JP2010077206A - Composite material containing polyamide resin and layered silicate, and blow molded part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material which has high mechanical strength, heat resistance, and liquid or vapor barrier properties, has better low water absorption properties, chemical resistance, hydrolysis resistance, etc. than a conventional nylon 6-based composite material, has a wider moldable temperature range and better melt moldability than a composite material based on a polyamide resin using a 1, 9-nonanediamine singly as a diamine component, can attain high molecular weight, and can produce a tough molded product. <P>SOLUTION: The composite material includes a polyamide resin and a layered silicate dispersed in the polyamide resin. In the polyamide resin, the dicarboxylic acid component is composed of oxalic acid; the diamine component is composed of a mixture of 1, 9-nonanediamine and 2-methyl-1, 8-octanediamine (hereinafter, referred to as a "C9 diamine mixture") and 1, 6-hexanediamine (hereinafter, referred to as "C6 diamine"); and the molar ratio of the C9 diamine mixture to the C6 diamine is 1:99 to 99:1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a novel composite material. Specifically, it is a composite material comprising a polyamide resin composition and a layered silicate dispersed in the polyamide resin composition, having high mechanical strength, heat resistance, and barrier properties against liquid or vapor, Compared to conventional nylon 6-based composite materials, it has superior water absorption, chemical resistance, hydrolysis resistance, etc., and is molded more than polyamide resin-based composite materials using 1,9-nonanediamine alone as a diamine component. The present invention relates to a composite material having a wide possible temperature range and excellent melt moldability and capable of producing a tough molded body capable of increasing the molecular weight.

  Crystalline polyamides typified by nylon 6, nylon 66, 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. Is required to have higher mechanical strength and heat resistance, and 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, low water absorption, There is a demand for polyamides having excellent performance such as mechanical strength and chemical resistance.

It is known that mechanical strength, heat resistance, and barrier properties against liquid or vapor can be improved by dispersing layered silicate in crystalline polyamide and forming a composite material (for example, Patent Document 1). .
Patent Document 1 discloses an example of a composite material using nylon 6 as a crystalline polyamide. Further, in Table 2, these composite materials have a tensile strength and a tensile modulus as compared with the original nylon 6. It is disclosed that mechanical strength such as the above and heat resistance are improved. However, the composite material disclosed in Patent Document 1 has problems such as high water absorption due to nylon 6 and low chemical resistance and hydrolysis resistance, and it is desired to improve them. ing.

  On the other hand, a polyamide resin using oxalic acid as a dicarboxylic acid component is called a polyoxamide resin, and has a high melting point and low water absorption compared to other polyamide resins having the same amino group concentration (Patent Document 2). Changes in physical properties due to water absorption are a problem, and utilization in fields where conventional polyamides have been difficult to use is expected.

  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 a thermal decomposition temperature (1% weight loss temperature in nitrogen; about 310 ° C.) (Non-patent Document 1). Therefore, melt polymerization and melt molding are difficult and cannot be practically used.

  Regarding a polyoxamide resin (hereinafter abbreviated as PA92) in which the diamine component is 1,9-nonanediamine, L.M. Franco et al. Discloses a production method and crystal structure thereof 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 product that cannot form a tough molded product is obtained. Patent Document 3 shows that PA92 having an intrinsic viscosity of 0.99 dL / g and a melting point of 248 ° C. was produced using dibutyl oxalate as a dicarboxylic acid ester. 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.

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).
However, this polyamide resin uses oxalic acid as the dicarboxylic acid component, and has a specific ratio of three diamines of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine as the diamine component. It is not the polyoxamide resin used in 1.

S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1988) JP-A-62-74957 JP 2006-57033 A Special table 5-506466 WO2008 / 072754

  The present invention has been made on the basis of the above circumstances, and the present invention has high mechanical strength, heat resistance, and barrier property against liquid or vapor, and is low in comparison with conventional nylon 6-based composite materials. Excellent water absorption, chemical resistance, hydrolysis resistance, etc., and has a wider moldable temperature range than polyamide resin-based composite materials using 1,9-nonanediamine alone as a diamine component, and excellent melt moldability. It is an object of the present invention to provide a composite material capable of producing a tough molded body capable of high molecular weight without impairing the low water absorption observed in aliphatic linear polyoxamide resins.

