JP2013095804A - Polyamide resin composition for extrusion and extrusion molding obtained by extruding the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin composition for extrusion which comprises a polyamide resin which, in comparison with conventional aliphatic polyamide resins, achieves a sufficient relative viscosity ηr, have a wide moldable temperature range, have excellent heat resistance and melt moldability, can reduce the molding cycle, and have excellent chemical resistance, hydrolysis resistance and fuel barrier properties without impairing low water absorbability, and an extrusion molding which is obtained by extruding the polyamide resin composition and has excellent mechanical strength and ductility and/or barrier properties.SOLUTION: In the polyamide resin composition for extrusion comprising a polyamide resin (component A), the component A is obtained by bonding a unit derived from a dicarboxylic acid to 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), 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 polyamide resin composition for extrusion molding and an extrusion molded body obtained by extrusion molding.

Hereinafter, the name of the polyamide resin may be based on JIS K 6920-1.
Crystalline polyamides such as nylon 6 (PA6) and nylon 66 (PA66) 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 there is an increasing demand for polyamides with better dimensional stability and chemical resistance. ing.

  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. For example,
Non-Patent Document 1 discloses a polyoxamide resin using 1,6-hexanediamine as a diamine component,
Non-Patent Document 2 discloses a polyoxamide resin (hereinafter also referred to as PA92) in which the diamine component is 1,9-nonanediamine,
Patent Document 2 discloses a polyoxamide resin using various diamine components and dibutyl oxalate as a dicarboxylic acid ester,
Patent Document 3 discloses a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component in a specific ratio.

JP 2006-57033 A Japanese National Patent Publication No. 5-506466 WO2008 / 072754

S. W. Shalaby, J. et al. Polym. Sci. , 11, 1 (1973) L. Franco, et al. , Macromolecules, 31, 3912 (1998).

However,
Regarding the polyoxamide resin disclosed in Non-Patent Document 1, the melting point (about 320 ° C.) is close to the thermal decomposition temperature (1% weight loss temperature in nitrogen; about 310 ° C.), so that melt polymerization and melt molding are difficult. It is not something that can withstand practical use,
The polyoxamide resin disclosed in Non-Patent Document 2 discloses a production method and crystal structure when diethyl oxalate is used as the oxalic acid source, and PA92 obtained here has an intrinsic viscosity of 0.97 dL / g. , A polymer having a melting point of 246 ° C., and only a low molecular weight body that cannot be formed into a tough molded body has been obtained,
Regarding the polyoxamide resin disclosed in Patent Document 2, it is shown that PA92 having an intrinsic viscosity of 0.99 dL / g and a melting point of 248 ° C. is produced, but the low molecular weight is such that a tough molded body cannot be molded. There is a problem that only the body is obtained,
Regarding the polyoxamide resin disclosed in Patent Document 3, a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component in a specific ratio is shown. However, these polyoxamide resins have a wide moldable temperature range, excellent moldability, and low water absorption, chemical resistance, hydrolysis resistance, fuel barrier properties, etc., but the melting point is around 240 ° C., Heat resistance is slightly inferior for electrical and electronic equipment applications that require molding cycle properties and a high melting point.
Furthermore, when these conventional polyamide resins are extruded as, for example, filaments, the mechanical strength and elongation are not sufficient, and when extruded as a film, barrier properties against liquid, vapor and gas (hereinafter, In some cases, the barrier property was not sufficient.

The problem to be solved by the present invention is:
Compared with conventional polyoxamide resin,
Melting point Tm (° C.) measured by differential scanning calorimetry measured at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere and measurement at a rate of temperature increase of 10 ° C./min under a nitrogen atmosphere Moldable temperature estimated from temperature difference (Td-Tm) (° C.) (hereinafter also referred to as temperature difference (Td-Tm)) from 1% weight loss temperature Td (° C.) (thermal decomposition temperature) in thermogravimetric analysis Wide,
Excellent heat resistance estimated from melting point Tm,
It has an appropriate melt viscosity and excellent melt moldability, and the molding cycle can be reduced.
Polyamide that can extrude molded products with superior chemical resistance, hydrolysis resistance, and fuel barrier properties compared to conventional aliphatic polyamide resins without impairing the low water absorption found in aliphatic linear polyoxamide resins An object of the present invention is to provide a polyamide resin composition for extrusion containing a resin, and an extruded product excellent in mechanical strength and elongation and / or barrier properties obtained by extrusion molding.

