50 mol% or more of terephthalic acid component units with respect to the total number of moles of the dicarboxylic acid component units, and the semi-aromatic polyamide resin (A ) Has a glass transition temperature measured by DSC of 90 ° C. to 180 ° C., and the modified olefin polymer (B) contains the functional group structural unit with respect to the total mass of the modified olefin polymer (B). A polyamide resin composition for an aiming nut of a vehicle lamp, comprising 0.03 to 2.0% by mass.

[2] The vehicle lamp according to [1], wherein the aliphatic diamine component unit of the semi-aromatic polyamide resin (A) satisfies at least one of the following requirement (a1) and requirement (a2): A polyamide resin composition for aiming nuts.
(A1) A linear alkylenediamine component unit having 4 to 18 carbon atoms is contained in an amount of 40 to 100 mol% based on the total number of moles of the aliphatic diamine component unit. (A2) Side chain alkylene having 4 to 18 carbon atoms The diamine 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 side chain alkylenediamine component unit is a 2-methyl-1,8-octanediamine component unit, and 2 -The polyamide resin composition for aiming nuts of a vehicle lamp according to [2], which is at least one of methyl-1,5-pentadiamine component units.
[4] The polyamide resin composition for an aiming nut of a vehicle lamp according to [1], wherein the aliphatic diamine component of the semi-aromatic polyamide resin (A) includes a 1,6-diaminohexane component unit.
[5] In [1], the aliphatic diamine component of the semi-aromatic polyamide resin (A) includes a 1,6-diaminohexane component unit and a 2-methyl-1,5-pentadiamine component unit. A polyamide resin composition for an aiming nut of a vehicle lamp as described.

[6] The aliphatic diamine component of the semi-aromatic polyamide resin (A) includes a 1,9-nonanediamine component unit and a 2-methyl-1,8-octanediamine component unit. Polyamide resin composition for aiming nut of vehicle lighting equipment.
[7] The dicarboxylic acid component unit of the semi-aromatic polyamide resin (A) further includes an isophthalic acid component unit, and the aliphatic diamine component unit of the semi-aromatic polyamide resin (A) has carbon atoms. The polyamide resin composition for aiming nuts of a vehicle lamp according to [1], wherein is an alkylenediamine component having 4 to 15.
[8] The molar ratio of the terephthalic acid component unit to the isophthalic acid component unit is 60/40 to 99.9 / 0.1, and the aliphatic diamine component unit is 1,6-diaminohexane. The polyamide resin composition for aiming nuts of a vehicle lamp according to [7], comprising component units.

[9] 75 to 97% by mass of the semi-aromatic polyamide resin (A) and 3 to 25% by mass of the modified olefin polymer (B) (provided that the semi-aromatic polyamide resin (A) and the modified The total of the olefin polymer (B) is 100% by mass), and the polyamide resin composition for the aiming nut of the vehicle lamp according to any one of [1] to [8].
[10] An aiming nut comprising the polyamide resin composition for the aiming nut of the vehicle lamp according to any one of [1] to [9].

  According to the polyamide resin composition for an aiming nut for a vehicle lamp of the present invention, an aiming nut for a vehicle lamp having high heat resistance and impact resistance and little dimensional change over a long period of time can be obtained.

It is a schematic sectional drawing for showing the structure of a general vehicle lamp.

1. Polyamide resin composition for aiming nut of vehicle lamp The polyamide resin composition for aiming nut for vehicle lamp of the present invention (hereinafter also simply referred to as “polyamide resin composition”) is mainly used for obtaining an aiming nut of a vehicle lamp. It is the resin composition used. A schematic sectional view of a general vehicle lamp is shown in FIG. In addition, FIG. 1 is a figure for demonstrating the structure of a general vehicle lamp, and does not reproduce the dimension of each member.

  As shown in FIG. 1, the vehicle lamp 100 includes a lamp housing 1, a light source 2, a reflector 3, an aiming nut 4, and an aiming screw 5. In the vehicle lamp 100, the light from the light source 2 is collected by a reflector and emitted from at least one surface of the lamp housing 1. At this time, the light emission direction (optical axis) is determined by the vertical and horizontal tilt angles of the reflector 3.

  On the other hand, the aiming nut 4 and the aiming screw 5 are members for adjusting the inclination angle of the reflector 3; the aiming nut 4 is disposed so as to be connected to a part of the reflector 3 described above. On the other hand, the aiming nut 4 is also connected (screwed) to the aiming screw 5 inserted into the lamp housing through the through hole of the lamp housing 1.

  In such a vehicle lamp 100, the aiming screw 5 moves forward and backward in the axial direction by operating the aiming screw 5 with a jig from the outside of the lamp housing 1. Then, the aiming nut 4 screwed into the aiming screw 5 moves forward and backward in the axial direction of the aiming screw 5, and the tilt angle of the reflector 3 is changed, so that the optical axis can be adjusted in a desired direction.

  As described above, it has been studied to apply a polyamide resin to an aiming nut for a vehicle lamp, but the conventional polyamide resin has insufficient heat resistance, and the aiming nut is deformed by heat from a light source, Creep deformation was likely to occur. And when a deformation | transformation arises in an aiming nut, the slidability with an aiming screw and an aiming nut will fall, and the subject that angle adjustment of a reflector became difficult occurred. Furthermore, aiming nuts are also required to have impact resistance against vibration during vehicle travel. However, with conventional polyamide resin compositions, it is difficult to achieve both heat resistance and impact resistance. It was difficult to obtain a highly durable aiming nut with little change.

  In contrast, the polyamide resin composition of the present invention includes a semi-aromatic polyamide resin (A) having high heat resistance and high rigidity, and a modified olefin polymer (B) having high toughness. And a semi-aromatic polyamide resin (A) and a modified olefin polymer (B) are fully disperse | distributed because a specific functional group structural unit contains predetermined amount in a modified olefin polymer (B). As a result, the polyamide resin composition has both heat resistance, rigidity and impact resistance; when the polyamide resin composition is used as an aiming nut for a vehicle lamp, the light source (for example, LED) of the vehicle lamp is used. It becomes stable to heat. As a result, the dimensional change is less likely to occur, and it can be satisfactorily slid with the aiming screw over a long period of time. In addition, the aiming nut is less likely to be damaged even when subjected to vibrations caused by running of the vehicle, and can be used stably for a long period of time.

1-1. Semi-aromatic polyamide resin (A)
The semi-aromatic polyamide resin (A) contains at least a component derived from an aromatic carboxylic acid and a component derived from an aliphatic diamine. The semi-aromatic polyamide resin (A) may be included in the polyamide resin composition, or two or more thereof.

  Here, the glass transition temperature (Tg) of the semi-aromatic polyamide resin (A) measured by differential scanning calorimetry (DSC) is 90 to 180 ° C., preferably 110 to 150 ° C. When the Tg of the semi-aromatic polyamide resin (A) is in this range, the heat resistance of the polyamide resin composition is increased, and the resulting aiming nut is difficult to be thermally deformed. In addition, when 2 or more types of semi-aromatic polyamide resins are contained in a polyamide resin composition, these mixtures are handled as a semi-aromatic polyamide resin (A). That is, in such a case, the glass transition temperature (Tg) of the mixture is measured by differential scanning calorimetry (DSC). The mixture as long as it satisfies the glass transition temperature (Tg); the semiaromatic polyamide resin (A) contains a part of the semiaromatic polyamide resin that does not satisfy the glass transition temperature (Tg). May be.

  Moreover, it is preferable that melting | fusing point (Tm) measured by differential scanning calorimetry (DSC) of a semi-aromatic polyamide resin (A) is 280-330 degreeC, and it is more preferable that it is 290-330 degreeC. When the melting point of the semi-aromatic polyamide resin (A) is within the above range, the moldability of the polyamide resin composition is likely to increase. For example, when the semi-aromatic polyamide resin (A) having an excessively high melting point is contained in the polyamide resin composition, it is necessary to set the molding temperature for molding into the shape of the aiming nut high. As a result, the modified olefin polymer (B), which will be described later, is thermally decomposed and desired impact resistance cannot be obtained, or mold contamination occurs, making continuous molding difficult. On the other hand, if the melting point of the semi-aromatic polyamide resin (A) is in the above range, the polyamide resin composition can be molded at an appropriate temperature. The glass transition temperature and melting point of the semi-aromatic polyamide resin (A) are determined depending on the dicarboxylic acid component unit and the aliphatic diamine component unit constituting the semi-aromatic polyamide resin (A), the semi-aromatic polyamide resin (A). It is adjusted by molecular weight.

