JP2013095793A - Polyamide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition capable of producing a rigid molded product which has high impact-resistance, is improved in low water-absorption properties, chemical resistance, hydrolysis resistance and the like in comparison with conventional nylon-6 and nylon-66-based compositions, has a wider moldable temperature range than a polyamide resin composition using a 1,6-hexanediamine alone as a diamine component, and is excellent in melt moldability and further increased in molecular weight.SOLUTION: The polyamide resin composition includes a polyamide resin (component A) and an impact improver (component B). The component A is produced by binding a unit derived from a dicarboxylic acid to a unit derived from a diamine, wherein the dicarboxylic acid includes an oxalic acid (compound a), the diamine includes a 1,6-hexanediamine (compound b) and a 2-methyl-1,5-pentanediamine (compound c), and the molar ratio of the compound b to the compound c is 99:1 to 50:50.

Description

  The present invention relates to a novel polyamide resin composition. Specifically, it is a polyamide resin composition containing a polyamide resin (component A) and an impact modifier (component B), has high impact resistance, and is compared with conventional nylon 6 and nylon 66 series compositions. And excellent in low water absorption, chemical resistance, hydrolysis resistance, etc., and has a wider moldable temperature range than a polyamide resin composition using 1,6-hexanediamine alone as a diamine component, and excellent in melt moldability, Further, the present invention relates to a polyamide resin composition capable of producing a tough molded body capable of increasing the molecular weight.

Hereinafter, the name of the polyamide resin may be based on JIS K 6920-1.
Crystalline polyamide resins represented by nylon 6 (PA6), nylon 66 (PA66), etc. are widely used as textiles for clothing, industrial materials, or general-purpose engineering plastics because of their excellent properties and ease of melt molding. However, on the other hand, problems such as changes in physical properties due to water absorption, acid, high-temperature alcohol, deterioration in hot water, etc. have been pointed out, and polyamides with excellent low water absorption, chemical resistance, hydrolysis resistance, etc. There is an increasing demand for resins.

  A polyamide resin using oxalic acid as a dicarboxylic acid component is called a polyoxamide resin, and is known to have a higher melting point and lower water absorption than other polyamide resins having the same amino group concentration (Patent Document 1). It is expected to be used in fields where the use of conventional polyamides, where changes in physical properties have become a problem, is difficult.

  So far, polyoxamide resins using various aliphatic linear diamines as diamine components have been proposed. However, for example, a polyoxamide resin using 1,6-hexanediamine as a diamine component has a melting point (about 320 ° C.) higher than the thermal decomposition temperature (1% weight loss temperature in nitrogen; about 310 ° C.) (non-patent document). 1) Melt polymerization and melt molding were difficult and could not withstand practical use.

  For a polyoxamide resin whose diamine component is 1,9-nonanediamine (hereinafter abbreviated as PA92), L. Franco et al. Discloses a production method and its crystal structure when diethyl oxalate is used as the oxalic acid source ( Non-patent document 2). The PA 92 obtained here is a polymer having an intrinsic viscosity of 0.97 dL / g and a melting point of 246 ° C., but only a low molecular weight substance that cannot form a tough molded article is obtained. In addition, JP-A-5-506466 discloses that PA92 having an intrinsic viscosity of 0.99 dL / g and a melting point of 248 ° C. was produced when dibutyl oxalate was used as the dicarboxylic acid ester ( Patent Document 2). In this case as well, there is a problem that only a low molecular weight body that cannot be formed into a tough molded body is obtained.

  On the other hand, parts used under harsh conditions such as electric tools, general industrial parts, machine parts, electronic parts, parts inside and outside the car, parts inside the engine room, car parts, etc. have low water absorption, chemical resistance and In addition to being excellent in hydrolysis resistance and the like, high impact resistance is required (for example, Patent Document 3).

The present inventors use oxalic acid as a dicarboxylic acid component, and a polyamide resin using 1,9-nonanediamine and 2-methyl-1,8-octanediamine in a specific ratio as a diamine component has low water absorption, It was disclosed that it is a polyamide resin (PA92C) having a wide melt molding temperature range and excellent properties (Patent Document 4).
In the above prior art documents, there is no specific disclosure of a polyoxamide resin using two kinds of diamines of 1,6-hexanediamine and 2-methyl-1,5-pentanediamine as a diamine component in a specific ratio.

JP 2006-57033 A Special table 5-506466 JP 2000-129122 A WO2008 / 072754

S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1988)

  The present invention has been made based on the above circumstances. The present invention has high impact resistance, and has low water absorption, chemical resistance and resistance compared to conventional nylon 6 and nylon 66-based compositions. Excellent hydrolyzability, etc., and has a wider moldable temperature range than a polyamide resin composition using 1,6-hexanediamine alone as a diamine component, and is excellent in melt moldability. Further, it is found in aliphatic linear polyoxamide resins. It is an object of the present invention to provide a polyamide resin composition that is excellent in mechanical properties at the time of water absorption and can produce a tough molded article without impairing low water absorption.

  As a result of intensive studies in order to solve the above problems, the present inventors have obtained oxalic acid diester as a oxalic acid source, 1,6-hexanediamine and 2-methyl-1,5-pentanediamine as diamine components. It has been found that the above-mentioned problems can be solved by using a polyamide resin composition comprising a polyamide resin comprising an impact modifier (hereinafter also referred to as “PX6”), and the present invention has been completed.

Specifically, the present invention relates to the following aspects.
(1) A polyamide resin composition comprising a polyamide resin (component A) and an impact modifier (component B),
The component A is composed of a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid (compound a);
The diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
The polyamide resin composition whose molar ratio of the said compound b and the said compound c is 99: 1-50: 50.

(2) The polyamide resin composition according to the above (1), comprising 10 to 100 parts by mass of an impact modifier (component B) with respect to 100 parts by mass of the polyamide resin (component A).
(3) A molded article of the polyamide resin composition according to the above (1) or (2).

  The polyamide resin composition comprising the polyamide resin of the present invention (component A) and the impact modifier (component B) has high impact resistance and is compared with conventional nylon 6 and nylon 66 series compositions. Low water absorption, chemical resistance and hydrolysis resistance, excellent mechanical properties at the time of water absorption, etc., and has a wider moldable temperature range than a polyamide resin composition using 1,6-hexanediamine alone as a diamine component, and melt molding It is possible to produce a tough molded body that is excellent in properties and can be increased in molecular weight.