The present invention
(1) A polyamide resin composition for extrusion molding comprising a polyamide resin (component A),
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);
An extrusion molding polyamide resin composition in which the molar ratio of the compound b to the compound c is 99: 1 to 50:50, and (2) the extrusion molding polyamide resin composition described in the above (1) is extruded. It is the obtained extrusion molding.

According to the present invention,
Compared with conventional polyoxamide resin,
The moldable temperature range estimated from the temperature difference (Td−Tm) is wide.
Excellent heat resistance estimated from the melting point Tm,
It has an appropriate melt viscosity and excellent melt moldability, and the molding cycle can be reduced.
Polyamide that can extrude molded products with superior chemical resistance, hydrolysis resistance, and fuel barrier properties compared to conventional aliphatic polyamide resins without impairing the low water absorption found in aliphatic linear polyoxamide resins The present invention can provide a polyamide resin composition for extrusion containing a resin and an extruded product excellent in mechanical strength, elongation and / or barrier properties obtained by extrusion molding.

[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 1.8 to 6.0, more preferably 1.8 to 4.5, more preferably 1.8 to 3.0, still more preferably. May be 1.85 to 2.5, more preferably 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 to 600 Pa · s, still more preferably 120 to 500 Pa · s, still more preferably 130 to 400 Pa · s, and further Preferably it is 150-300 Pa.s, More preferably, it is 160-220 Pa.s, More preferably, it is 170-200 Pa.s.

  Furthermore, from the same viewpoint, the number average molecular weight (Mn) of Component A is preferably 10,000 to 50,000, more preferably 11,000 to 40,000, and still more preferably 11,000 to 35,000.

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 (NH ₂ ) = 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 (NH 2): The total number of terminal amino groups of PX6-2 (Compound b / Compound c = 90/10).
N (NH ₂ ): number of terminal amino groups per molecule.
S (NH ₂ ): 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 (NH ₂ ): The number of hydrogens (2) counted in the integrated value S (NH ₂ ).
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. Particularly contributes to 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 MPa, preferably 1 MPa to 0.2 MPa 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.

(5) 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.

(6) Molding of component A As the molding method of component A, all known molding methods applicable to polyamide such as injection, extrusion, hollow, press, roll, foaming, vacuum / pressure air, and stretching can be used. From the viewpoint of shortening the molding cycle property, it is particularly suitable for molding by extrusion molding, and can be processed into films, sheets, molded articles, fibers, etc. by these molding methods.

[Polyamide resin composition for extrusion molding]
(Content of component A)
The polyamide resin composition for extrusion molding of the present invention (hereinafter also referred to as a resin composition) has a good moldable temperature range, heat resistance, and melt moldability (hereinafter referred to as thermal characteristics) for improving productivity during extrusion molding. From the viewpoint of ensuring low water absorption, chemical resistance, hydrolysis resistance, and mechanical strength and elongation and / or barrier properties of the extruded product.
The content of component A in the resin composition is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 92 to 100% by mass, and still more preferably. It is 95-100 mass%.

(Other ingredients)
For extrusion molding, it is preferable to include the following as other components.

(1) Polymer other than Component A In the resin composition of the present invention, if necessary, in order to utilize the characteristics of each polymer,
Other polyamides other than component A, such as at least one polyamide selected from the group consisting of polyoxamides, aromatic polyamides, aliphatic polyamides and alicyclic polyamides, and / or polymers other than polyamides, such as thermoplastic polymers An elastomer can be included.

  The polymer other than Component A is not particularly limited as long as it does not impair the effects of the present invention, but is preferably 0.1 to 100 parts by weight, more preferably 0.1 to 50 parts by weight with respect to 100 parts by weight of Component A. Part, more preferably 0.5 to 30 parts by mass.

(2) Additive The resin composition of the present invention can contain an additive as long as the effects of the present invention are not impaired. Examples of additives include reinforcing agents, barrier property improving components, fillers, stabilizers such as copper compounds, colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, and crystallization accelerators. , Glass fiber, plasticizer, lubricant, heat-resistant agent and the like.