  The melting point (Tm) and glass transition temperature (Tg) of the semi-aromatic polyamide resin (A) are measured with a differential scanning calorimeter (for example, DSC220C type, manufactured by Seiko Instruments Inc.). Specifically, about 5 mg of semi-aromatic polyamide resin (A) 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 semi-aromatic polyamide resin (A), it is maintained at 330 ° C. for 5 minutes and then cooled to 30 ° C. at 10 ° C./min. Then, after 5 minutes at 30 ° C., the second heating is performed to 330 ° C. at 10 ° C./min. The peak temperature (° C.) in the second heating is defined as the melting point (Tm) of the semi-aromatic polyamide resin (A), and the displacement point corresponding to the glass transition is defined as the glass transition temperature (Tg).

  The intrinsic viscosity [η] of the semi-aromatic polyamide resin (A) measured at 25 ° C. and 96.5% sulfuric acid is preferably 0.7 to 1.6 dl / g, 0.8 More preferably, it is -1.2 dl / g. When the intrinsic viscosity [η] of the semi-aromatic polyamide resin (A) is in the above range, the mechanical strength of the polyamide resin composition is likely to be sufficiently increased. On the other hand, if the intrinsic viscosity is within the above range, the fluidity at the time of molding the polyamide resin composition is likely to increase, and it becomes easy to mold into a desired shape. The intrinsic viscosity [η] is adjusted by the molecular weight of the semi-aromatic polyamide resin (A).

The intrinsic viscosity is about 0.5 g of semi-aromatic polyamide resin (A) dissolved in 50 ml of 96.5% concentrated sulfuric acid, and the resulting solution was allowed to flow under conditions of 25 ° ± 0.05 ° C. The number is a value calculated using an Ubbelohde viscometer and calculated based on the following equation.
[Η] = ηSP / (C (1 + 0.205ηSP))
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
t: Number of seconds that the sample solution flows (seconds)
t0: number of seconds (seconds) that the blank sulfuric acid flows down
ηSP = (t−t0) / t0

  Here, if the semi-aromatic polyamide resin (A) satisfies the glass transition temperature and includes a component unit derived from a dicarboxylic acid such as terephthalic acid and an aliphatic diamine component unit, the structure is as follows. There is no particular limitation.

  The dicarboxylic acid component unit includes at least a terephthalic acid component unit. The amount of the terephthalic acid component unit contained in the semi-aromatic polyamide resin (A) is 50 mol% or more based on the total number of moles of the dicarboxylic acid component units constituting the semi-aromatic polyamide resin (A), preferably Is 60 to 100 mol%, more preferably 65 to 100 mol%. If the dicarboxylic acid component unit contains 50 mol% or more of the terephthalic acid component unit, the crystallinity of the semi-aromatic polyamide resin (A) increases, and the heat resistance and rigidity of the resulting aiming nut increase. As described above, when two or more kinds of semi-aromatic polyamide resins are contained in the polyamide resin composition, these mixtures are handled as the semi-aromatic polyamide resin (A). Therefore, when the semi-aromatic polyamide resin (A) includes a plurality of semi-aromatic polyamide resins, the total amount of terephthal component units may be 50 mol% or more with respect to the total number of moles of these dicarboxylic acid component units. That is, the semi-aromatic polyamide resin (A) may partially include a semi-aromatic polyamide resin whose terephthalic acid component amount does not satisfy the above range.

  Here, the semi-aromatic polyamide resin (A) may contain a component unit derived from dicarboxylic acid other than terephthalic acid as the dicarboxylic acid component unit. Examples of dicarboxylic acids other than terephthalic acid include aromatic dicarboxylic acids such as isophthalic acid, 2-methylterephthalic acid and naphthalenedicarboxylic acid; furandicarboxylic acids such as 2,5-furandicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid; malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethyl Glutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, suberic acid, and aliphatic dicarboxylic acids having 11 or more carbon atoms. The semi-aromatic polyamide resin (A) may contain only one type of component unit derived from these, or two or more types of component units. The dicarboxylic acid component unit other than the terephthalic acid component unit is preferably a component unit derived from an aromatic dicarboxylic acid, and more preferably an isophthalic acid component unit.

  When the dicarboxylic acid component unit of the semi-aromatic polyamide resin (A) includes a terephthalic acid component unit and an isophthalic acid component unit, these molar ratios (terephthalic acid component unit / isophthalic acid component unit) are 60/40 to 99. 0.9 / 0.1 is preferable, more preferably 60/40 to 90/10, and still more preferably 60/40 to 85/15. When the amount of the terephthalic acid component unit is in the above range, as described above, the heat resistance and rigidity of the resulting aiming nut are easily increased. On the other hand, when the amount of the isophthalic acid component unit is within the above range, the impact resistance of the resulting aiming nut is likely to be increased.

  Further, the structure of the aliphatic diamine component unit constituting the semi-aromatic polyamide resin (A) is not particularly limited, but it is a component unit having 4 to 18 carbon atoms and derived from a linear alkylenediamine ( Hereinafter, it is also referred to as “linear alkylenediamine component unit”), or a component unit derived from alkylenediamine having 4 to 18 carbon atoms and having a side chain (hereinafter also referred to as “side chain alkylenediamine component unit”). It is preferable that at least one of these is included. The number of carbon atoms in the side chain alkylenediamine is a number including the number of carbon atoms contained in the side chain. Only one or both of these may be contained in the semi-aromatic polyamide resin (A).

  When the vehicle is used in a cold region, calcium chloride or zinc chloride is sprayed on the road as a snow melting agent or a road antifreezing agent. When such calcium chloride or zinc chloride adheres to the aiming nut, stress corrosion cracking or the like of the aiming nut is likely to occur. The adhesion of calcium chloride or zinc chloride to the aiming nut is more likely to occur when the polyamide resin composition has high water absorption. On the other hand, when the number of carbon atoms in the aliphatic diamine component unit of the semi-aromatic polyamide resin (A) is 4 or more, the hygroscopicity and water absorption of the polyamide resin composition are lowered, and calcium chloride and zinc chloride are adhered. It is difficult to cause stress corrosion cracking.

  Here, it is preferable that 40 mol% or more of linear alkylenediamine component units are contained with respect to the total number of moles (100 mol%) of aliphatic diamine component units. When the linear alkylenediamine component unit is contained in a certain amount or more, the water resistance of the polyamide resin composition tends to increase.

  The number of carbon atoms of the linear alkylenediamine component unit is preferably 4-15, and more preferably 6-12. Specific examples of the linear alkylenediamine component unit include 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-octanediamine, 1,9-diaminononane, 1,10- Diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane and the like are included. The semi-aromatic polyamide resin (A) may contain only one type of linear alkylenediamine component unit, or may contain two or more types. Among these, 1,6-diaminohexane and 1,9-nonanediamine are preferable, and it is preferable that they are contained in a total amount of 50 to 100 mol% with respect to the total number of moles of linear alkylenediamine (100 mol%). .

  On the other hand, the side chain alkylenediamine component unit is preferably contained in an amount of 60 mol% or less with respect to the total number of moles (100 mol%) of the aliphatic diamine component unit. When the semi-aromatic polyamide resin (A) contains a certain amount or less of the side chain alkylenediamine component unit, the impact resistance of the resulting aiming nut is likely to increase. Although the reason is not certain, it is considered that the dispersibility of the modified olefin polymer (B) is further improved by the side chain structure.

  The number of carbon atoms in the side chain alkylenediamine component unit is preferably 4-15, more preferably 6-12. Specific examples of the side chain alkylenediamine component unit include 2-methyl-1,5-pentanediamine, 2-methyl-1,6-diaminohexane, 2-methyl-1,7-diaminoheptane, and 2-methyl-1. , 8-octanediamine, 2-methyl-1,9-diaminononane, 2-methyl-1,10-diaminodecane, 2-methyl-1,11-diaminoundecane and the like. The semi-aromatic polyamide resin (A) may contain only one type of side chain alkylenediamine component unit, or may contain two or more types. Among these, 2-methyl-1,5-pentanediamine and 2-methyl-1,8-octanediamine are preferable.

  As described above, the semiaromatic polyamide resin (A) may include both a linear alkylenediamine component unit and a side chain alkylenediamine component unit as the aliphatic diamine component unit. As an example of these preferable combinations, a combination of a 1,6-diaminohexane component unit and a 2-methyl-1,5-pentadiamine component unit may be mentioned. At this time, the 1,6-diaminohexane component unit is more than 45 mol% and less than 55 mol%, and 2-methyl-1,5-pentadiamine is more than 45 mol% with respect to the total number of moles of the aliphatic diamine component unit. It is preferable to contain less than mol%. Another example of a preferable combination is a combination of a 1,9-nonanediamine component unit and a 2-methyl-1,8-octanediamine component unit. At this time, the 1,9-nonanediamine component unit is more than 45 mol% and less than 85 mol%, and the 2-methyl-1,8-octanediamine unit unit is more than 15 mol% with respect to the total number of moles of the aliphatic diamine component unit. It is preferable to contain less than 55 mol%.