[Component A]
(1) Configuration of Component A Component A, which is a polyamide resin in the present invention,
The dicarboxylic acid component is succinic acid and the diamine component consists of 1,6-hexanediamine and 2-methyl-1,5-pentanediamine,
A polyamide resin formed by bonding a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid (compound a);
The diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
The molar ratio of the compound b to the compound c is 99: 1 to 50:50,
Preferably, the relative viscosity ηr measured at 25 ° C. using a solution of Component A having a concentration of 1.0 g / dl in 96% sulfuric acid is 1.8 to 6.0.

  Component A uses compounds a, b and c, preferably polycondensation using a mixture thereof, so that it has a high molecular weight, a high melting point, a large difference between the melting point and the thermal decomposition temperature, and excellent melt moldability. Furthermore, it is excellent in chemical resistance, hydrolysis resistance and fuel barrier properties as compared with conventional polyamides without impairing the low water absorption seen in linear polyoxamide resins.

From the viewpoint of ensuring chemical resistance, hydrolysis resistance and fuel barrier properties, component A has a molar ratio of compound b to compound c:
Preferably, 99: 1 to 55:45 mol%,
More preferably, it is 99: 1-60: 40 mol%.
Hereinafter, the molar ratio of the compound b and the compound c also means the molar ratio of the unit derived from the compound b and the unit derived from the compound c in the component A.

When compound a (oxalic acid) is directly used as a raw material in the production of component A, compound a (succinic acid) itself is thermally decomposed, and the melting point of component A exceeds the thermal decomposition temperature. (Hereinafter, also referred to as oxalic acid source) and obtained by polycondensation of oxalic acid derived from the oxalic acid source and diamine. This oxalic acid is derived from an oxalic acid source such as oxalic acid diester, and any oxalic acid may be used as long as it has reactivity with an amino group.
As the oxalic acid source, oxalic acid diester is preferable from the viewpoint of suppressing side reactions in the polycondensation reaction. Dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) oxalate Examples thereof include oxalic acid diesters of aliphatic monohydric alcohols such as butyl, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, and oxalic acid diesters of aromatic alcohols such as diphenyl oxalate.
Among the oxalic acid diesters, oxalic acid diesters of aliphatic monohydric alcohols having more than 3 carbon atoms, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols are more preferable,
Among them, dibutyl oxalate and diphenyl oxalate are more preferable,
More preferred is dibutyl oxalate.

(2) Relative viscosity of component A
Using oxalic acid as compound a as the carboxylic acid component,
As the diamine component, 1,6-hexanediamine as compound b and 2-methyl-1,5-pentanediamine as compound c are polycondensed so that the melting point is preferably in the range of 200 to 330 ° C. Compared to a polyamide resin obtained by polycondensation of compound a and compound b with a melting point exceeding 330 ° C. (hereinafter also referred to as comparative component A2), in the melt polymerization in the post-polymerization step of component A described later, Since it is not necessary to use an excessively high temperature condition in which a side reaction occurs and inhibits high molecular weight, high molecular weight (increasing relative viscosity) is possible.
Therefore, Component A has an excellent melt moldability because it can increase the relative viscosity as compared with the conventional polyamide resin.
In view of avoiding the tendency of the molded product after melt molding to become brittle and lowering the physical properties, to avoid the tendency to increase the melt viscosity at the time of melt molding and deteriorate the molding processability, the relative viscosity ηr and the melt viscosity are more than a certain level. From the viewpoint of being suitable for uses such as automobile parts and electrical / electronic parts that are preferably high and not excessively high, a 96% concentrated sulfuric acid solution having a concentration of component A of 1.0 g / dl is used. The relative viscosity ηr measured at 25 ° C. is
Preferably it is 1.8-6.0,
More preferably, it is 1.8-4.5,
More preferably, it is 1.8-3.0,
More preferably 1.85 to 2.5,
More preferably, it may be 1.85 to 2.2.
In the melt polymerization in the post-polymerization step of component A described later, the relative viscosity ηr can be increased by increasing the degree of vacuum.

From the same viewpoint, the melt viscosity of component A is
Preferably 100 to 700 Pa · s,
More preferably 110-600 Pa · s,
More preferably, 120 to 500 Pa · s,
More preferably, 130 to 400 Pa · s,
More preferably, 150 to 300 Pa · s,
More preferably, 160 to 220 Pa · s,
More preferably, it is 170-200 Pa.s,

Furthermore, from the same viewpoint, the number average molecular weight of component A is
Preferably it is 10000-50000,
More preferably, it is 11000-40000,
More preferably, it is 11000-35000.