  As the reinforcing agent, for example, a layered silicate can be preferably used. Here, the layered silicate can impart excellent mechanical strength obtained by good rigidity, high elasticity, high pull-out force, etc., and excellent texture without impairing the elongation of the filament of the present invention. .

  Examples of the barrier property improving component include layered silicate. The layered silicate can improve the mechanical strength, heat resistance, barrier properties against liquids (especially alcohol and water) and gases (especially oxygen and gasoline) of the polyamide film of the present invention.

The method for adding the polymer and / or additive other than the above component A is not particularly limited as long as each method can be dispersed in component A, and the component can be added at any time that does not impair the effect. A can be added.
For example, polymers and / or additives other than component A
It can also be added during or after the polycondensation reaction of component A.

(3) Layered silicate The resin composition of the present invention can produce an extrusion-molded body excellent in mechanical strength and elongation and / or barrier properties only with Component A, but further has stable mechanical strength and In applications where elongation and / or barrier properties are required, it is preferable to further include a layered silicate in the resin composition of the present invention.

  The layered silicate is preferably a flat plate having a side length of 0.002 to 1 μm and a thickness of 6 to 20 mm. Moreover, when the said layered silicate is disperse | distributed in the component A, it is preferable that each layer maintains the interlayer distance of about 18 mm or more, and is disperse | distributed uniformly.

  Here, “interlayer distance” refers to the distance between the centroids of the plate-like layered silicate, and “uniformly dispersed” means that each layer exists mainly in a random state, and the layered silicate 50% by mass or more, preferably 70% by mass or more is dispersed in a single layer without forming a multilayer.

  As a raw material of the said layered silicate, the layered phyllosilicate mineral comprised from the layer of magnesium silicate or an aluminum silicate, ie, the aluminum silicate phyllosilicate, or the magnesium silicate phyllosilicate can be illustrated. Specific examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, halloysite, and the like. It may be what was done.

  In order to disperse the layered silicate in component A, a swelling agent is usually used. The swelling agent has a role of expanding the interlayer of the clay mineral and a role of giving the clay mineral a force for taking up the interlayer polymer. In the present invention, it is preferable to use 1,6-hexanediamine and 2-methyl-1,5-pentanediamine as the swelling agent.

  The layered silicate is preferably pulverized using a mixer, a ball mill, a vibration mill, a pin mill, a jet mill, a beating machine, or the like to have a desired shape and size in advance.

  The amount of the layered silicate is not particularly limited as long as the effect of improving mechanical strength and texture is obtained, but is preferably 0.05 with respect to 100 parts by mass of Component A used in the present invention. -10 parts by mass, more preferably 0.05-8 parts by mass, particularly preferably 0.05-5 parts by mass. When the ratio of the layered silicate decreases, the improvement effect tends to decrease, and when the ratio increases, the fluidity of the resin composition and the physical properties of the obtained molded product, particularly the impact strength, tend to decrease.

Examples of the method for uniformly dispersing the layered silicate in the component A include the following methods.
When the raw material of the layered silicate is a multilayered clay mineral, the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as 1,6-hexanediamine and 2-methyl-1,5-pentanediamine is added thereto. Add and widen the space between each layer of layered silicate in advance. Next, a polyamide raw material can be introduced between the layers, and the raw materials can be polymerized between the layers.

  Alternatively, using a polymer compound as a swelling agent, the layers may be preliminarily spread to about 100 mm or more, melt-mixed with the polyamide resin, and each layer may be dispersed in the polyamide resin.

(Extruded product)
In the polyamide resin composition for extrusion molding of the present invention, as a molding method, a molding process using various types of extruders such as a single screw or a twin screw is preferably used, and a melt molding process is particularly preferably used. The polyamide resin composition for extrusion molding of the present invention is a material suitable for processing various filaments, films and the like by a melt molding method.

(1) Filament The filament of the present invention can be used as various monofilaments and multifilaments, and as uses, bristle for brush, fishing line, hook-and-loop fastener, tire cord artificial turf, carpet, seat for automobile seat, fish net, Examples include ropes, sills, filter threads, lawn mower filaments, toothbrushes, and automobile floor mats.