  As a result of intensive studies to solve the above problems, the present inventors have found that the dicarboxylic acid component is oxalic acid, and the diamine component is a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine. (Hereinafter also referred to as “C9 diamine mixture”) and 1,6-hexanediamine (hereinafter also referred to as “C6 diamine”), and the molar ratio of C9 diamine mixture to C6 diamine is 1:99 to 99: Surprisingly, the same as the polyamide resin (PA92C) previously disclosed by the present inventors in Patent Document 3 by using the polyamide resin 1 (hereinafter also referred to as “PA92 / 62T”) as the composite material. In addition, it has excellent mechanical properties and chemical resistance, but has a high molecular weight, a sufficiently large difference between the melting point and the thermal decomposition temperature, and excellent melt moldability. Without impairing the low water absorption observed in the polyamide resin, not only can a polyamide resin composition excellent in hydrolysis resistance as compared with the conventional polyamide be obtained, but also this novel polyamide resin (PA92 / 62T) Compared with PA92C, it has a higher melting point, better mechanical properties such as flexural modulus and deflection temperature under load, and is advantageous in terms of cost. As a result, the present invention has been completed.

Specifically, the present invention relates to the following aspects.
[Aspect 1]
A composite material comprising a polyamide resin and a layered silicate dispersed in the polyamide resin,
The dicarboxylic acid component of the polyamide resin comprises oxalic acid, the diamine component comprises a C9 diamine mixture (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6-hexanediamine, and A composite material having a molar ratio of C9 diamine mixture (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6-hexanediamine of 1:99 to 99: 1.

[Aspect 2]
In aspect 1, the relative viscosity (ηr) of the polyamide resin measured at 25 ° C. using a polyamide resin solution having a concentration of 1.0 g / dl using 96% sulfuric acid as a solvent is 1.8 to 6.0. The composite material described.
[Aspect 3]
1% weight loss temperature in thermogravimetric analysis of the polyamide resin measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and differential scanning calorimetry measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. The composite material according to aspect 1 or 2, wherein the temperature difference from the melting point measured by the step is 50 ° C or more.

[Aspect 4]
The composite material according to any one of aspects 1 to 3, wherein the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 95: 5.
[Aspect 5]
The composite material according to any one of aspects 1 to 4, wherein the content of the layered silicate is 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin.

[Aspect 6]
The composite material according to any one of aspects 1 to 5, wherein 50% by mass or more of the layered silicate is dispersed in a single layer in the polyamide resin.
[Aspect 7]
The composite material according to any one of aspects 1 to 6, wherein the layered silicate is an aluminum silicate phyllosilicate or a magnesium silicate phyllosilicate.

  The composite material containing the polyamide resin and the layered silicate of the present invention has high mechanical strength, heat resistance, and liquid or vapor barrier properties, and has low water absorption and resistance compared to conventional nylon 6-based composite materials. Excellent chemical properties and hydrolysis resistance, and has a wider moldable temperature range than polyamide resin composites using 1,9-nonanediamine alone as the diamine component. A tough molded body can be produced.

Hereinafter, the present invention will be described in detail.
[Polyamide resin]
In the polyamide resin used in the present invention, the dicarboxylic acid component is composed of oxalic acid, and C9 diamine (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6-hexanediamine are used as the diamine component. And the molar ratio of C9 diamine (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) to 1,6-hexanediamine is from 1:99 to 99: 1.

  As the oxalic acid source as the dicarboxylic acid source of the polyamide resin used in the present invention, oxalic acid diester is used, and there is no particular limitation as long as it has reactivity with an amino group. Dimethyl oxalate, diethyl oxalate, oxalic acid Di-n- (or i-) propyl, oxalic acid diesters of aliphatic monohydric alcohols such as di-n- (or i-, or t-) butyl oxalate, oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate, diphenyl oxalate, etc. And oxalic acid diesters of aromatic alcohols.

  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 preferred, and among them, dibutyl oxalate and diphenyl oxalate are particularly preferred.

  In the polyamide resin used in the present invention, oxalic acid is used as the dicarboxylic acid source, but other dicarboxylic acid components can be blended within a range that does not impair the effects of the present invention. Examples of dicarboxylic acid components other than succinic acid include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3, Aliphatic dicarboxylic acids such as 3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and terephthalic acid , Isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1,3-phenylenedioxydiacetic acid, dibenzoic acid Acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfuric acid Down-4,4'-dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid aromatic dicarboxylic acids such as such alone or may be added any mixtures thereof during the polycondensation reaction. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  The blending amount of the other dicarboxylic acid is not particularly limited as long as the effects of the present invention are not impaired. In general, it is preferably 5 mol% or less with respect to the total amount of the dicarboxylic acid.