The number average molecular weight (Mn) is based on the signal intensity obtained from the 1H-NMR spectrum, for example, dibutyl oxalate as the oxalic acid source, 1,6-hexanediamine (compound b) and 2-methyl-1, as the diamine component. In the case of a polyamide produced using 5-pentanediamine (compound c) at a molar ratio of 90:10 [hereinafter abbreviated as PX6-2 (compound b / compound c = 90/10)], it is calculated by the following formula. did.
Mn = np × 170.21 + n (NH ₂ ) × 115.20 + n (OBu) × 129.13 + n (NHCHO) × 29.14
In addition, the measurement conditions of 1H-NMR are as follows.
・ Model used: Bruker Biospin AVANCE500
-Solvent: Bisulfuric acid-Integration frequency: 1024 times Each term in the above formula is defined as follows.
Np = Np / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
・ N (NH ₂ )
= N (NH ₂ ) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
・ N (NHCHO)
= N (NHCHO) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
・ N (OBu)
= N (OBu) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
Np = Sp / sp-N (NHCHO)
_{· N (NH2) = S (} NH 2) / s (NH 2)
N (NHCHO) = S (NHCHO) / s (NHCHO)
N (OBu) = S (OBu) / s (OBu)
However, each term has the following meaning.
Np: Total number of repeating units in the molecular chain excluding terminal units of PA62 (compound B / compound C = 90/10).
Np: the number of repeating units in the molecular chain per molecule.
Sp: PX6-2 (compound b / compound c = 90/10) excluding the signal based on the proton of the methylene group adjacent to the oxamide group in the repeating unit in the molecular chain (around 3.1 ppm) Integration value.
Sp: The number of hydrogens (4) counted in the integral value Sp.
* N (NH2): Total number of terminal amino groups of PX6-2 (compound b / compound c = 90/10).
N (NH2): number of terminal amino groups per molecule.
S (NH2): Integral value of a signal (around 2.6 ppm) based on the proton of the methylene group adjacent to the terminal amino group of PX6-2 (compound b / compound c = 90/10).
· S (NH2): integrated value S number of hydrogens counted in the (NH ₂₎ (2 pieces).
N (NHCHO): total number of terminal formamide groups of PX6-2 (compound b / compound c = 90/10).
N (NHCHO): number of terminal formamide groups per molecule.
-S (NHCHO): The integral value of the signal (7.8 ppm) based on the proton of the formamide group of PX6-2 (compound b / compound c = 90/10).
S (NHCHO): The number of hydrogens (one) counted in the integral value S (NHCHO).
N (OBu): the total number of terminal butoxy groups of PX6-2 (compound b / compound c = 90/10).
N (OBu): number of terminal butoxy groups per molecule.
S (OBu): integrated value of a signal (around 4.1 ppm) based on the proton of the methylene group adjacent to the oxygen atom of the terminal butoxy group of PX6-2 (compound b / compound c = 90/10).
S (OBu): The number of hydrogens (two) counted in the integral value S (OBu).

(3) Physical properties of component A Component A further changes the polycondensation ratio of compounds b and c,
The temperature difference (Td−Tm) is large compared to the comparative component A2, and small compared to the polyamide resin obtained by polycondensation of the compound a and the compound c (hereinafter also referred to as the comparative component A1).
The melting point Tm is low compared to the comparative component A2, high compared to the comparative component A1,
1% weight loss temperature Td is higher than the comparative component A1,
The saturated water absorption rate can be smaller than the comparative component A2 and larger than the comparative component A1.

That is, the component A is compared with the conventional polyoxamide resin,
Relative viscosity ηr (high molecular weight),
Moldable temperature range estimated from the temperature difference (Td−Tm),
Heat resistance estimated from melting point Tm,
Both melt moldability estimated from melt viscosity and low water absorption can be sufficiently secured.

  Component A has sufficient chemical resistance, resistance to resistance due to the high polymerization ratio (molar ratio) of compound b after sufficiently ensuring the moldable temperature range, heat resistance, melt moldability and low water absorption. Excellent hydrolyzability and fuel barrier properties.

From the viewpoint of sufficiently ensuring all of the moldable temperature range, heat resistance, melt moldability and low water absorption,
Tm is preferably 260 to 330 ° C, more preferably 265 to 330 ° C,
Td is preferably 341 to 370 ° C, more preferably 345 to 370 ° C, still more preferably 350 to 365 ° C,
The temperature difference (Td−Tm) is preferably 10 to 95 ° C., more preferably 20 to 95 ° C., still more preferably 25 to 95 ° C.,
The saturated water absorption is preferably 0 to 2.4, more preferably 1 to 2.4, still more preferably 2 to 2.4, and still more preferably 2.3 to 2.4.

(4) Production of Component A Component A can be produced using any method known as a method for producing polyamide, but from the viewpoint of high molecular weight and productivity,
Preferably, it is obtained by polycondensation reaction of diamine and oxalic acid diester batchwise or continuously.
More preferably, the diamine and the oxalic acid diester are obtained by a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step, or a pressure polymerization method described in WO2008-072754.
More preferable two-stage polymerization method and pressure polymerization method are specifically shown by the following operations.

(4-1) Two-stage polymerization method (i) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then diamine (compounds b and c) and oxalic acid diester which is the oxalic acid source of compound a are mixed. When mixing, a solvent in which both the diamine and the oxalic acid diester are soluble may be used. As a solvent in which both the diamine component and the oxalic acid source component are soluble, toluene, xylene, trichlorobenzene, phenol, trifluoroethanol, and the like can be used, and toluene is particularly preferably used. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid diester is added with respect to this.
At this time, the charging ratio between the oxalic acid diester and the diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), from the viewpoint of increasing the molecular weight. Ratio), more preferably 0.99 to 1.01 (molar ratio).

  The temperature in the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C., preferably 100 to 140 ° C. The reaction time at the final temperature reached is 3-6 hours.

(Ii) Post-polycondensation step: In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. From the final ultimate temperature of the pre-polycondensation step in the temperature rising process, that is, preferably from 80 to 150 ° C., finally,
The temperature is preferably 295 ° C. or higher and 350 ° C. or lower, more preferably 298 ° C. or higher and 345 ° C. or lower, more preferably 298 ° C. or higher and 340 ° C. or lower.
It is preferable to carry out the reaction while keeping the temperature rising time preferably 1 to 8 hours, more preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. A preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa to 0.1 MPa.

(4-2) Pressurized polymerization method First, diamine is placed in a pressure vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, the oxalic acid compound is injected into the pressure vessel while maintaining the sealed pressure state at the reaction temperature, and the polycondensation reaction is started. The reaction temperature is not particularly limited as long as the polyamide produced by the reaction of the diamine and the oxalic acid compound can maintain a slurry or solution state and does not thermally decompose. For example, in the case of Component a, the reaction temperature is preferably 150 ° C to 250 ° C. Here, the charging ratio of dibutyl oxalate and diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), in terms of the molar amount of dibutyl oxalate / total molar amount of diamine. More preferably, it is 0.99 to 1.01 (molar ratio).
Next, while maintaining the inside of the pressure vessel in a sealed pressure state, the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of Component a, since the melting point is 245 to 300 ° C., the temperature is raised to 250 to 350 ° C., preferably 255 to 340 ° C., more preferably 260 to 335 ° C. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. A preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa to 0.1 MPa.