  The method for forming the filament of the present invention is not limited to these. For example, the polyamide resin composition for extrusion molding containing component A is melted in a melt extruder such as a single screw, and the discharge amount is set. The melt can be produced by extruding the melt from a spinneret through a gear pump that is controlled quantitatively and taking it at a predetermined take-up speed while cooling with air or water. The filaments thus obtained may be further stretched at various magnifications depending on the application. Also, melt spinning and stretching may be performed simultaneously.

  The filament may be a monofilament or a multifilament, and may or may not be twisted. The cross section of the filament may be circular, or may be an irregular cross section such as a hollow shape or a star shape.

(2) Film The film of the present invention may be a stretched film or an unstretched film, and can be molded using any molding method known in the field of films.

  More specifically, for example, a predetermined amount of component A and various other components used as necessary is melt-kneaded with an extruder, the kneaded product is extruded into a film form from a T-die, and cast on the casting roll surface. An unstretched film can be formed by applying a T-die method for cooling the film, a tubular method in which the kneaded product is extruded from a ring die into a cylindrical shape, and then air-cooled or water-cooled. In addition, the stretched film can be formed by a method of stretching the unstretched film uniaxially or biaxially and heat-setting as necessary below the melting point of the polymer constituting the unstretched film.

  You may use the polyamide film of this invention as what comprises one or more layers in a multilayer laminated film. In this case, the layers other than the film of the present invention include, for example, a polyolefin film made of low density polyethylene, high density polyethylene, polypropylene, etc., a polyester film, a copolymer film made of an ethylene-vinyl acetate copolymer, and an ionomer resin. A film or the like can be used depending on the purpose.

  The laminated film can be formed using a known method such as an adhesion method or a coextrusion method. In the bonding method, the polyamide film of the present invention and one or more other films may be bonded with an adhesive. In the co-extrusion method, the raw material polymer melts of the polyamide film of the present invention and one or more other films may be melt-coextruded from a multilayer die via an adhesive resin as necessary.

  The film of the present invention can be suitably used for applications such as industrial materials, industrial materials, household goods, and more specifically for food packaging, especially for retort, where the contents are liquid, and used for metal coating. An antirust effect can also be imparted.

[Examples and Comparative Examples]
In Examples 1-1 to 5, the polyamide resin composition for extrusion molding of the present invention was produced.
In Examples 2-1 to 5, filaments (monofilaments) using the polyamide resin composition for extrusion molding of the present invention were produced.
In Examples 3-1 to 5, single-layer tubes using the polyamide resin composition for extrusion molding of the present invention were produced.

(1) Example 1-1 (component A: PX6-1)
In 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 with a diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator and polymer outlet.
Mixture of compound a (1,6-hexanediamine) 15.407 kg (132.58 mol) and compound b (2-methyl-1,5-pentanediamine) 811.1 g (6.98 mol) (compound a and compound the molar ratio of b is 95: 5),
After pressurizing the interior of the pressure vessel to 0.5 MPa with nitrogen gas having a purity of 99.9999%,
Next, the operation of releasing nitrogen gas to normal pressure was repeated 5 times, and after nitrogen replacement,
The system was heated while stirring under a sealing pressure.
After bringing the temperature of dibutyl oxalate to 80 ° C. over about 30 minutes,
At the same time, 28.230 kg (139.56 mol) of dibutyl oxalate was supplied into the reaction vessel over about 17 minutes at a flow rate of 1.49 liters / minute by means of a diaphragm pump.
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.

(2) Example 1-2 (component A: PX6-2)
A mixture of 14.717 kg (126.64 mol) of compound a and 1.635 kg (14.07 mol) of compound b (molar ratio of compound a and compound b is 90:10) is charged.
Except for charging 28.462 kg (140.71 mol) of dibutyl oxalate,
Reaction was carried out in the same manner as in Production Example 1 to obtain polyamide.
The obtained polyamide was a white tough polymer with ηr = 2.05.