  For the polyamide resin used in the present invention, 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine are used as the diamine component, but the range does not impair the effects of the present invention. Other diamine components can be blended. Other diamine components other than 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine include ethylenediamine, propylenediamine, 1,4-butanediamine, and 1,8-octanediamine. 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1 Aliphatic diamines such as cyclohexandiamine, methylcyclohexanediamine and isophoronediamine, p-phenylenediamine, m-phenylenediamine, p -Xylenediamine, m-xylenediamine, 4,4'-diamy Diphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-aromatic diamines diaminodiphenyl ether or the like, etc. alone, or can be added any mixture thereof during the polycondensation reaction.

  Although it will not specifically limit if it is a range which does not impair the effect of this invention as a compounding quantity of said other diamine component, It is preferable that it is 5 mol% or less with respect to the total amount of a diamine component.

  The molar ratio of the 1,9-nonanediamine component to the 2-methyl-1,8-octanediamine component in the C9 diamine mixture used in the polyamide resin of the present invention is generally 1:99 to 99: 1, preferably 5:95 to 95: 5, more preferably 5:95 to 40:60 or 60:40 to 95: 5, especially 5:95 to 30:70 or 70:30 to 90:10. By copolymerizing 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine in the above specific amounts, the moldable temperature range is wide, the melt moldability is excellent, and the water absorption is low. Polyamide having excellent properties, chemical resistance, hydrolysis resistance, transparency and the like can be obtained.

  In the polyamide resin of the present invention, as the diamine component, the C9 diamine mixture (1,9-nonanediamine and 2-methyl-1,8-octanediamine) mixed with 1,6-hexanediamine is used. The molar ratio of C9 diamine mixture to 1,6-hexanediamine is 1:99 to 99: 1. By mixing 1,6-hexanediamine in a molar ratio of 1/99 or more with respect to the C9 diamine mixture, the above excellent effect of the polyamide resin (PA92C) comprising oxalic acid as the dicarboxylic acid component and C9 diamine mixture as the diamine component Can be maintained (particularly without impairing melt moldability and low water absorption), the melting point of the polyamide resin can be increased, and particularly the mechanical properties can be improved. The molar ratio of the C9 diamine mixture to 1,6-hexanediamine is preferably 5.1: 94.9 to 99: 1, more preferably 10:90 to 99: 1, and even more preferably 20:80 to 99: 1. It is. In particular, it is preferably 30:70 to 98: 2, and more preferably 30:70 to 90:10 (further 30:70 to 70:30). In this polyamide resin, the change to the melting point appears clearly by copolymerizing 1,6-hexanediamine in a molar ratio of 1/99 or more with respect to the C9 diamine mixture, and the melting point of the resin rises. If 6-hexanediamine is within a molar ratio of 99/1, an acceptable melt moldability can be obtained. If the molar ratio of 1,6-hexanediamine is within 80/20, the melting point of the polyamide resin will be 300 ° C. or lower, and polymerization and molding (melt moldability) will be easier, and within 70/30. It is more preferable because the melting point becomes 280 ° C. or lower and the melt moldability becomes easier.

[Production method of polyamide resin]
The polyamide resin used in the present invention can be produced by any method known as a method for producing polyamide. According to the study by the present inventors, it is preferable to synthesize the polyamide resin by subjecting diamine and oxalic acid diester to a polycondensation reaction in a batch or continuous manner. Specifically, it is preferable to carry out in the order of (i) pre-polycondensation step and (ii) post-polycondensation step as shown by the following operations.

  (I) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then diamine (diamine component) and oxalic acid diester (oxalic acid source) are mixed. When mixing, a solvent in which both the diamine and the oxalic acid diester are soluble may be used. The solvent in which both the diamine component and the oxalic acid source are soluble is not particularly limited, but toluene, xylene, trichlorobenzene, phenol, trifluoroethanol, and the like can be used, and particularly, toluene can be 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 of the oxalic acid diester and the diamine is oxalic acid diester / the diamine, 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), more preferably 0. .99 to 1.01 (molar ratio).