(6) Component which can be used as dicarboxylic acid in component A In component A, other dicarboxylic acid components other than compound a can be used within a range not impairing the effects of the present invention.
As other dicarboxylic acid components other than compound a (oxalic acid),
Malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid , Aliphatic dicarboxylic acids such as suberic acid,
In addition, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid,
Further, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydi Aromatic dicarboxylic acids such as acetic acid, dibenzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid These may be added alone, or any mixture thereof may be added during the polycondensation reaction.
Furthermore, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used as long as melt molding is possible.
When other dicarboxylic acid components are used, the proportion thereof is 25 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, and more preferably 5 mol% or less with respect to compound a (succinic acid). More preferably, it is more preferably 0 mol% (that is, the dicarboxylic acid component consists only of compound a). The molar ratio of the other dicarboxylic acid component to the compound a (succinic acid) also means the molar ratio of the unit derived from the compound a and the unit derived from the other dicarboxylic acid component in the component A.

In component A, other diamine components other than compounds b and c can be used within the range not impairing the effects of the present invention.
As other diamine components other than 1,6-hexanediamine and 2-methyl-1,5-pentanediamine, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,9-nonanediamine, 2-methyl-1, 8-octanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine,
1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5- Aliphatic diamines such as methyl-1,9-nonanediamine,
Furthermore, alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, and isophoronediamine,
Furthermore, aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylether ,
These may be added alone, or any mixture thereof may be added during the polycondensation reaction.

  When other diamine components are used, the proportion thereof is 25 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, still more preferably 5 mol% or less, with respect to compounds b and c. More preferably, it is 0 mol% (that is, the diamine component consists only of compounds b and c). In addition, the molar ratio of the other diamine component with respect to the compounds b and c also means the molar ratio of the units derived from the compounds b and c and the units derived from the other diamine components in the component A.

[Impact modifier (component B)]
The impact modifier (component B) is a component that improves the impact resistance of the polyamide resin (component A).
The impact modifier (component B) is not particularly limited as long as it improves the impact resistance of the polyamide resin (component A), and examples thereof include elastomers. As the said elastomer, it is preferable that the bending elastic modulus measured based on ASTM D-790 is 500 Mpa or less. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.

  As the impact modifier (component B), (ethylene and / or propylene) · α-olefin copolymer, (ethylene and / or propylene) · (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid) Ester) copolymers, ionomer polymers, aromatic vinyl compound / conjugated diene compound block copolymers, and these can be used alone or in combination.

  The above (ethylene and / or propylene) · α-olefin copolymer is a polymer obtained by copolymerizing ethylene and / or propylene and an α-olefin having 3 or more carbon atoms, and α- having 3 or more carbon atoms. Examples of olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 4-methyl-1-butene, 3-methyl-1-pentene, 3- Ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1 Pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof.

  In addition, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8- Decatriene (DMDT), dicyclopentadiene, cyclohexadiene, dicyclooctadiene, methylene norbornene, 5-vinyl norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl-5-isopropylene-2-norbornene, 2,3-diisopropylidene- - norbornene, 2-ethylidene-3-isopropylidene-5-norbornene may be copolymerized non-conjugated diene polyene such as 2-propenyl-2,2-norbornadiene.

  The above (ethylene and / or propylene) · (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer is ethylene and / or propylene and α, β-unsaturated carboxylic acid and A polymer obtained by copolymerizing an unsaturated carboxylic acid ester monomer. Examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid, and α, β-unsaturated. Examples of saturated carboxylic acid ester monomers include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, decyl esters, and the like of these unsaturated carboxylic acids. A mixture is mentioned. Among these, a maleic acid-modified ethylene-butene copolymer and / or a maleic acid-modified ethylene-propylene copolymer is preferable from the viewpoint of improving impact resistance while maintaining strength during water absorption.

  The ionomer polymer is obtained by ionizing at least part of the olefin and the carboxyl group of the α, β-unsaturated carboxylic acid copolymer by neutralization of metal ions. Ethylene is preferably used as the olefin, and acrylic acid and methacrylic acid are preferably used as the α, β-unsaturated carboxylic acid, but are not limited to those exemplified here, The body may be copolymerized. In addition, metal ions include alkali metals and alkaline earth metals such as Li, Na, K, Mg, Ca, Sr, Ba, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, Cd, etc. Can be mentioned.

  The aromatic vinyl compound / conjugated diene compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene polymer block, and the aromatic vinyl compound polymer block. And a block copolymer having at least one conjugated diene polymer block. In the block copolymer, the unsaturated bond in the conjugated diene polymer block may be hydrogenated.

  The aromatic vinyl compound polymer block is a polymer block mainly composed of structural units derived from an aromatic vinyl compound. In this case, aromatic vinyl compounds include styrene, α-methyl styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, 2,4-dimethyl styrene, 2,6-dimethyl styrene, vinyl naphthalene and vinyl. Anthracene, 4-propyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned. It is possible to have a structural unit consisting of one or more of the above monomers. In addition, the aromatic vinyl compound-based polymer block may optionally have a structural unit composed of a small amount of other unsaturated monomer.

  Conjugated diene polymer blocks are 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3- A polymer block formed from one or more conjugated diene compounds such as hexadiene, and hydrogenated aromatic vinyl compound / conjugated diene block copolymer is unsaturated in the conjugated diene polymer block. A part or all of the bonding portion is saturated by hydrogenation. Here, the distribution in the polymer block mainly composed of conjugated diene may be random, tapered, partially blocky, or any combination thereof.

  The molecular structure of the aromatic vinyl compound / conjugated diene block copolymer and the hydrogenated product thereof may be linear, branched, radial, or any combination thereof. Among them, in the present invention, as an aromatic vinyl compound / conjugated diene block copolymer and / or a hydrogenated product thereof, one aromatic vinyl compound polymer block and one conjugated diene polymer block are linear. Triblock copolymer in which three polymer blocks are linearly bonded in the order of bonded diblock copolymer, aromatic vinyl compound polymer block-conjugated diene polymer block-aromatic vinyl compound polymer block And one or more of these hydrogenated products are preferably used, and unhydrogenated or hydrogenated styrene / butadiene copolymer, unhydrogenated or hydrogenated styrene / isoprene copolymer, unhydrogenated or hydrogenated. Styrene / isoprene / styrene copolymer, unhydrogenated or hydrogenated styrene / butadiene / styrene copolymer, unhydrogenated or hydrogenated styrene / (isoprene / butylene) Diene) / styrene copolymer, and the like.