  The aliphatic diamine component unit has an aliphatic carbon diamine component unit having a larger number of carbon atoms than the linear alkylene diamine component unit or side chain alkylene diamine component unit as long as the effects of the present invention are not impaired. May be included. The semi-aromatic polyamide resin (A) may contain diamine component units other than the aliphatic diamine component units as long as the effects of the present invention are not impaired. Examples of the diamine component unit other than the aliphatic diamine component unit include an alicyclic diamine component unit and an aromatic diamine component unit.

  As an example of a resin particularly preferable as the semi-aromatic polyamide resin (A), the dicarboxylic acid component unit is a terephthalic acid component unit, and the aliphatic diamine component unit is 1,6-diaminohexane and 2-methyl-1,5. -Resin that is pentadiamine; Resin in which dicarboxylic acid component unit is terephthalic acid component unit and aliphatic diamine component unit is 1,9-nonanediamine and 2-methyl-1,8-pentadiamine; dicarboxylic acid component unit Is a terephthalic acid component unit and an isophthalic acid component unit, and an aliphatic diamine component unit is 1,6-diaminohexane; a dicarboxylic acid component unit is a terephthalic acid component unit and an adipic acid component unit, and is aliphatic. Examples thereof include resins whose diamine component unit is 1,6-diaminohexane. The polyamide resin composition of the present invention may contain only one kind or two or more kinds.

  Here, the semi-aromatic polyamide resin (A) may be sealed with a terminal sealing agent. End capping agents can be, for example, monocarboxylic acids and monoamines. By sealing the terminal carboxyl group and / or amino group of the semi-aromatic polyamide resin (A) with the end-capping agent, the amount of carboxyl group and amino group of the semi-aromatic polyamide resin (A) is adjusted. The

  The amount of terminal amino groups in the molecular chain of the semi-aromatic polyamide resin (A) is preferably 0.1 to 200 mmol / kg, more preferably 0.1 to 150 mmol / kg, and particularly preferably 0.1 to 120 mmol / kg. If an amino group of 0.1 mmol / kg or more exists at the terminal of the semi-aromatic polyamide resin (A), the semi-aromatic polyamide resin (A) and the functional group of the modified olefin polymer (B) are likely to interact with each other. These dispersibility tends to increase. As a result, the heat resistance, rigidity, and impact resistance of the resulting aiming nut are likely to increase.

  On the other hand, if the amount of terminal amino groups is too large, the hygroscopicity and water absorption of the aiming nut are likely to increase, but if the amount of terminal amino groups is 200 mmol / kg or less, the water absorption of the semi-aromatic polyamide resin (A) is high. Since it can be kept low, the calcium chloride resistance and zinc chloride resistance of the aiming nut are likely to increase.

  The amount of terminal amino groups of the semi-aromatic polyamide resin (A) is adjusted based on the ratio of the diamine and dicarboxylic acid used when preparing the semi-aromatic polyamide resin (A) and the amount of the end-capping agent. For example, the terminal amino group content is obtained by adding a terminal blocking agent composed of a monocarboxylic acid or the like to a system containing a diamine and a dicarboxylic acid at the time of preparing the semi-aromatic polyamide resin (A) and sealing a part of the terminals. Is adjusted.

The amount of the terminal amino group is measured by the following method. 1 g of semi-aromatic polyamide resin (A) is dissolved in 35 mL of phenol, and 2 mL of methanol is mixed to obtain a sample solution. Then, using thymol blue as an indicator, the sample solution is titrated using a 0.01 N aqueous HCl solution to specify the amount of terminal amino groups ([NH ₂ ], unit: mmol / kg).

  The semi-aromatic polyamide resin (A) can be produced in the same manner as known semi-aromatic polyamides. For example, it can be produced by polycondensation of dicarboxylic acid and diamine in a homogeneous solution. More specifically, a low-order condensate is obtained by heating dicarboxylic acid and diamine in the presence of a catalyst as described in WO 03/085029, and then this low-order condensate. It can be produced by polycondensation by applying shear stress to the melt.

  Moreover, when adjusting the intrinsic viscosity of a semi-aromatic polyamide resin (A), it is preferable to mix | blend a molecular weight regulator (for example, terminal blocker) with a reaction system. Molecular weight modifiers can be, for example, monocarboxylic acids and monoamines. Examples of monocarboxylic acids that can be molecular weight modifiers include aliphatic monocarboxylic acids having 2 to 30 carbon atoms, aromatic monocarboxylic acids, and alicyclic monocarboxylic acids. According to these molecular weight regulators, the molecular weight of the semi-aromatic polyamide resin (A) can be adjusted, and the amount of terminal amino groups of the semi-aromatic polyamide resin (A) can be adjusted. In addition, the aromatic monocarboxylic acid and the alicyclic monocarboxylic acid may have a substituent in the cyclic structure portion.

  Examples of the above aliphatic monocarboxylic acids include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, oleic acid and linoleic acid, etc. Is included. Examples of the aromatic monocarboxylic acid include benzoic acid, toluic acid, naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. Examples of the alicyclic monocarboxylic acid include cyclohexanecarboxylic acid. It is.

  The 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, with respect to 1 mol of the total amount of dicarboxylic acid. By using the molecular weight adjusting agent in such an amount, at least a part of the molecular weight adjusting agent is incorporated into the polyamide, whereby the molecular weight of the polyamide, that is, the intrinsic viscosity [η] is adjusted within a desired range.

1-2. Modified olefin polymer (B)
The modified olefin polymer (B) is a functional group structural unit containing a hetero atom (hereinafter also simply referred to as “functional group structural unit”) 0.03 to 2. It is a polymer containing 0% by mass. The functional group structural unit includes a functional group containing a hetero atom, and examples of the functional group include a carboxylic acid group (including a carboxylic anhydride group), an ester group, an ether group, an aldehyde group, and a ketone group. included.

  When the modified olefin polymer (B) is contained in the polyamide resin composition, the functional group reacts with or interacts with the terminal group of the semi-aromatic polyamide resin (A). At this time, when the functional group structural unit amount of the modified olefin polymer (B) is within the above range, the semi-aromatic polyamide resin (A) and the modified olefin polymer (B) are bonded or interacted. Thus, the heat resistance and rigidity of the obtained aiming nut are easily compatible with the impact resistance.

  In addition, when the amount of the functional group structural unit is excessive, the bond and interaction become too strong, and the melt fluidity of the polyamide resin composition may be lowered. However, the functional group structural unit amount is 2.0. If it is at most mass%, the melt fluidity of the polyamide resin composition will be sufficiently maintained. The amount of the functional group structural unit is preferably 0.1 to 2.0% by mass, more preferably 0.3 to 2.0% by mass. More preferably, it is 0.3-1.2 mass%.

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

Specifically, the following conditions can be illustrated as examples of conditions for specifying the amount of the functional group structural unit. However, the conditions are not limited.
^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 integration is 500 times or more. The standard chemical shift is 0 ppm for tetramethylsilane hydrogen, but the same result can also be obtained by setting the peak derived from the residual hydrogen of deuterated orthodichlorobenzene to 7.10 ppm as the standard value for chemical shift. Can be obtained. A peak such as ¹ H of the functional group-containing structural unit can be assigned by a conventional method.

^In the case of ¹³ C-NMR measurement, an ECP500 type nuclear magnetic resonance apparatus manufactured by JEOL Ltd. is used as the measurement apparatus, and the solvent is ortho-dichlorobenzene / heavy benzene (80/20 vol%) mixed solvent. Also, 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, integration number is 10,000 times or more, 27.50 ppm of chemical shift Use the reference value. Assignment of various signals is performed based on a conventional method, and quantification can be performed based on an integrated value of signal intensity.

  Moreover, the following method is also mentioned as a method for simply measuring the amount of the functional group structural unit. A plurality of modified olefin polymers having different functional group structural unit amounts are prepared, and the content of each functional group is specified by NMR measurement. And the infrared spectroscopy (IR) measurement is performed about the modified olefin polymer by which functional group content was specified, respectively. A calibration curve is created from the intensity ratio of the specific peak of the obtained infrared spectroscopy (IR) spectrum and the functional group content. If the said calibration curve is used, the quantity of a functional group structural unit can be specified about arbitrary polymers. This method is simpler than the NMR measurement described above, but basically, it is necessary to prepare a corresponding calibration curve depending on the type of base resin and functional group. For this reason, this method is preferably used for process management in resin production at a commercial plant, for example.

Here, the density measured by JIS K7112 of the modified olefin polymer (B) is preferably 0.80 to 0.95 g / cm ³ , and is 0.85 to 0.95 g / cm ^3. Is more preferable.