  While stirring and / or nitrogen bubbling in the reactor charged with the above raw materials, the temperature is raised under normal pressure. 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. In the temperature rising process, the final temperature of the prepolycondensation step, that is, from 80 to 150 ° C, is finally 220 ° C to 300 ° C, preferably 230 ° C to 280 ° C, more preferably 240 ° C to 270 ° C. Reach the range. It is preferable to carry out the reaction for 1 to 8 hours including the temperature raising time, preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final ultimate pressure in the case of performing the vacuum polymerization is less than 0.1 MPa to 13.3 Pa.

  Next, the specific example of the manufacturing method of the polyamide resin used for this invention is demonstrated. First, the raw oxalic acid diester is charged into the container. The container is not particularly limited as long as it can withstand the temperature and pressure of the polycondensation reaction to be performed later. Thereafter, the container is heated to a temperature at which it is mixed with the raw material diamine, and then the diamine is injected to start the polycondensation reaction. The temperature at which the raw materials are mixed is not particularly limited as long as it is a temperature not lower than the boiling point and lower than the boiling point of the oxalic acid diester and diamine, and the polyoxamide generated by the polycondensation reaction of the oxalic acid diester and diamine does not thermally decompose. For example, a mixture of 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,6-hexanediamine, and a C9 diamine mixture (1,9-nonanediamine and 2-methyl-1,8-octane) In the case of a polyoxamide resin using diamine and dibutyl oxalate as raw materials in which the molar ratio of diamine mixture) to 1,6-hexanediamine is 1:99 to 99: 1, the mixing temperature is preferably 15 ° C to 300 ° C. When the molar ratio of C9 diamine mixture (1,9-nonanediamine and 2-methyl-1,8-octanediamine mixture) and 1,6-hexanediamine is 5:95 to 90:10, it is liquid at room temperature. Or it is more preferable because it is easy to handle because it liquefies only by heating to about 50 ° C. When the mixing temperature is equal to or higher than the boiling point of the alcohol produced by the condensation reaction, it is desirable to use a container equipped with a device for distilling and condensing the alcohol. In addition, when pressure polymerization is performed in the presence of an alcohol produced by a condensation reaction, a pressure vessel is used. The charging ratio of oxalic acid diester to diamine is oxalic acid diester / the above diamine, 0.8 to 1.2 (molar ratio), preferably 0.91 to 1.09 (molar ratio), more preferably 0.98 to 1. 0.02 (molar ratio).

  Next, the inside of the container is heated to a temperature not lower than the melting point of the polyoxamide resin and not higher than the temperature at which it is not thermally decomposed. For example, a C9 diamine mixture (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6-hexanediamine, and a C9 diamine mixture (1,9-nonanediamine and 2-methyl- 1,8-octanediamine) and 1,6-hexanediamine molar ratio is 50:50, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 50:50. In the case of the polyoxamide resin using diamine and dibutyl oxalate as raw materials, the melting point is 261 ° C., so it is preferable to raise the temperature from 270 ° C. to 300 ° C. (pressure is 2 MPa to 4 MPa). While distilling off the produced alcohol, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. When the raw materials are mixed in a pressure-resistant vessel and subjected to pressure polymerization in the presence of an alcohol produced by a condensation reaction, the pressure is first released while the produced alcohol is distilled off. Thereafter, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. The preferable final pressure in the case of carrying out the vacuum polymerization is 760 to 0.1 Torr. The temperature is preferably 270 to 300 ° C. The alcohol is cooled and liquefied by a water-cooled condenser and recovered.

[Characteristics of polyamide resin]
There is no particular restriction on the molecular weight of the polyamide resin used in the present invention, but the relative viscosity ηr measured at 25 ° C. using a 96% concentrated sulfuric acid solution of 1.0 g / dl is more preferably 1.8 to 6.0. Is a molecular weight in the range of 2.0 to 5.5, particularly preferably in the range of 2.5 to 4.5. When the molecular weight is low, the molded product becomes brittle and the physical properties tend to decrease. On the other hand, when the molecular weight increases, the melt viscosity increases and the melt moldability tends to deteriorate.