  Further, (ethylene and / or propylene) · α-olefin copolymer, (ethylene and / or propylene) · (α, β-unsaturated carboxylic acid and / or unsaturated) used as an impact modifier (component B) As the block copolymer of a carboxylate ester-based copolymer, an ionomer polymer, and an aromatic vinyl compound and a conjugated diene compound, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such a component, a functional group having affinity for the polyamide resin is included in the molecule.

Examples of functional groups having an affinity for polyamide resin include carboxylic acid groups, carboxylic anhydride groups, carboxylic acid ester groups, carboxylic acid metal bases, carboxylic acid imide groups, carboxylic acid amide groups, and epoxy groups. . Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4- Cyclohexene-1,2-dicarboxylic acid, endobicyclo [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, acrylic Ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, Itaconic anhydride, no Citraconic acid, Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, acrylic Examples thereof include glycidyl acid, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid.
From the viewpoint of improving impact resistance while maintaining strength at the time of water absorption, Component B is (ethylene and / or propylene) .α-olefin copolymer, (ethylene and / or propylene). (Α, β- One or more polymers selected from the group consisting of (unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) -based copolymer and ionomer are preferable, maleic acid-modified ethylene-butene copolymer and maleic acid-modified ethylene One or more polymers selected from the group consisting of a propylene copolymer, an epoxy-modified styrene block copolymer, and an ionomer are more preferable.

[Polyamide resin composition]
The polyamide resin composition of the present invention includes a polyamide resin (component A) and an impact modifier (component B).
In the polyamide resin composition of the present invention, the amount of the impact modifier (component B) is not particularly limited as long as the impact resistance of the polyamide resin (component A) is improved. A) The amount of the impact modifier (component B) with respect to 100 parts by mass is preferably 10 to 100 parts by mass. When the amount of the impact modifier (component B) decreases, the impact resistance does not improve. On the other hand, when the impact modifier (component B) increases, the effect of the wide moldable temperature range of the polyamide resin composition is not recognized. From the viewpoint of impact resistance and moldable temperature range, the content of component A in the polyamide resin composition is preferably 50 to 95% by mass, more preferably 60 to 90% by mass, and still more preferably 70 to 90% by mass. The amount of the impact modifier (component B) with respect to 100 parts by mass of the polyamide resin (component A) is preferably 10 to 100 parts by mass, more preferably 10 to 50 parts by mass, and particularly preferably 10 -30 mass parts.

  The polyamide resin composition of the present invention can further contain the following components as optional components in addition to the polyamide resin (component A) and the impact modifier (component B).

(1) Other polymer The dicarboxylic acid component used in the present invention comprises oxalic acid, the diamine component comprises 1,6-hexanediamine and 2-methyl-1,5-pentanediamine, and 1,6-hexanediamine The polyamide resin having a molar ratio with 2-methyl-1,5-pentanediamine of 99: 1 to 50:50 can be partially substituted with other polymer components as long as the effects of the present invention are not impaired. . Examples of other polymer components include other polyamides such as polyoxamide, aromatic polyamide, aliphatic polyamide, alicyclic polyamide, and polymers other than polyamide, such as thermoplastic polymers and elastomers.

  The substitution ratio by the other polymer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass with respect to 100 parts by mass of Component A. More preferably, it is 0-30 mass parts.

(2) Additives Other additives can be added to the polyamide resin composition of the present invention as long as the effects of the present invention are not impaired. For example, pigments, dyes, colorants, heat agents, antioxidants, weathering agents, UV absorbers, light stabilizers, lubricants, crystal nucleating agents, crystallization accelerators, mold release agents, antistatic agents, plasticizers, Examples thereof include stabilizers such as copper compounds, antistatic agents, flame retardants, glass fibers, lubricants, fillers, reinforcing fibers, and the like.

  As the heat-resistant agent, a copper-containing compound is preferable, and copper halides such as copper iodide and copper bromide are particularly preferable. The addition amount of the compound is preferably an addition amount of 10 to 1000 ppm as the copper content in the polyamide resin composition of the present invention. Usually, an alkyl halogen compound is further added as a heat-resistant auxiliary agent.

  In addition, a phenolic antioxidant can be added to the polyamide resin composition of the present invention. The said antioxidant and the said heat-resistant agent can also be used together.

  Examples of the phenol-based oxidizing agent include triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol bis [3- (3, 5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 5-di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, N, N'-hexamethylenebis (3,5-di -T-butyl-4-hydroxy-hydrocinnamamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t Butyl-4-hydroxybenzyl) benzene, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2, 4,8,10-tetraoxaspiro [5,5] undecane and the like, among others, pentaerythrityl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide).

  A phosphorus-based and / or sulfur-based antioxidant adjuvant can be added together with the phenol-based oxidizing agent. Examples of the phosphorus-based antioxidant auxiliary agent include tris (2,4-di-t-butylphenyl) phosphite, 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [ d, f] [1,3,2] dioxaphosphine 6-yl] oxy] -N, N-bis [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl)] Dibenzo [d, f] [1,3,2] dioxaphosphenine 6-yl] oxy] -ethyl] ethanamine, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphos Among them, 2-[[2,4,8,10-tetrakis (1,1-dimethylether) dibenzo [d, f] [1,3,2] dioxaphosphine 6- Yl] oxy] -N, N-bis [2 And [[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine6-yl] oxy] -ethyl] ethanamine. .

  Examples of sulfur-based antioxidant adjuvants include 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tetrakis [methylene-3- (dodecylthio) propionate]. Mention may be made of methane and the like.

  The method for adding the other polymer and the additive is not particularly limited as long as each of them can be dispersed in the polyamide resin, and the polyamide resin can be added to the polyamide resin at any time without impairing its effect. Can be added. For example, the other polymers and additives can be added immediately after the post polycondensation step of the polyamide resin.

[Production method of polyamide resin composition]
The production method of the polyamide resin composition of the present invention is not particularly limited, and is performed by melt-kneading the polyamide resin (component A) and the impact modifier (component B) with a single-screw, bi-screw or multi-screw extruder. It is possible to use other kneaders. Furthermore, the above-mentioned other polymers and additives can be added at the time of melt-kneading the polyamide resin (component A) and the impact modifier (component B).