  The intrinsic viscosity [η] measured in a 135 ° C. decalin (decahydronaphthalene) solution of the modified olefin polymer (B) is preferably 0.5 to 4.0 dl / g, more preferably 1. It is 0-3 dl / g, More preferably, it is 1.5-3 dl / g. If the intrinsic viscosity [η] is within the above range, the impact resistance and melt flowability of the polyamide resin composition of the present invention can be compatible at a high level. The intrinsic viscosity [η] in 135 ° C. decalin of the modified olefin polymer (B) is measured as follows based on a conventional method. 20 mg of a sample is dissolved in 15 ml of decalin, and the specific viscosity (ηsp) is measured in an atmosphere of 135 ° C. using an Ubbelohde viscometer. After adding 5 ml of decalin to the decalin solution and diluting, the same specific viscosity is measured. Based on the measurement result obtained by repeating this dilution operation and viscosity measurement twice more, the “ηsp / C” value when the concentration (C) is extrapolated to zero is defined as the intrinsic viscosity [η].

  The modified olefin polymer (B) is obtained by modifying the olefin polymer with a compound having the above-mentioned functional group. Preferable examples of the compound having a functional group for obtaining the modified olefin polymer (B) include an unsaturated carboxylic acid or a derivative thereof. Specific examples of the unsaturated carboxylic acid or derivative thereof include acrylic acid, methacrylic acid, α-ethylacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid and endocis-bicyclo [ 2,2,1] hept-5-ene-2,3-dicarboxylic acid (nadic acid [registered trademark]) and other unsaturated carboxylic acids or unsaturated dicarboxylic acids, and their acid halides, amides, imides, acid anhydrides And derivatives such as esters. Among these, unsaturated dicarboxylic acids or acid anhydrides thereof are preferable, and maleic acid, nadic acid (registered trademark), and acid anhydrides thereof are particularly preferable.

  The compound having the functional group is particularly preferably maleic anhydride. Maleic anhydride has high reactivity with the olefin polymer that is the skeleton of the modified olefin polymer (B). On the other hand, since polymerization between maleic anhydrides hardly occurs, it can be reacted with an olefin polymer stably.

  On the other hand, examples of the olefin polymer that becomes the skeleton of the modified olefin polymer (B) include known polymers such as ethylene polymers, propylene polymers, butene polymers, and copolymers of these olefins. Is included. A particularly preferred olefin polymer is a copolymer of ethylene and an olefin having 3 or more carbon atoms, that is, an ethylene / α-olefin copolymer.

  An ethylene / α-olefin copolymer is a copolymer of ethylene and another olefin; ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and 1 -A copolymer with an α-olefin having 3 to 10 carbon atoms such as decene. Specific examples of the ethylene / α-olefin copolymer include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer and ethylene / 4-methyl-1-pentene copolymer and the like are included. Among these, an ethylene / propylene copolymer, an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, and an ethylene / 1-octene copolymer are particularly preferable.

  The ethylene / α-olefin copolymer preferably contains 70 to 99.5 mol% of structural units derived from ethylene, more preferably 80 to 99 mol%. On the other hand, it is preferable to contain 0.5-30 mol% of structural units derived from α-olefin, more preferably 1-20 mol%.

  The ethylene / α-olefin copolymer has a melt flow rate (MFR) at 190 ° C. and a load of 2.16 kg according to ASTM D1238 of 0.01 to 20 g / 10 minutes, preferably 0.05 to 20 g / 10 minutes. Some are desirable.

  The production method of the ethylene / α-olefin copolymer which becomes the skeleton of the modified olefin polymer (B) is not particularly limited. For example, titanium (Ti), vanadium (V), chromium (Cr), or zirconium It can be prepared by a known method using a transition metal catalyst such as (Zr) series. More specifically, ethylene is copolymerized with one or more α-olefins having 3 to 10 carbon atoms in the presence of a Ziegler catalyst or a metallocene catalyst composed of a V compound and an organoaluminum compound. A method using a metallocene catalyst is particularly suitable.

  On the other hand, the modified olefin polymer (B) is obtained by graft-modifying the ethylene / α-olefin copolymer with a compound having a functional group. The graft modification can be performed by a known method. For example, after dissolving an ethylene / α-olefin copolymer in an organic solvent, an unsaturated carboxylic acid or a derivative thereof (compound having a functional group) is added to the solution, and these are reacted, thereby modifying the modified olefin polymer. (B) is obtained. From the viewpoint of reaction efficiency and the like, it is preferable to add a radical initiator to the reaction solution. The temperature of the reaction solution is usually about 60 to 350 ° C, preferably 80 to 190 ° C. Moreover, reaction time is 0.5 to 15 hours normally, Preferably it is 1 to 10 hours.

  Examples of the radical initiator include organic peroxides, organic peresters, and azo compounds. Examples of organic peroxides and organic peroxides include benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (peroxide benzoate) hexyne-3,1 , 4-bis (t-butylperoxyisopropyl) benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2 , 5-di (t-butylperoxy) hexane, t-butylperbenzoate, t-butylperphenylacetate, t-butylperisobutyrate, t-butylper-sec-octoate, t-butylperpivalate, cumyl Perpivalate and t-butylperdiethyla It includes Tate. Examples of the azo compound include azobisisobutyronitrile and dimethylazoisobutyrate. Among these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3,2,5-dimethyl-2,5-di (t- Dialkyl peroxides such as butylperoxy) hexane and 1,4-bis (t-butylperoxyisopropyl) benzene are preferred. The radical initiator is preferably added in a proportion of usually 0.001 to 1 part by weight with respect to 100 parts by weight of the ethylene / α-olefin copolymer before modification.

  Further, the organic solvent for preparing the modified olefin polymer (B) is not particularly limited, but aromatic hydrocarbon solvents such as benzene, toluene and xylene; and aliphatic hydrocarbon solvents such as pentane, hexane and heptane, etc. included.

  On the other hand, other examples of the preparation method of the modified olefin polymer (B) include an ethylene / α-olefin copolymer and a compound having a functional group (unsaturated carboxylic acid or A method of reacting the derivative) and the like is also included. In this case, the reaction temperature is preferably equal to or higher than the melting point of the ethylene / α-olefin copolymer, specifically, preferably 100 to 350 ° C. The reaction time is usually 0.5 to 10 minutes.

1-3. Other Components The polyamide resin composition of the present invention may contain a fibrous filler, various additives, and other resins as long as the effects of the present invention are not impaired.

  The fibrous filler that can be contained in the polyamide resin composition is not particularly limited, and may be any of a fibrous filler made of a known inorganic compound and a fibrous filler made of a known organic compound. Examples of fibrous fillers include glass fiber, carbon fiber, wholly aromatic polyamide fiber (eg, polyparaphenylene terephthalamide fiber, polymetaphenylene terephthalamide fiber, polyparaphenylene isophthalamide fiber, polymetaphenylene isophthalamide fiber). , Fibers obtained from condensates of diaminodiphenyl ether and terephthalic acid or isophthalic acid), boron fibers, liquid crystal polyester fibers, and the like. The polyamide resin composition may contain only one type of fibrous filler or two or more types of fibrous filler.

  The surface of the fibrous filler may be treated with various treatment agents. When the fibrous filler is surface-treated, an interaction occurs between the fibrous filler and the semi-aromatic polyamide resin (A) or the modified olefin polymer (B), and the adhesive strength thereof is improved. . Examples of the surface treatment agent for surface-treating the fibrous filler include coupling agents such as a silane coupling agent, a titanium coupling agent, and an aluminate coupling agent, a sizing agent, and the like. A surface treating agent may be used individually by 1 type, and 2 or more types may be used together.

  The length of the fibrous filler is not particularly limited, and is appropriately selected according to the dimensions of the aiming nut, desired strength, and the like. The length of the fibrous filler can be about 1 μm to 20 mm. The fiber diameter of the fibrous filler may be about 0.1 μm to 100 μm.

  In addition, the polyamide resin composition of the present invention may contain an optional additive depending on the range and use without impairing the effects of the present invention. Examples of additives include antioxidants (phenols, amines, sulfurs, phosphorus, etc.), fillers (clay, silica, alumina, talc, kaolin, quartz, mica, graphite, etc.), heat stabilizers ( Lactone compounds, vitamin Es, hydroquinones, copper halides, iodine compounds, etc.), light stabilizers (benzotriazoles, triazines, benzophenones, benzoates, hindered amines, ogizanides, etc.), flame retardants (bromine-based, Chlorine, phosphorus, antimony, inorganic, etc.), lubricants, fluorescent brighteners, plasticizers, thickeners, antistatic agents, mold release agents, pigments, crystal nucleating agents, and various known additives. .

  The polyamide resin composition includes a polymer other than the semi-aromatic polyamide resin (A) and the modified olefin polymer (B) (olefin homopolymers such as polyethylene; ethylene / propylene copolymer, ethylene -Ethylene / α-olefin copolymer such as 1-butene copolymer; Propylene / α-olefin copolymer such as propylene / 1-butene copolymer; Polystyrene; Polyamide; Polycarbonate; Polyacetal; Polyrphone; Polyphenylene oxide; Fluorine resin; silicone resin; LCP, etc.) may be included.