  The polyamide resin used in the present invention uses oxalic acid as the carboxylic acid component and copolymerizes 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the diamine component, so that oxalic acid and 1,9-nonanediamine are copolymerized. The relative viscosity can be increased, that is, the molecular weight can be increased as compared with the polyamide made of The polyamide resin PA92 / 62T used in the present invention uses oxalic acid as the carboxylic acid component, and 1,9-nonanediamine and 2-methyl-1,8-octanediamine as the diamine component and further 1,6-hexamethylenediamine. By copolymerizing, it is possible to raise the melting point of the resin as compared with polyamides composed of succinic acid, 1,9-nonanediamine and 2-methyl-1,8-octanediamine.

[Layered silicate]
Layered silicate is a component that imparts mechanical properties and heat resistance to a polymer material.
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 a polyamide resin, 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.

  Further, in order to disperse the layered silicate in the polyamide resin, 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 1,9-nonanediamine and 2-methyl-1,8-octanediamine 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.

[Composite material]
The composite material of the present invention includes the polyamide resin and a layered silicate dispersed in the polyamide resin.
The amount of the layered silicate in the composite material of the present invention is not particularly limited as long as the mechanical properties and heat resistance of the composite material of the present invention are improved. Is preferably 0.05 to 10 parts by mass, more preferably 0.05 to 8 parts by mass, and particularly preferably 0.05 to 5 parts by mass. When the ratio of the layered silicate decreases, the mechanical strength and heat resistance tend to decrease, and when the ratio increases, the physical properties, particularly fluidity and impact strength of the composite material tend to decrease.

  The composite material of the present invention can further contain the following components as optional components in addition to the polyamide and the layered silicate.

(1) Other polymer The dicarboxylic acid component used in the present invention comprises oxalic acid, and the diamine component is a C9 diamine mixture (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6- The polyamide resin composed of hexanediamine and having a molar ratio of 1:99 to 99: 1 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.

Although it will not specifically limit if it is the range which does not impair the effect of this invention as said substitution ratio by said other polymer, Preferably it is less than 50 mass%, More preferably, it is 30 mass% or less.
Hereinafter, when simply referred to as “polyamide” or “polyamide resin”, the dicarboxylic acid component is composed of oxalic acid, and the diamine component is a C9 diamine mixture (1,9-nonanediamine and 2-methyl-1,8-octane). A mixture of diamines) and 1,6-hexanediamine, and the molar ratio of these is 1:99 to 99: 1.

(2) Additives Other additives can be added to the composite material 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.

  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 composite material]
The method for producing the composite material of the present invention is not particularly limited as long as the layered silicate can be uniformly dispersed in the polyamide resin. For example, when the raw material of the layered silicate is a multilayered clay mineral, as disclosed in Patent Document 1, the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as 1,9- Nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine are added to widen the space between the layers of the 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, an organic compound may be used as a swelling agent, and the layers may be preliminarily spread to about 100 mm or more and melt-mixed with the polyamide resin to disperse each layer in the polyamide resin.

  The polyamide resin composition of the present invention can be formed into a molded product by, for example, extrusion molding, blow molding, compression molding, injection molding or the like.

  Molded articles formed from the composite material of the present invention include automotive parts, industrial materials, industrial materials, electrical and electronic parts, machine parts, office equipment parts, household goods, containers, sheets, films, fibers, and any other uses and It can be various shaped products. More specifically, automotive fuel piping tubes or hoses, automotive radiator hoses, brake hoses, air conditioner hoses, wire coating materials, optical fiber coating materials and other tubes, hoses, agricultural films, linings, architectural interior materials (wallpapers) Etc.), films such as laminated steel sheets, sheets, automobile radiator tanks, chemical liquid bottles, chemical liquid tanks, bags, chemical liquid containers, tanks such as gasoline tanks, tire inner liners, tank valves, fuel delivery pipes, quick connectors, EGR parts Can be.

[Polyamide resin composition for engine cooling water system parts]
The polyamide resin composition for engine cooling water system parts of this invention contains a polyamide resin and an inorganic filler.
The amount of the inorganic filler is not particularly limited as long as it can improve the above characteristics and the like, but for example, 5 to 150 parts by weight, preferably 10 to 120 parts by weight, with respect to 100 parts by weight of the polyamide resin. More preferably, it is 25-100 mass parts. When the amount of the inorganic filler is decreased, the mechanical strength of the polyamide resin is not improved, and when it is more than 150 parts by mass, there is a tendency that problems of moldability and surface condition occur.