  The polyamide resin composition of the present invention can be molded into various molded products by known molding methods such as injection molding, extrusion molding, blow molding, vacuum molding, press molding and the like. It is particularly useful in the fields of injection molding and blow molding.

  In the polyamide resin composition of the present invention, the polyamide resin (component A) preferably forms a matrix phase. When the polyamide resin (component A) forms a continuous phase, the heat resistance and mechanical properties are excellent. On the other hand, when the polyamide resin (component A) forms a discontinuous phase, the mechanical properties and heat resistance of the resulting resin composition are excellent. Tend to be low.

  The polyamide resin composition of the present invention has a wide moldable temperature range, such as automobile-related parts, in particular, interior / exterior parts, engine room interior parts, automobile electrical parts, etc., and electrical, electronic parts, electric tools, and general industries. Suitable for machine parts such as parts, gears and cams.

  Furthermore, the polyamide resin composition of the present invention is used for, for example, thin electrical and electronic parts such as motor insulators and coil bobbins, molded products having a thin part, such as precision gear parts, bearing retainers and retainer housings. Can do. For example, clips, bands, parts that require snap fit, various sealing materials, housing materials, and the like that are used in an engine room of an automobile under high temperature and high humidity.

  Although the polyamide resin composition of the present invention is not particularly limited, for example, gear, cam, slider, lever, arm, clutch, felt clutch, idler gear, pulley, roller, roller, key stem, key top, shutter Office automation equipment such as reels, shafts, joints, shafts, bearings, guides, and other mechanical parts, outsert molding resin parts, insert molding resin parts, chassis, trays, side plates, printers and copiers Parts, video tape recorders, digital video cameras, cameras and parts for digital cameras, video equipment parts, cassette players, CD players, DVD players and other music players, CD-ROM, CD-R, DVD-ROM , DVD -R and other optical disk drives, other optical disk drives, automotive parts such as gasoline tanks, fuel pump modules, valves, gasoline tank flanges and other fuel parts, door locks, door handles, window regulators, speaker grills, etc. Suitable for seat belt peripheral parts typified by representative door parts, seat belt slip rings, press buttons and the like. Further, it can be suitably used as industrial parts such as toys, fasteners, chains, conveyors, buckles, sports equipment, vending machines, furniture, musical instruments, and housing equipment.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited to these Examples.

[Physical property measurement, molding, evaluation method]
The characteristic value was measured by the following method.
(1) Relative viscosity (ηr)
ηr was measured at 25 ° C. with an Ostwald viscometer using a 96% sulfuric acid solution of polyamide (concentration: 1.0 g / dl).

(2) Melting point (Tm):
Tm was measured under a nitrogen atmosphere using a PYRIS Diamond DSC manufactured by PerkinELmer.
Tm in Production Examples 1 and 2 and Comparative Production Example 1 was raised from 30 ° C. to 350 ° C. at a rate of 10 ° C./min (called temperature rise first run), held at 350 ° C. for 3 minutes, and then −100 The temperature was lowered to 10 ° C./min at a rate of 10 ° C./min (referred to as a temperature-decreasing first run), and then raised to 350 ° C. at a rate of 10 ° C./min (referred to as a temperature-rising second run).
Production Examples 3 to 5, Tm of Nylon 6 and Nylon 66 were heated from 30 ° C. to 310 ° C. at a rate of 10 ° C./min (called temperature rising first run), held at 310 ° C. for 3 minutes, − The temperature was decreased to 100 ° C. at a rate of 10 ° C./min (referred to as a temperature decrease first run), and then the temperature was increased to 310 ° C. at a rate of 10 ° C./min (referred to as a temperature increase second run).
The endothermic peak temperature of the elevated temperature second run was defined as Tm.

(3) 1% weight loss temperature (Td)
Td was measured by thermogravimetric analysis (TGA) using THERMOGRAVIMETRIC ANALYZER TGA-50 manufactured by Shimadzu Corporation. The temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./min under a nitrogen stream of 20 ml / min, and Td was measured.
(4) Melt viscosity The melt viscosity is 300 ° C (Production Examples 3 to 5), 340 in nitrogen with a 25 mm cone plate attached to a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan. The measurement was performed under the conditions of ° C. (Production Examples 1 and 2, Comparative Production Example 1), 260 ° C. when nylon 6 was used, 290 ° C. when nylon 66 was used, and a shear rate of 0.1 s ⁻¹ .

(5) Film formation Film formation was performed using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. In a reduced pressure atmosphere of 500 to 700 Pa, 300 ° C. (Production Examples 3 to 5), 340 ° C. (Production Examples 1 and 2, Comparative Production Example 1), 260 ° C. when nylon 6 is used, and 290 when nylon 66 is used. After being melted by heating at 5 ° C. for 5 minutes, the film was formed by pressing at 5 MPa for 1 minute. Next, the reduced-pressure atmosphere was returned to normal pressure, and then cooled and crystallized at room temperature of 5 MPa for 1 minute to obtain a film.

(6) Saturated water absorption rate A film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass of about 0.05 g) formed under the conditions of (5) above is immersed in ion-exchanged water at 23 ° C., and every predetermined time. The film was taken out and the mass of the film was measured. When the rate of increase in the film mass lasts 3 times within the range of 0.2%, it is judged that the absorption of moisture into the polyamide resin film has reached saturation, and the mass (Xg) of the film before being immersed in water The saturated water absorption (%) was calculated from the mass (Yg) of the film when reaching saturation with the following equation (1).
Saturated water absorption (%) = 100 × (Y−X) / X (1)

(7) Chemical resistance After immersing the film molded under the above condition (5) in the chemicals listed below for 7 days, changes in weight residual ratio (%) and appearance of the film were observed. Tests were conducted on samples immersed in concentrated hydrochloric acid, 64% sulfuric acid, 30% NaOH aqueous solution, and 5% K ₂ MnO ₄ at 23 ° C. and benzyl alcohol at 50 ° C.

(8) Hydrolysis resistance The film molded under the above condition (5) is put in an autoclave, and water (pH = 7), 0.5 mol / l sulfuric acid (pH = 1) or 1 mol / l sodium hydroxide aqueous solution ( Within pH = 14), the residual weight ratio (%) and the appearance change after treatment at 121 ° C. for 60 minutes were examined.