  Furthermore, a polyamide resin other than the above-mentioned semi-aromatic polyamide resin (A) (hereinafter also referred to as “other polyamide resin”) may be included as long as the effects of the present invention are not impaired. Examples of other polyamide resins include polycaproamide (nylon 6), polyundecanamide (nylon 11), polydodecanamide (nylon 12), polytetramethylene adipamide (nylon 46), polyhexamethylene adipamide (Nylon 66), polymetaxylylene adipamide (nylon MXD6), polyparaxylylene adipamide (nylon PXD6), polytetramethylene sebacamide (nylon 410), polyhexamethylene sebacamide (nylon 610), Polydecamethylene adipamide (nylon 106), polydecamethylene sebamide (nylon 1010), polyhexamethylene dodecamide (nylon 612), polydecamethylene dodecamide (nylon 1012), polyhexamethylene isophthalamide (nylon 6I) ) Hexamethylene hexahydroterephthalamide (nylon 6T (H)), polybis (3-methyl-4-aminohexyl) methane isophthalamide (nylon PACMI), polybis (3-methyl-4-aminohexyl) methane dodecamide (nylon PACM12 ), Polybis (3-methyl-4-aminohexyl) methanetetradecamide (nylon PACM14), and the like. One kind of these polyamide resins may be contained in the polyamide resin composition, or two or more kinds thereof may be contained.

1-4. Composition of polyamide resin composition for aiming nut As described above, the polyamide resin composition contains at least a semi-aromatic polyamide resin (A) and a modified olefin polymer (B), and if necessary, filled with a fiber. Agents, various additives, and other resins.

  The amount of the semi-aromatic polyamide resin (A) in the polyamide resin composition of the present invention is 75 to 97% by mass with respect to the total of the semi-aromatic polyamide resin (A) and the modified olefin polymer (B). More preferably, it is 78-97 mass%, More preferably, it is 80-97 mass%. When the semi-aromatic polyamide resin (A) is included in the above range, the heat resistance of the resulting aiming nut is likely to be increased, and the rigidity is likely to be increased.

  On the other hand, the amount of the modified olefin polymer (B) in the semi-aromatic polyamide resin composition is 3% by mass or more and 25% by mass with respect to the total of the semi-aromatic polyamide resin (A) and the modified olefin polymer (B). % Or less, more preferably 3 to 20% by mass, and even more preferably 5 to 18% by mass. When the modified olefin polymer (B) is included in the above range, the impact resistance of the resulting aiming nut is likely to increase.

  When the polyamide resin composition contains a polymer other than the semi-aromatic polyamide resin (A) and the modified olefin polymer (B) (for example, an olefin polymer), these are polyamide resin compositions. It is preferably 5% by mass or less, more preferably 3% by mass or less, based on the total mass of the product.

  Further, when the polyamide resin composition of the present invention contains the other polyamide resin described above, the amount thereof is appropriately selected depending on the type of the resin, but the semi-aromatic polyamide resin (A) and the olefin polymer (B) It is preferable that other polyamide resin is 3.5 mass parts or less with respect to a total of 100 mass parts.

2. Process for producing polyamide resin composition for aiming nut The semi-aromatic polyamide resin composition of the present invention comprises the above-mentioned semi-aromatic polyamide resin (A), modified olefin polymer (B), and other components as required. And a known method, for example, a method of mixing with a Henschel mixer, a V blender, a ribbon blender, a tumbler blender or the like. Further, after mixing the respective components, it may be further kneaded and granulated or pulverized by a single screw extruder, a multi-screw extruder, a kneader, a Banbury mixer or the like.

3. Aiming nut for vehicle lamp The aiming nut of the present invention may be obtained by molding the above-described polyamide resin composition for aiming nut by various molding methods. The molding method is not particularly limited, and may be a known method such as an injection molding method.

  The shape of the aiming nut of the present invention is not particularly limited, and is appropriately selected according to the structure of the vehicle lamp. The aiming nut can be, for example, a nut having a known structure called a so-called self-locking nut or an optical axis adjusting nut.

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

1. Preparation of semi-aromatic polyamide resin (A) [Synthesis Example 1] Preparation of semi-aromatic polyamide resin (A-1) 1,12-diaminohexane (1312 g, 11.1 mol), 2-methyl-1,5-pentane Diamine 1312 g (11.1 mol), terephthalic acid 3655 g (22.0 mol), benzoic acid 34.2 g (0.28 mol), sodium hypophosphite 5.5 g (5.2 × 10 ⁻² mol) as a catalyst ), And 640 ml of ion-exchanged water were charged into a 1 liter reactor, and after purging with nitrogen, the reaction was carried out for 1 hour under the conditions of 250 ° C. and 35 kg / cm ² . The molar ratio of 1,6-diaminohexane and 2-methyl-1,5-pentanediamine was 50:50. After 1 hour, the reaction product produced in the reactor was withdrawn into a receiver connected to the reactor and set at a pressure of about 10 kg / cm ² lower, and the intrinsic viscosity [η] was 0.15 dl / A polyamide precursor g was obtained.
Next, this polyamide precursor was dried and melt polymerized at a cylinder setting temperature of 330 ° C. using a twin screw extruder to obtain a semi-aromatic polyamide resin (A-1). The composition of this aromatic polyamide resin (A-1) was as follows.
The 1,6-diaminohexane component unit content in the diamine component unit was 50 mol%, and the 2-methyl-1,5-pentanediamine component unit content was 50 mol%. The obtained semiaromatic polyamide resin (A-1) has an intrinsic viscosity [η] of 1.0 dl / g, a terminal amino group content of 45 mmol / kg, a melting point Tm of 300 ° C., and a glass transition temperature of 140. ° C. The obtained results are summarized in Table 1.

[Synthesis Example 2] Preparation of semi-aromatic polyamide resin (A-2) 1787 g (13.1 mol) of terephthalic acid, 2800 g (24.1 mol) of 1,6-diaminohexane, 1921 g (10.8 mol) of adipic acid Then, 36.6 g (0.30 mol) of benzoic acid, 5.7 g of sodium hypophosphite monohydrate, and 554 g of distilled water were placed in an autoclave having an internal volume of 13.6 L, and the atmosphere was replaced 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 3.01 MPa. The reaction was continued for 1 hour as it was, and then discharged from the spray nozzle installed at the bottom of the autoclave to extract the low condensate.
Thereafter, the low condensate was cooled to room temperature, pulverized to a particle size of 1.5 mm or less with a pulverizer, and dried at 110 ° C. for 24 hours. The obtained low condensate had a water content of 3600 ppm and an intrinsic viscosity [η] of 0.14 dl / g. Next, this low condensate was placed in a shelf type solid phase polymerization apparatus, and after the nitrogen substitution, the temperature was raised to 220 ° C. over about 1 hour 30 minutes. Then, it was made to react for 1 hour and it was made to cool to room temperature. The intrinsic viscosity [η] of the obtained compound was 0.48 dl / g.
Thereafter, it was melt polymerized by a twin screw extruder with a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply speed of 6 kg / h, and a semi-aromatic polyamide resin (A -2) was prepared. The obtained semi-aromatic polyamide resin (A-2) has an intrinsic viscosity [η] of 1.0 dl / g, a terminal amino group amount of 45 mmol / kg, a melting point Tm of 310 ° C., and a glass transition temperature of 85 ° C. there were. The obtained results are summarized in Table 1.

[Synthesis Example 3] Preparation of semi-aromatic polyamide resin (A-3) 1,6-diaminohexane 2800 g (24.1 mol), 2774 g (16.7 mol) terephthalic acid, 1196 g (7.2 mol) isophthalic acid Then, 36.6 g (0.30 mol) of benzoic acid, 5.7 g of sodium hypophosphite monohydrate, and 545 g of distilled water were placed in an autoclave having an internal volume of 13.6 L 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 3.03 MPa. The reaction was continued for 1 hour as it was, and then discharged from the spray nozzle installed at the bottom of the autoclave to extract the low condensate. Then, after cooling to room temperature, the low condensate was pulverized to a particle size of 1.5 mm or less with a pulverizer and dried at 110 ° C. for 24 hours. The obtained low condensate had a water content of 4100 ppm and an intrinsic viscosity [η] of 0.15 dl / g. Next, this low condensate was put into a shelf type solid phase polymerization apparatus, and after the nitrogen substitution, the temperature was raised to 180 ° C. over about 1 hour 30 minutes. Thereafter, the reaction was performed for 1 hour 30 minutes, and the temperature was lowered to room temperature. The intrinsic viscosity [η] of the obtained compound was 0.20 dl / g.
Thereafter, in a twin screw extruder having a screw diameter of 30 mm and L / D = 36, melt polymerization was performed at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply rate of 6 Kg / h, and a semi-aromatic polyamide resin ( A-3) was prepared. The obtained polyamide resin had an intrinsic viscosity [η] of 1.0 dl / g, a terminal amino group amount of 30 mmol / kg, a melting point Tm of 330 ° C., and a glass transition temperature of 125 ° C. The obtained results are summarized in Table 1.