(3) Example 1-3 (component A: PX6-3)
A mixture of 12.16 kg (104.64 mol) of compound a and 5.212 kg (44.85 mol) of compound b (the molar ratio of compound a to compound b is 70:30) is charged.
At the same time, 30.238 kg (149.49 mol) of dibutyl oxalate was supplied into the reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute over about 17 minutes.
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.
The temperature was raised from normal pressure 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.

(4) Example 1-4 (component A: PX6-4)
A mixture of 10.294 kg (88.583 mol) of compound a and 6.863 kg (59.057 mol) of compound b (molar ratio of compound a to compound b is 60:40) is charged.
29.864 kg (147.64 mol) of dibutyl oxalate was supplied into the reaction vessel at a flow rate of 1.49 liter / min by a diaphragm pump over about 17 minutes, and the temperature was raised.
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.
From the normal pressure, the temperature was raised 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.

(5) Example 1-5 (component A: PX6-5)
A mixture of 8.361 kg (71.947 mol) of compound a and 8.361 kg (71.947 mol) of compound b (molar ratio of compound a and compound b is 50:50),
At the same time, 29.107 kg (143.89 mol) of dibutyl oxalate was supplied into the reaction vessel at a flow rate of 1.49 liters / minute over about 17 minutes by a diaphragm pump.
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.

(6) Comparative Example 1-1: (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, and the pressure inside the reaction tube is reduced to 13.3 Pa or less. 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.

(7) Comparative Example 1-2
As the polyamide resin of the resin composition for extrusion molding,
A pellet of nylon 6 (Ube Industries, UBE nylon 1015B: PA6) (Comparative Example 1) was used.

(8) Examples 2-1 to 5 and Comparative Example 2-2
Each of the polyamide resin compositions of Examples 1-1 to 5 and Comparative Example 1-2 was
Using an extruder with a screw diameter of 30 mm, the cylinder set temperature in the case of Examples 2-3 to 5 and Comparative Example 2-2 was 280 to 310 ° C,
In the case of Examples 2-1 and 340 ° C.
In
Melt extrusion from a nozzle with a diameter of 1.47 mm and 8 holes,
Cool in cold water at 7 ℃,
Stretching with the first roller, and stretching the second roller with a take-up speed of 3.9 times that of the first roller (stretching temperature 310 ° C.)
Furthermore, the take-up speed of the third roller is 5 times that of the first roller, and further stretched (stretching temperature 300 ° C.),
Finally, the fourth roller is taken up at the same take-off speed as the third roller, and the temperature is set between 230 to 260 ° C. and heat-fixed to obtain monofilaments of Examples 2-1 to 5 and Comparative Example 2-2, respectively. It was.

(9) Examples 3-1 to 5 and Comparative Example 3-2
About the polyamide resin and PA6 which were manufactured in Examples 1-5, the outer diameter 1/2 inch and thickness 1mm were used using the extruder (cylinder temperature 250-340 degreeC) of the screw diameter 30mm made from Japan Steel Works. Single layer tubes were produced.

About component A or polyamide resin in Examples 1-1 to 5 and Comparative Examples 1-1 to 2,
Relative viscosity, melting point, 1% weight loss temperature, melt viscosity, saturated water absorption, chemical resistance, hydrolysis resistance, physical properties in dry and wet conditions, ethanol permeability coefficient, oxygen permeability coefficient and moisture permeability,
For the monofilaments in Examples 2-1 to 5 and Comparative Example 2-2, the fineness, chemical resistance, tensile strength, tensile elongation, tensile modulus, and hot water shrinkage force
About the single layer tube in Examples 3-1 to 5 and Comparative Example 3-2, the ethanol permeability coefficient and moisture permeability were
It measured on the conditions mentioned later.
The results are shown in Table 1.

[Physical property measurement, molding, evaluation conditions]
The following contents were used.

(1) Relative viscosity ηr of polyamide resin
ηr was measured at 25 ° C. using an Ostwald viscometer using a 96% sulfuric acid solution (concentration: 1.0 g / dl) of each polyamide resin of Examples 1-1 to 5 and Comparative Examples 1-1 and 2 did.