(9) Mechanical properties [1] to [4] shown below are measured using the following test pieces at a resin temperature of 300 ° C. (Production Examples 3 to 5, Examples 2, 4, 5 and 7), 340 ° C. ( Production Examples 1-2, Examples 1, 3, 6 and 8), when nylon 6 is used, 260 ° C., when nylon 66 is used, 290 ° C., and mold temperature is 80 ° C. It was performed using. The ones evaluated at 23 ° C. without conditioning immediately after molding are shown in the table as dry, and the ones evaluated at 23 ° C. after conditioning at a humidity of 65% and a temperature of 23 ° C. after molding are shown in the table.
[1] Bending test (flexural modulus): Measured at 23 ° C. in accordance with ASTM D790 using a test piece having a test piece size of 127 mm × 12.7 mm × 3.2 mm.
[2] Deflection temperature under load: Measured with a load of 1.82 MPa in accordance with ASTM D648 using a test piece with a test piece size of 127 mm × 12.7 mm × 3.2 mm.
[3] Izod impact strength: Measured at 23 ° C. in accordance with ASTM D256 using a test piece having a test piece size of 3.2 mm × 12.7 mm × 127 mm.
[4] Tensile strength: Measured according to ASTM D638 using a Type I test piece described in ASTM D638.

(10) Water absorption rate The water absorption rate (%) was calculated according to the measurement method of (6) saturated water absorption rate, except that it was placed under conditions of 23 ° C. and humidity 65% RH.

(11) Resistance to calcium chloride The film molded under the condition (5) was immersed in a saturated calcium chloride aqueous solution at 23 ° C. After one day, the appearance of the film was visually observed to evaluate the presence or absence of cracks.

[Production Example 1: Polyamide resin (A): PX6-1]
A pressure vessel with an internal volume of about 150 liters equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected to the diaphragm pump, nitrogen gas inlet, pressure relief port, pressure regulator and polymer outlet , 6-hexanediamine 15.407 kg (132.58 mol) and 2-methyl-1,5-pentanediamine YYY 811.1 g (6.98 mol) (1,6-hexanediamine and 2-methyl-1, Operation in which the molar ratio of 5-pentanediamine is 95: 5), the inside of the pressure vessel is pressurized to 0.5 MPa with nitrogen gas having a purity of 99.9999%, and then the nitrogen gas is released to normal pressure. Was repeated 5 times, and after nitrogen substitution, the system was heated while stirring under a sealing pressure. After the temperature of dibutyl oxalate was raised to 80 ° C. over about 30 minutes, 28.230 kg (139.56 mol) of dibutyl oxalate was placed in the reaction vessel with a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes. The temperature was raised simultaneously with the supply. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 330 ° C. over 2 hours. Meanwhile, the internal pressure was adjusted to 0.75 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 330 ° C., butanol was extracted from the pressure relief port over about 20 minutes, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, and the reaction was carried out for 4.5 hours. Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel. The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer. The obtained polyamide was a white tough polymer with ηr = 1.95.

[Production Example 2: Polyamide resin (A): PX6-2]
A mixture of 14.717 kg (126.64 mol) of 1,6-hexynediamine and 1.635 kg (14.07 mol) of 2-methyl-1,5-pentanediamine (1,6-hexanediamine and 2-methyl-1, Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of 5-pentanediamine was 90:10) and 28.462 kg (140.71 mol) of dibutyl oxalate was charged. The obtained polyamide was a white tough polymer with ηr = 2.05.

[Production Example 3: Polyamide resin (A): PX6-3]
A mixture of 12.16 kg (104.64 mol) of 1,6-hexanediamine and 5.212 kg (44.85 mol) of 2-methyl-1,5-pentanediamine (1,6-hexanediamine and 2-methyl-1, The molar ratio of 5-pentanediamine is 70:30), and 30.238 kg (149.49 mol) of dibutyl oxalate is fed into the reaction vessel through a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes. At the same time, the temperature rose. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 290 ° C. over 1.5 hours. Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 290 ° C., butanol was extracted from the pressure relief port over about 20 minutes, and the internal pressure was brought to normal pressure. Starting from normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was brought to 310 ° C. over about 1 hour, and the reaction was carried out at 310 ° C. for 1.5 hours. . Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel. The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer. The obtained polyamide was a white tough polymer with ηr = 2.40.

[Production Example 4: Polyamide resin (A): PX6-4]
A mixture of 10.294 kg (88.583 mol) of 1,6-hexanediamine and 6.863 kg (59.057 mol) of 2-methyl-1,5-pentanediamine (1,6-hexanediamine and 2-methyl-1 , 5-pentanediamine in a molar ratio of 60:40), and 29.864 kg (147.64 mol) of dibutyl oxalate was placed in the reaction vessel with a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes. The temperature was raised simultaneously with the supply. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 275 ° C. over 1.5 hours. Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 270 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. The temperature was raised from normal pressure while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was changed to 290 ° C. over about 1 hour, and the reaction was carried out at 290 ° C. for 2 hours. Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel. The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer. The obtained polyamide was a white tough polymer, and ηr = 2.68.

[Production Example 5: Polyamide resin (A): PX6-5]
A mixture of 8.361 kg (71.947 mol) of 1,6-hexanediamine and 8.361 kg (71.947 mol) of 2-methyl-1,5-pentanediamine (1,6-hexanediamine and 2-methyl-1) , 5-pentanediamine in a molar ratio of 50:50), and 29.107 kg (143.89 mol) of dibutyl oxalate was placed in the reaction vessel with a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes. The temperature was raised simultaneously with the supply. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 260 ° C. over 1.5 hours. Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 260 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. The temperature was raised from normal pressure while flowing nitrogen gas at 1.5 liters / minute, and the temperature of the polycondensate was changed to 275 ° C. over about 1 hour, and the reaction was carried out at 275 ° C. for 3 hours. Thereafter, the stirring was stopped and the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes. Then, the pressure was released to an internal pressure of 0.1 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel. The string-like polymer was immediately cooled with water, and the water-cooled string-like resin was pelletized with a pelletizer. The obtained polyamide was a white tough polymer, and ηr = 2.61.