Synthesis Example 4 Preparation of Semi-aromatic Polyamide Resin (A-4) 4537.7 g (27.3 mol) of terephthalic acid, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine [1 , 9-nonanediamine / 2-methyl-1,8-octanediamine = 80/20 (molar ratio)] 4385 g (27.5 mol), benzoic acid 41.5 g (0.34 mol), sodium hypophosphite 9.12 g of hydrate (0.1% by mass with respect to the total mass of the raw material) and 2.5 liters of distilled water were placed in an autoclave having an internal 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 increased 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, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2 MPa.
Next, the pressure was reduced to 1 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer having an intrinsic viscosity [η] of 0.15 dl / g. This was dried at 100 ° C. under reduced pressure for 12 hours and pulverized to a particle size of 2 mm or less. This was subjected to solid state polymerization at 230 ° C. and 13 Pa (0.1 mmHg) for 10 hours to prepare a semi-aromatic polyamide resin (A-4). The obtained semiaromatic polyamide resin (A-4) has an intrinsic viscosity [η] of 1.2 dl / g, a terminal amino group amount of 40 mmol / kg, a melting point Tm of 300 ° C., and a glass transition temperature of 125 ° C. there were. The obtained results are summarized in Table 1.

[Synthesis Example 5] Preparation of semi-aromatic polyamide resin (A-5) 1787 g (10.8 mol) of terephthalic acid, 2800 g (24.9 mol) of 1,6-diaminohexane, 1921 g (13.1 mol) of adipic acid Then, 36.6 g (0.30 mol) of benzoic acid, 5.7 g of sodium hypophosphite monohydrate, and 554 g of distilled water were placed in an autoclave having an internal volume of 13.6 L 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 3.01 MPa. The reaction was continued for 1 hour as it was, and then discharged from the spray nozzle installed at the bottom of the autoclave to extract the low condensate.
Thereafter, the low condensate was cooled to room temperature, pulverized to a particle size of 1.5 mm or less with a pulverizer, and dried at 110 ° C. for 24 hours. The obtained low condensate had a water content of 3600 ppm and an intrinsic viscosity [η] of 0.14 dl / g. Next, this low condensate was placed in a shelf type solid phase polymerization apparatus, and after the nitrogen substitution, the temperature was raised to 220 ° C. over about 1 hour 30 minutes. Then, it was made to react for 1 hour and it was made to cool to room temperature. The intrinsic viscosity [η] of the obtained compound was 0.48 dl / g.
Thereafter, it was melt polymerized by a twin screw extruder with a screw diameter of 30 mm and L / D = 36 at a barrel set temperature of 330 ° C., a screw rotation speed of 200 rpm, and a resin supply speed of 6 kg / h, and a semi-aromatic polyamide resin (A -5) was prepared. The semi-aromatic polyamide resin (A-5) obtained had an intrinsic viscosity [η] of 0.8 dl / g, a terminal amino group content of 48 mmol / kg, a melting point Tm of 295 ° C., and a glass transition temperature of 75 ° C. It was. The obtained results are summarized in Table 1.

Synthesis Example 6 Preparation of Aliphatic Polyamide (A′-1) 0.3 kg of caprolactam, 0.4 g of acetic acid, and 10 g of distilled water were placed in an autoclave having an internal volume of 1 L and purged with nitrogen. The internal temperature was raised to 180 ° C. over 2 hours. At this time, the internal pressure of the autoclave was increased to 10 kg / cm ² . Next, the internal temperature was raised to 240 ° C. over 2 hours while maintaining the internal pressure. Then, the pressure of the autoclave was released, and a polymerization reaction was further performed at 240 ° C. for 2 hours.
Thereafter, the reaction product was extruded into a pellet and pelletized, and unreacted monomer was extracted and dried using boiling water. The obtained aliphatic polyamide resin (A′-1) has an intrinsic viscosity [η] of 1.0 dl / g, a terminal amino group amount of 50 mmol / kg, a melting point Tm of 225 ° C., and a glass transition temperature of 50 ° C. there were. The obtained results are summarized in Table 1.

[Measurement method of each physical property]
The water content of the low condensate during preparation of the semi-aromatic polyamide resin, the intrinsic viscosity, the terminal amino group amount, and the melting point Tm of the semi-aromatic polyamide resin were determined by the following methods, respectively.

〔amount of water〕
The water content of the low condensate during preparation of each semi-aromatic polyamide resin is obtained by weighing about 0.2 g of sample, heating to 200 ° C. with a Karl Fischer moisture meter, and measuring the amount of water generated at that time. (Solid vaporization method).

[Intrinsic viscosity [η]]
The intrinsic viscosity [η] of the obtained semi-aromatic polyamide resin was measured as follows. 0.5 g of semi-aromatic polyamide resin was dissolved in 50 ml of a 96.5% sulfuric acid solution. The number of seconds flowing down under the condition of 25 ° C. ± 0.05 ° C. of the obtained solution was measured using an Ubbelohde viscometer, and “Formula: [η] = ηSP / (C (1 + 0.205ηSP)) ”Based on
[Η]: Intrinsic viscosity (dl / g)
ηSP: specific viscosity C: sample concentration (g / dl)
t: Number of seconds that the sample solution flows (seconds)
t ₀ : The number of seconds (seconds) that the blank sulfuric acid flows down
ηSP = (t−t ₀ ) / t ₀

[Terminal amino group content]
As for the amount of terminal amino groups of the semi-aromatic polyamide resin, 0.5 to 0.7 g of the semi-aromatic polyamide resin was precisely weighed and dissolved in 30 mL of m-cresol. Then, 1 to 2 drops of 0.1% thymol blue / m-cresol solution as an indicator was added to prepare a sample solution. The sample solution was titrated with a 0.02 N p-toluenesulfonic acid solution until the color changed from yellow to blue-violet, and the terminal amino group content ([NH ₂ ], unit: μ equivalent / g) was specified.

[Melting point (Tm) and glass transition temperature (Tg)]
The melting point (Tm) of the semi-aromatic polyamide resin) was measured using a differential scanning calorimeter (DSC220C type, manufactured by Seiko Instruments Inc.) as a measuring device. Specifically, about 5 mg of semi-aromatic polyamide resin was 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 semi-aromatic polyamide resin, it was held at 330 ° C. for 5 minutes and then cooled to 30 ° C. at 10 ° C./min. After 5 minutes at 30 ° C., the second heating was performed to 330 ° C. at 10 ° C./min. The peak temperature (° C.) at the second heating was defined as the melting point (Tm) of the semi-aromatic polyamide resin, and the displacement point corresponding to the glass transition was defined as the glass transition temperature (Tg).

2. Preparation of Modified Olefin Polymer (B) [Synthesis Example 7] Preparation of Modified Olefin Polymer (B-1) High-density polyethylene (density: 0.95, MFR = 5 g / 10 min) 100 parts by mass, maleic anhydride 0. 8 parts by mass and 0.07 part by mass of organic peroxide [Nippon Yushi Co., Ltd., Perhexin-25B] were mixed with a Henschel mixer, and the resulting mixture was melt grafted with a 65 mmφ single screw extruder set at 230 ° C. By modification, a modified olefin polymer (B-1) (graft-modified polyethylene) was obtained. The maleic anhydride graft amount of the modified olefin polymer (B-1) was 0.7% by mass. The obtained results are summarized in Table 2.

[Synthesis Example 8] Preparation of modified olefin polymer (B-2) 100 parts by mass of linear low density polyethylene (density: 0.92, MFR = 4 g / 10 min), 1.0 part by mass of maleic anhydride, and organic By modifying 0.07 part by weight of a peroxide [Nippon Yushi Co., Ltd., Perhexin-25B] with a Henschel mixer, the resulting mixture was melt graft modified with a 65 mmφ single screw extruder set at 230 ° C. An olefin polymer (B-2) (graft-modified polyethylene) was obtained.
The amount of maleic anhydride grafted in this modified olefin polymer (B-2) was 0.9% by mass. The obtained results are summarized in Table 2.

[Synthesis Example 9] Preparation of Modified Olefin Polymer (B-3) 0.63 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was placed in a glass flask sufficiently substituted with nitrogen, and methylaluminoxane was further added. A catalyst solution was obtained by adding 1.57 ml of a toluene solution (Al; 0.13 mmol / liter) and 2.43 ml of toluene.
Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and the temperature inside the system was raised to 80 ° C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml of the catalyst solution prepared as above (0.0005 mmol as Zr) were injected into the system together with ethylene to initiate the polymerization reaction. By continuously supplying ethylene, the total pressure was kept at 8.0 kg / cm ² -G, and polymerization was carried out at 80 ° C. for 30 minutes.