(2) Melt Viscosity of Polyamide Resin The melt viscosities of the polyamide resins of Examples 1-1 to 5 and Comparative Examples 1-1 and 2 were 25 mm on a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan. Wearing a cone plate, in nitrogen,
340 ° C. when PA 6-1 to 2 and 6 are included as the polyamide resin,
300 ° C. when PA 6-3 is included as the polyamide resin,
260 ° C when PA6 is included as the polyamide resin,
Measurement was performed under conditions of a shear rate of 0.1 s- ¹ .

(3) Melting point of polyamide resin (Tm)
Tm of each polyamide resin of Examples 1-1 to 5 and Comparative Examples 1-1 to 2 was measured under a nitrogen atmosphere using PYRIS Diamond DSC manufactured by PerkinELmer.
Tm when PA 6-1 to 2 and 6 are included as the polyamide resin is
The temperature is raised from 30 ° C. to 350 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run),
After holding at 350 ° C for 3 minutes,
The temperature is decreased to -100 ° C at a rate of 10 ° C / min (referred to as a temperature decrease first run),
Next, the temperature was raised to 350 ° C. at a rate of 10 ° C./min (referred to as a temperature raised second run).
Tm when PA6-3-5 and PA6 are included as the polyamide resin is
The temperature is increased from 30 ° C. to 310 ° C. at a rate of 10 ° C./min (referred to as a temperature rising first run),
After holding at 310 ° C for 3 minutes,
The temperature is decreased to -100 ° C at a rate of 10 ° C / min (referred to as a temperature decrease first run),
Next, the temperature was raised to 310 ° C. at a rate of 10 ° C./min (referred to as a temperature rise second run).
The endothermic peak temperature of the elevated temperature second run was defined as Tm.

(4) 1% weight loss temperature Td of polyamide resin
Td of each polyamide resin of Examples 1-1 to 5 and Comparative Examples 1-1 to 2 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.

(5) Test Film and Plate Molding Conditions (5-1) Test Film Each polyamide of Examples 1 to 5 and Comparative Examples 1 to 3 was formed using a vacuum press machine TMB-10 manufactured by Toho Machinery Co., Ltd. A film for test of saturated water absorption, chemical resistance, hydrolysis resistance and water absorption of the resin was obtained.
Under a reduced pressure atmosphere of 500 to 700 Pa,
340 ° C. when PA 6-1 to 2 and 6 are included as the polyamide resin,
300 ° C. when PA 6-3 is included as the polyamide resin,
260 ° C when PA6 is included as the polyamide resin,
After 5 minutes of heating and melting,
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 test film.

(5-2) Test plate Resin temperature 340 ° C. when PA6-1-2 and 6 are included as the polyamide resin,
300 ° C. when PA 6-3 is included as the polyamide resin,
260 ° C when PA6 is included as the polyamide resin,
A test plate was obtained by injection molding at a mold temperature of 80 ° C.
The injection molding conditions were: injection pressure: primary pressure 650 kg / cm ² , injection time: 11 seconds, cooling time: 20 seconds.

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

(7) Chemical resistance of polyamide resin After the test film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass about 0.05 g) was immersed in the chemicals listed below for 7 days, the weight residual ratio of the film (%) And changes in appearance 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 of polyamide resin A test film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass about 0.05 g) was placed in an autoclave, and water (pH = 7), 0.5 mol / l The weight residual ratio (%) and appearance change after treatment for 60 minutes at 121 ° C. in sulfuric acid (pH = 1) or 1 mol / l sodium hydroxide aqueous solution (pH = 14) were examined.

(9) Mechanical properties of polyamide resin
What was evaluated at 23 ° C. without conditioning immediately after molding was dried,
What was evaluated at 23 ° C. after conditioning at a humidity of 65% and a temperature of 23 ° C. after molding was described in the table as wet.

(9-1) Tensile strength: Measured according to ASTM D638 using a test plate formed into a dumbbell shape of a Type I test piece described in ASTM D638.
(9-2) Flexural modulus: Measured according to ASTM D790 using a test plate.
(9-3) Deflection temperature under load (thermal deformation temperature): Measured with a load of 1.82 MPa in accordance with ASTM D648 using a test plate.