[Comparative Production Example 1: Polyamide resin: PX6-6]
(I) Pre-polycondensation step: The inside of a 1 L separable flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a raw material inlet is replaced with nitrogen gas having a purity of 99.9999%.
500 ml of dehydrated toluene,
1,6-hexanediamine 58.7209 g (0.5053 mol) was charged.
After this separable flask was placed in an oil bath and heated to 50 ° C,
Dibutyl oxalate (102.1956 g, 0.5053 mol) was charged.
Next, the temperature of the oil bath was raised to 130 ° C., and the reaction was carried out for 5 hours under reflux.
Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 50 ml / min.

(Ii) Post-polycondensation step: The prepolymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube. Then, the operation of introducing nitrogen gas to normal pressure was repeated 5 times, and then the mixture was transferred to a salt bath maintained at 290 ° C. under a nitrogen stream of 50 ml / min. After the temperature of the salt bath was set to 340 ° C. over 1 hour, the pressure in the container was reduced to about 66.5 Pa, and the reaction was further continued for 2 hours.
Subsequently, after introducing nitrogen gas to normal pressure, it was removed from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide resin. The obtained polymer was a yellow polymer, and ηr = 1.65.

  Production Examples 1-5, Polyamides PX6-1 to PX6-6 produced in Comparative Production Example 1, and nylon 6 (Ube Industries, UBE nylon 1015B: PA6) and nylon 66 (Ube Industries, UBE nylon 2020B: PA66) The relative viscosity, melting point, 1% weight loss temperature, melt viscosity, saturated water absorption, chemical resistance, hydrolysis resistance, and mechanical properties in dry and wet conditions were measured. The results are shown in Table 1.

From Table 1, the polyamide resin used in the present invention has low water absorption compared to nylon 6 and nylon 66, excellent chemical resistance, hydrolysis resistance, excellent mechanical properties under wet conditions, and It can be seen that it is possible to produce a tough molded body having a wider moldable temperature range and excellent melt moldability than that of a polyamide resin using 1,6-hexanediamine alone as a diamine component, and capable of increasing the molecular weight.
The polyamide resin composition of the present invention includes an impact modifier (component B) in addition to the polyamide resin (component A). The polyamide resin composition basically includes a polyamide resin (component A). ) Characteristics.

[Example 1]
100 parts by weight of PX6-1 pellets, 40 parts by weight of Mitsui DuPont's Himiran 1706 pellets (Ionomer) (B-1) are blended in advance, and the resulting mixed pellets are fed to a Japanese-made TEX44 twin screw extruder for melt kneading. The strand was cooled and solidified in a cooling water tank, and then a pellet-like sample was obtained with a pelletizer. The pellet was dried under reduced pressure, and the pellet was subjected to evaluation.

[Example 2]
Except for following the formulation in Table 2, pellets were prepared in the same manner as in Example 1, and the pellets were subjected to evaluation.

[Example 3]
The impact-improving material (B) was made by Mitsui DuPont, made by HiMilan 1855 pellets (ionomer) (B-2), and the pellets were prepared in the same manner as in Example 1 except that the composition shown in Table 2 was followed, and the pellets were evaluated. It was used for.

[Example 4]
The impact modifier (B) was Exxor Chemical VA1801 (maleic acid-modified ethylene-propylene resin) (B-3) manufactured by Exxon Chemicals, and pellets were prepared in the same manner as in Example 1 except that the formulation shown in Table 2 was followed. The pellet was subjected to evaluation.

[Example 5]
Except for following the formulation in Table 2, pellets were prepared in the same manner as in Example 4, and the pellets were subjected to evaluation.
[Example 6]
The impact modifier (B) was made by Mitsui Chemicals, Tuffmer MH5020 (maleic acid-modified ethylene-butene resin) (B-4), and a pellet was prepared in the same manner as in Example 1 except that the formulation shown in Table 2 was followed. The pellet was subjected to evaluation.

[Example 7]
The impact-improving material (B) was manufactured by Mitsui Chemicals, Tuffma-MH7020 (maleic acid-modified ethylene-butene resin) (B-5), and pellets were produced in the same manner as in Example 6 except that the composition shown in Table 2 was followed. The pellet was used for evaluation.
[Example 8]
The impact-improving material (B) was manufactured by Asahi Kasei Corporation, Tuftec M1943 (epoxy-modified styrene block copolymer resin) (B-6), and a pellet was prepared in the same manner as in Example 1 except that the composition in Table 2 was followed. The pellet was subjected to evaluation.

[Comparative Example 1]
A pellet was prepared in the same manner as in Example 1 except that 100 parts by mass of Ube Industries 1015B pellet (nylon 6) and 18 parts by mass of B-3 were used, and the pellet was subjected to evaluation.

[Comparative Example 2]
A pellet was prepared in the same manner as in Example 1 except that 100 parts by mass of Ube Industries 2020B pellet (nylon 66) and 25 parts by mass of B-4 were used, and the pellet was subjected to evaluation.
In addition, the polyamide resin composition using PX6-6 could not be melt-kneaded and molded because Td-Tm was small.

  The polyamide resin composition comprising the polyamide resin of the present invention (component A) and the impact modifier (component B) has high impact resistance and is compared with conventional nylon 6 and nylon 66 series compositions. Excellent water absorption, chemical resistance, hydrolysis resistance, etc., and a wider moldable temperature range than polyamide resin composition using 1,6-hexanediamine alone as the diamine component. It is possible to manufacture tough molded bodies that can be made molecular weight, and widely used as various functional parts such as electric tools, general industrial parts, machine parts, electronic parts, automotive interior and exterior parts, engine room interior parts, automotive electrical parts, etc. This is industrially useful.

Claims (3)

A polyamide resin composition comprising a polyamide resin (component A) and an impact modifier (component B),
The component A is composed of a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid (compound a);
The diamine comprises 1,6-hexanediamine (compound b) and 2-methyl-1,5-pentanediamine (compound c);
The polyamide resin composition whose molar ratio of the said compound b and the said compound c is 99: 1-50: 50.   Impact modifier (component B) is (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) • (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) The polyamide resin composition according to claim 1, wherein the polyamide resin composition is at least one polymer selected from the group consisting of a copolymer and an ionomer.   A molded article of the polyamide resin composition according to claim 1 or 2.