A small amount of ethanol was introduced into the system to stop the polymerization, and then unreacted ethylene was purged. The obtained solution was poured into a large excess of methanol to precipitate a white solid. This white solid was collected by filtration and dried overnight under reduced pressure to obtain a white solid (ethylene / 1-butene copolymer) (density = 0.87 g / cm ³ , MFR (ASTM D1238 standard, 190 ° C.). : 2.16 kg load) = 0.7 g / 10 min, 1-butene structural unit content: 4 mol%).
To 100 parts by mass of the obtained ethylene / 1-butene copolymer, 1.0 part by mass of maleic anhydride and 0.04 part by mass of peroxide (Perhexine (registered trademark) 25B, manufactured by NOF Corporation) are added. Mixed. The resulting mixture was melt graft modified with a single screw extruder set at 230 ° C. to obtain a modified olefin polymer (B-3) (acid-modified ethylene / 1-butene copolymer). The amount of maleic anhydride graft modification in the modified olefin polymer (B-3) was 0.9% by mass. The obtained results are summarized in Table 2.

Synthesis Example 10 Preparation of Modified Olefin Polymer (B-4) 0.63 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was placed in a glass flask sufficiently substituted with nitrogen, and methylaluminoxane was further added. A catalyst solution was obtained by adding 1.57 ml of a toluene solution (Al; 0.13 mmol / liter) and 2.43 ml of toluene.
Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and the temperature inside the system was raised to 80 ° C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml of the catalyst solution prepared as above (0.0005 mmol as Zr) were injected into the system together with ethylene to initiate the polymerization reaction. By continuously supplying ethylene, the total pressure was kept at 8.0 kg / cm ² -G, and polymerization was carried out at 80 ° C. for 30 minutes.

A small amount of ethanol was introduced into the system to stop the polymerization, and then unreacted ethylene was purged. The obtained solution was poured into a large excess of methanol to precipitate a white solid. This white solid was collected by filtration and dried overnight under reduced pressure to obtain a white solid (ethylene / 1-butene copolymer) (density = 0.87 g / cm ³ , MFR (ASTM D1238 standard, 190 ° C.). : 2.16 kg load) = 0.7 g / 10 min, 1-butene structural unit content: 4 mol%).
To 100 parts by mass of the obtained ethylene / 1-butene copolymer, 2.6 parts by mass of maleic anhydride and 0.1 part by mass of peroxide (Perhexine (registered trademark) 25B, manufactured by NOF Corporation) are added. Mixed. The obtained mixture was melt-grafted with a single screw extruder set at 230 ° C. to obtain a modified olefin polymer (B-4) (acid-modified ethylene / 1-butene copolymer). The amount of maleic anhydride graft modification in the modified olefin polymer (B-4) was 2.5% by mass. The obtained results are summarized in Table 2.

[Synthesis Example 11] Preparation of Modified Olefin Polymer (B-5) 0.63 mg of bis (1,3-dimethylcyclopentadienyl) zirconium dichloride was placed in a glass flask sufficiently purged with nitrogen, and further methylaluminoxane. A catalyst solution was obtained by adding 1.57 ml of a toluene solution (Al; 0.13 mmol / liter) and 2.43 ml of toluene.
Next, 912 ml of hexane and 320 ml of 1-butene were introduced into a 2 liter stainless steel autoclave sufficiently purged with nitrogen, and the temperature inside the system was raised to 80 ° C. Subsequently, 0.9 mmol of triisobutylaluminum and 2.0 ml of the catalyst solution prepared above (0.0005 mmol as Zr) were injected into the system together with ethylene to initiate the polymerization reaction. By continuously supplying ethylene, the total pressure was kept at 8.0 kg / cm ² -G, and polymerization was carried out at 80 ° C. for 30 minutes.

A small amount of ethanol was introduced into the system to stop the polymerization, and then unreacted ethylene was purged. The obtained solution was poured into a large excess of methanol to precipitate a white solid. This white solid was collected by filtration and dried overnight under reduced pressure to obtain a white solid (ethylene / 1-butene copolymer) (density = 0.87 g / cm ³ , MFR (ASTM D1238 standard, 190 ° C.). : 2.16 kg load) = 0.7 g / 10 min, 1-butene structural unit content: 4 mol%). To 100 parts by mass of the obtained ethylene / 1-butene copolymer, 0.01 part by mass of maleic anhydride and peroxide (Perhexine (registered trademark) 25B, manufactured by NOF Corporation) 0.4 × 10 ⁻³ The mass part was mixed. The obtained mixture was melt-grafted with a single screw extruder set at 230 ° C. to obtain a modified olefin polymer (B-5) (acid-modified ethylene / 1-butene copolymer). In the modified olefin polymer (B-5), the maleic anhydride graft modification amount was 0.01% by mass. The obtained results are summarized in Table 2.

[Measurement method of each physical property]
The composition, density, melt flow rate, and functional group bond amount (maleic acid modification amount) of the modified olefin polymer were determined by the following methods.

〔composition〕
The composition of the modified olefin polymer and the content (mol%) of the functional group structural unit were measured by ¹³ C-NMR. The measurement conditions are as follows.
Measuring apparatus: Nuclear magnetic resonance apparatus (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 Accumulated number: 10,000 times or more Solvent: Orthodichlorobenzene / 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

[Melt flow rate (MFR)]
The melt flow rate (MFR) of the ethylene / 1-butene copolymer was measured at 190 ° C. under a load of 2.16 kg in accordance with ASTM D1238. The unit is g / 10 min.

〔density〕
The density of the ethylene / 1-butene copolymer was measured at a temperature of 23 ° C. using a density gradient tube in accordance with JIS K7112.

[Functional group binding amount of modified olefin polymer (B)]
Titration using a sample solution prepared by dissolving 5 g of a pellet of the modified olefin polymer (B) in 170 mL of toluene and adding 30 mL of ethanol, and using 0.1 N KOH ethanol solution with phenolphthalein as an indicator. The functional group bonding amount (unit: mmol / kg) in the modified olefin polymer (B) was specified.

3. Preparation of polyamide resin composition for aiming nut (Examples 1 to 8 and Comparative Examples 1 to 4)
3-1. Preparation of Aiming Nut Polyamide Resin Composition With the composition ratio shown in Table 3, semi-aromatic polyamide resin (A) or aliphatic polyamide resin (A′-1) and modified olefin polymer (B) are used as a tumbler blender. The raw materials were melt kneaded at a cylinder temperature (melting point (Tm) of semi-aromatic polyamide resin + 15) ° C. with a twin-screw extruder (TEX30α manufactured by Nippon Steel Works). Thereafter, the kneaded product was extruded into a strand shape and cooled in a water bath. Thereafter, the strand was taken up with a pelletizer and cut to obtain a pellet-shaped polyamide resin composition for aiming nuts.

3-2. Evaluation About the polyamide resin composition for aiming nuts, a test piece was prepared and tested under the following conditions. The obtained results are shown in Table 3.

(Tensile strength)
A test piece of ASTM-1 (dumbbell piece) having a thickness of 3 mm prepared by using the following injection molding machine for each resin composition prepared by the above method under a temperature of 23 ° C. under a nitrogen atmosphere. Left for 24 hours. Next, a tensile test was performed in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50%, and the tensile strength was measured.
Molding machine: Sodick Plastic Co., Ltd. Tupal TR40S3A
Molding machine cylinder temperature: melting point (Tm) of semi-aromatic polyamide resin (A) + 15 ° C.
Mold temperature: Tg of semi-aromatic polyamide resin (A) + 20 ° C

(Bending test (bending strength))
Using the following injection molding machine, a test piece having a thickness of 3.2 mm adjusted under the following molding conditions was allowed to stand for 24 hours at a temperature of 23 ° C. in a nitrogen atmosphere. Next, a bending test was performed in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% at a bending tester: AB5 manufactured by NTSCO, span 51 mm, bending speed 12.7 mm / min, and the elastic modulus was measured.
Molding machine: Sodick Plastic Co., Ltd. Tupal TR40S3A
Molding machine cylinder temperature: melting point (Tm) of semi-aromatic polyamide resin (A) + 15 ° C.
Mold temperature: Tg of semi-aromatic polyamide resin (A) + 20 ° C

(IZOD impact strength)
Using the following injection molding machine, a test piece with a notch and a thickness of 3.2 mm adjusted under the following molding conditions was prepared, and in accordance with ASTM D256, in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% and IZOD impact strength was measured in an atmosphere at a temperature of −40 ° C. and a relative humidity of 50%.
Molding machine: SE50DU, manufactured by Sumitomo Heavy Industries, Ltd.
Molding machine cylinder temperature: melting point (Tm) of semi-aromatic polyamide resin (A) + 15 ° C.
Mold temperature: Tg of semi-aromatic polyamide resin (A) + 20 ° C

(Load deflection temperature)
Using the following injection molding machine, a test piece with a thickness of 3.2 mm adjusted under the following molding conditions was fixed to a span of 100 mm, and a pressure of 1.8 MPa was applied from 35 ° C. at a heating rate of 120 ° C./hr. It was over. The temperature at which the deflection amount reached 0.254 mm was taken as the deflection temperature under load.
Molding machine: Sodick Plastic Co., Ltd. Tupal TR40S3A
Molding machine cylinder temperature: melting point (Tm) of semi-aromatic polyamide resin (A) + 15 ° C.
Mold temperature: Tg of semi-aromatic polyamide resin (A) + 20 ° C

(Creep deformation)
(1) Preparation of sample for creep test Using the following injection molding machine, a test piece having a length of 125 mm, a width of 13 mm, and a thickness of 1.6 mm adjusted under the following molding conditions was prepared.
Molding machine: Sodick Plastic Tupal TR40S3A
Molding machine cylinder temperature: (melting point (Tm) +15 of semi-aromatic polyamide resin (A)) ° C.
Mold temperature: Tg of semi-aromatic polyamide resin (A) + 20 ° C
(2) A load of 1.6 MPa was applied with a creep tester (manufactured by A & D Co., Ltd., model number: CP6-L-250) using the above sample under the condition of 80 ° C. × 95% RH. The amount of creep deformation after 24 hours was determined.