(10) Water absorption rate of polyamide resin Except that it was placed under conditions of 23 ° C. and humidity 65% RH using a test film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; mass about 0.05 g). (6) The water absorption rate (equilibrium water absorption rate) (%) was calculated according to the method for measuring the saturated water absorption rate.

(11) Oxygen permeability coefficient of polyamide resin For test pieces cut out from a test film (thickness 30 μm), using a MOCON tester OX-TRAN 2 / 20-MH, under conditions of a temperature of 23 ° C. and a humidity of 97% RH , Measured based on "ASTM D3985".
(12) Tensile strength, tensile elongation, and tensile modulus of monofilament The tensile strength, tensile elongation, and tensile modulus of the monofilament were measured according to JIS L1070 and L1073.

(13) Hydrothermal contraction force of monofilament The monofilament is allowed to stand at 23 ° C in a relative humidity of 65% until the mass becomes constant,
Then, cut to a length of 1000 mm, soaked in 100 ° C. water for 15 minutes,
Measure the dimensions immediately after that,
Hot water shrinkage (%)
= [(Dimension before immersion) − (Dimension after immersion at 100 ° C. for 15 minutes)] / (Dimension before immersion) × 100
Thus, the hot water shrinkage force was calculated as a percentage.

(14) Chemical resistance of monofilament After the above monofilament was immersed in the following chemicals for 7 days, the residual mass (%) of monofilament and changes in appearance 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.

(15) Single-layer tube ethanol permeability coefficient One end of a single-layer tube cut to 30 cm is sealed, ethanol is put inside, the other end is sealed, the whole weight is measured, and then the test tube is placed at 60 ° C. The inside of the tank was flushed with nitrogen at 50 ml / min.
The change in weight over time was measured, and when the rate of change in weight per hour was stabilized, the fuel permeability coefficient was calculated from the following equation. The transmission area of the sample is 78.5 cm ² .
Ethanol permeability coefficient (g · mm / m ² · day)
= [Permeation weight (g) × film thickness (mm)] / [permeation area (mm ² ) × days (day)]

(16) Moisture permeability of single-layer tube The single-layer tube was cut into a length of 300 mm, filled with calcium chloride as a moisture absorbent therein, and sealed. Next, this tube was allowed to stand for 10 days or longer in an atmosphere at 40 ° C. and a relative humidity of 90%, and the average daily moisture permeability per unit area was measured.

The polyamide resin composition for extrusion molding of the present invention has low water absorption compared to materials such as nylon 6 and nylon 66, is excellent in chemical resistance and hydrolysis resistance, and is excellent in mechanical properties under wet conditions. And, a polyamide resin (PX6-6) using 1,6-hexanediamine alone as a diamine component has a wider moldable temperature range and excellent melt moldability, and can have a higher molecular weight.
Filaments obtained by extruding the polyamide resin composition for extrusion molding of the present invention have good mechanical strength and elongation, and low water absorption, but can be made high molecular weight by melt polymerization, Wide range of moldable temperature estimated from the difference between melting point and thermal decomposition temperature, excellent melt moldability, chemical resistance, hydrolysis resistance, for example, brush bristle, fishing line, hook-and-loop fastener, tire cord, artificial grass, It can be suitably used for applications such as carpets, seats for automobile seats, fishnets, ropes, sills, thread for filters,
The tube obtained by extruding the polyamide resin composition for extrusion molding according to the present invention has excellent barrier properties against liquids, vapors and / or gases, and has low water absorption, but can be made high molecular weight by melt polymerization. Because of its wide moldable temperature range and excellent melt moldability, and excellent chemical and hydrolysis resistance, it can be used for industrial materials, industrial materials, household goods, and more specifically for food packaging applications. It can be suitably used as a barrier film.
In addition, the polyamide resin composition using PX6-6 could not be melt-kneaded and molded because Td-Tm was small.

Claims (4)

A polyamide resin composition for extrusion molding comprising a polyamide resin (component A),
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);
A polyamide resin composition for extrusion molding, wherein the molar ratio of the compound b to the compound c is 99: 1 to 50:50.   An extruded product obtained by extrusion molding the polyamide resin composition for extrusion molding according to claim 1.   The extruded product according to claim 2, wherein the extruded product is a filament.   The extruded product according to claim 2, wherein the extruded product is a film.