(Calcium chloride resistance)
Using the following injection molding machine, a square plate having a length of 120 mm, a width of 130 mm, and a thickness of 4 mm adjusted under the following molding conditions was produced.
Molding machine: Toshiba Molding machine Cylinder temperature: (Semi-aromatic polyamide resin (A) melting point (Tm) +15) ° C
Mold temperature: Tg of semi-aromatic polyamide resin (A) + 20 ° C
The produced square plate was cut as a test piece having a width of 10 mm in the injection flow direction, and the test piece was left in water at 80 ° C. for 24 hours. Thereafter, a 4 mm strain was applied to the center of the test piece to fix it, and a saturated calcium chloride aqueous solution was applied to the test piece. Thereafter, the heat cycle test was carried out 10 times under the following conditions (the following (i) and (ii) were carried out alternately).
(I) Leave at 100 ° C. for 2 hours, (ii) Leave at room temperature for 1 hour. After heat cycle, check for cracks on the test piece. The case where a crack occurred was evaluated as “x”.

  As shown in Table 3, a semi-aromatic polyamide resin (A) containing 50 mol% or more of terephthalic acid component units with respect to all dicarboxylic acid component units and having a glass transition temperature of 90 to 180 ° C., and a functional group In the polyamide resin compositions (Examples 1 to 8) containing the olefin polymer (B) containing 0.03 to 2.0% by mass of the structural unit, the creep deformation amount is small, and IZOD impact strength and tensile strength. Excellent results were obtained in both bending strength. In particular, when the amount of the semi-aromatic polyamide resin (A) was 75% by mass or more of the polyamide resin composition (Examples 1 to 7), the creep deformation amount was particularly small. When the aromatic polyamide resin (A) is contained in an amount of 75% by mass, it is presumed that the heat resistance is high and the deformation due to heat is small.

  On the other hand, when the amount of terephthalic acid contained in the semi-aromatic polyamide resin (A) decreases and the glass transition temperature of the semi-aromatic polyamide resin (A) decreases (Comparative Example 1), the amount of creep deformation increases, and further IZOD Impact strength was low. In addition, the deflection temperature under load decreased. Since the amount of terephthalic acid is small, it is presumed that the heat resistance and rigidity of the polyamide resin composition are low, deformation due to heat occurs, and mechanical strength is low.

  Moreover, when the functional group bond amount in a modified olefin polymer (B) is 2.5 mass% (comparative example 2), and when the said functional group bond amount is 0.03-2.0 mass% ( In particular, the amount of creep deformation increased compared with Example 4). It is presumed that when the functional group bond amount is excessive, the polyamide reacted with the modified olefin polymer is excessively present, crystallization of the polyamide is inhibited, and the amount of creep deformation of the resin composition is increased.

  Moreover, when the functional group bond amount in the modified olefin polymer (B) is 0.01% by mass (Comparative Example 3), when the functional group bond amount is 0.03 to 2.0% by mass (particularly, Compared with Example 4), not only the creep deformation amount increased, but also the IZOD impact degree decreased greatly. Moreover, tensile strength, bending strength, etc. also decreased. Since the amount of functional group bonding is too small, the semi-aromatic polyamide resin (A) and the modified olefin polymer (B) are not sufficiently dispersed, and the characteristics (heat resistance and impact resistance) of each resin are exhibited. I guess it was difficult.

  Furthermore, the polyamide resin composition containing the aliphatic polyamide resin (A′-1) had a low IZOD impact strength and a low deflection temperature under load. Furthermore, the amount of creep deformation was also large (Comparative Example 4). In the comparative example, it is surmised that the aliphatic polyamide resin (A′-1) has a low glass transition temperature and also has a low rigidity, so that it is difficult to obtain sufficient performance. In Comparative Example 4, the calcium chloride resistance was also low. Since the aliphatic polyamide resin (A′-1) has high hydrophilicity, it is presumed that calcium chloride is easily attached and cracks are likely to occur.

  The aiming nut obtained from the polyamide resin composition for aiming nut of the present invention has little dimensional change even when exposed to heat, and can maintain good slidability with the aiming screw. Furthermore, it has high resistance to vibrations against vehicle travel. Therefore, it can be used stably over a long period of time.

DESCRIPTION OF SYMBOLS 1 Lamp housing 2 Light source 3 Reflector 4 Aiming nut 5 Aiming screw 100 Transparent conductor

Claims (10)

A semi-aromatic polyamide resin (A) composed of a dicarboxylic acid component unit and an aliphatic diamine component unit;
A modified olefin polymer (B) containing a functional group structural unit containing a hetero atom;
A polyamide resin composition comprising:
The semi-aromatic polyamide resin (A) contains 50 mol% or more of terephthalic acid component units with respect to the total number of moles of the dicarboxylic acid component units,
The semi-aromatic polyamide resin (A) has a glass transition temperature measured by DSC of 90 ° C. to 180 ° C.,
The modified olefin polymer (B) contains 0.03-2.0% by mass of the functional group structural unit with respect to the total mass of the modified olefin polymer (B), and a polyamide resin composition for an aiming nut of a vehicle lamp object. 2. The aiming nut for a vehicle lamp according to claim 1, wherein the aliphatic diamine component unit of the semi-aromatic polyamide resin (A) satisfies at least one of the following requirements (a1) and (a2): Polyamide resin composition.
(A1) A linear alkylenediamine component unit having 4 to 18 carbon atoms is contained in an amount of 40 to 100 mol% based on the total number of moles of the aliphatic diamine component unit. (A2) Side chain alkylene having 4 to 18 carbon atoms The diamine 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.   The vehicle lamp according to claim 2, wherein the side chain alkylenediamine component unit is at least one of a 2-methyl-1,8-octanediamine component unit and a 2-methyl-1,5-pentadiamine component unit. A polyamide resin composition for aiming nuts.   The polyamide resin composition for aiming nuts of a vehicle lamp according to claim 1, wherein the aliphatic diamine component of the semi-aromatic polyamide resin (A) includes a 1,6-diaminohexane component unit.   The vehicle lamp according to claim 1, wherein the aliphatic diamine component of the semi-aromatic polyamide resin (A) includes a 1,6-diaminohexane component unit and a 2-methyl-1,5-pentadiamine component unit. Polyamide resin composition for aiming nuts.   The vehicle lamp according to claim 1, wherein the aliphatic diamine component of the semi-aromatic polyamide resin (A) includes a 1,9-nonanediamine component unit and a 2-methyl-1,8-octanediamine component unit. Polyamide resin composition for aiming nuts. The dicarboxylic acid component unit of the semi-aromatic polyamide resin (A) further comprises an isophthalic acid component unit;
The polyamide resin composition for an aiming nut of a vehicle lamp according to claim 1, wherein the aliphatic diamine component unit of the semi-aromatic polyamide resin (A) is an alkylene diamine component having 4 to 15 carbon atoms. The molar ratio of the terephthalic acid component unit to the isophthalic acid component unit is 60/40 to 99.9 / 0.1, and the aliphatic diamine component unit is a 1,6-diaminohexane component unit. A polyamide resin composition for an aiming nut of a vehicle lamp according to claim 7. Containing 75 to 97% by mass of the semi-aromatic polyamide resin (A),
The modified olefin polymer (B) is contained in an amount of 3 to 25% by mass (provided that the total of the semi-aromatic polyamide resin (A) and the modified olefin polymer (B) is 100% by mass). The polyamide resin composition for aiming nuts of the vehicle lamp according to any one of 8.   The aiming nut containing the polyamide resin composition for aiming nuts of the vehicle lamp as described in any one of Claims 1-9.

Images