  The method for producing the polyamide resin composition for engine cooling water system parts of the present invention is not particularly limited. For example, normally known melt kneaders such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll. Is used. Examples of the blending order of the polyamide resin and the inorganic filler that are the raw materials of the polyamide resin composition include, for example, (i) a method in which all raw materials are blended and melt-kneaded using a twin-screw extruder, and (ii) one After mixing some raw materials, melt kneading and further mixing the remaining raw materials and melt kneading, or (iii) mixing some remaining raw materials and then mixing the remaining raw materials using a side feeder during melt kneading Any method such as a method may be used.

  Moreover, the polyamide resin composition for engine cooling water system parts of this invention can further contain the following components as an arbitrary component other than a polyamide resin and an inorganic filler.

(1) Other polymer The dicarboxylic acid component used in the present invention comprises oxalic acid, and the diamine component is a C9 diamine mixture (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6- The polyamide resin composed of hexanediamine and having a molar ratio of 1:99 to 99: 1 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.

  Examples of the thermoplastic polymer include general-purpose resin materials such as polyethylene, polypropylene, polystyrene, ABS resin, AS resin, and acrylic resin, polycarbonate, polyphenylene oxide, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, and other high heat resistant resins. It is done. In particular, when polyethylene or polypropylene is used in combination, it is desirable to use one modified with maleic anhydride or a glycidyl group-containing monomer.

Although it will not specifically limit if it is the range which does not impair the effect of this invention as said substitution ratio by said other polymer, Preferably it is less than 50 mass%, More preferably, it is 30 mass% or less.
Hereinafter, when simply referred to as “polyamide” or “polyamide resin”, the dicarboxylic acid component is composed of oxalic acid, and the diamine component is a C9 diamine mixture (1,9-nonanediamine and 2-methyl-1,8-octane). A mixture of diamines) and 1,6-hexanediamine, and the molar ratio of these is 1:99 to 99: 1.

(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.

More specifically, examples of the heat-resistant agent include hindered phenols, phosphites, thioethers, copper halosaponides and the like, and these can be used alone or in combination.
Examples of the weathering agent include hindered amines and salicylates, and these can be used alone or in combination.
Examples of the crystal nucleating agent include inorganic fillers such as talc and clay, and organic crystal nucleating agents such as fatty acid metal salts, and these can be used alone or in combination.

Examples of the crystallization accelerator include low molecular weight polyamides, higher fatty acids, higher fatty acid esters and higher aliphatic alcohols, which can be used alone or in combination.
Examples of the release agent include fatty acid metal salts, fatty acid amides, and various waxes, which can be used alone or in combination.
Examples of the antistatic agent include aliphatic alcohols, aliphatic alcohol esters, and higher fatty acid esters, which can be used alone or in combination.

  Examples of the flame retardant include metal hydroxides such as magnesium hydroxide, phosphorus, ammonium phosphate, ammonium polyphosphate, melamine cyanurate, ethylene dimelamine dicyanurate, potassium nitrate, brominated epoxy compounds, brominated polycarbonate compounds, bromine Polystyrene compound, tetrabromobenzyl polyacrylate, tribromophenol polycondensate, polybromobiphenyl ethers and chlorinated flame retardants can be mentioned, and these can be used alone or in combination.

  The polyamide resin composition of the present invention is used for engine cooling water system parts. Engine cooling water system parts here include radiator core parts, radiator tank parts such as the top and base of the radiator tank, coolant reserve tank, water pipe, water pump housing, water pump impeller, water jacket spacer, valve, thermostat case, etc. It is a part used in contact with cooling water in the engine room.

  The polyamide resin composition of the present invention can be suitably used for engine cooling water system parts, but other members requiring similar functions, for example, hot water pipes for floor heating, water sprinkling pipes for melting snow on roads, and other resin parts Also, it can be suitably used.

[Engine cooling water system parts]
The engine cooling water system component of the present invention is formed by a molding method usually performed in the industry, for example, by a method such as extrusion molding, blow molding, compression molding, injection molding or the like of the polyamide resin composition for the engine cooling water system component. It can be manufactured by molding.

[Hollow molded parts]
The hollow molded part of the present invention is produced using a polyamide resin and a layered silicate.
In this specification, the term “hollow molded part” means a part manufactured by hollow molding. Hollow molding includes rotational molding, slush molding, sheet blow molding, injection blow molding, and the like.

  The amount of the layered silicate is not particularly limited as long as the effect of the layered silicate is exhibited, but is preferably 0.05 to 10 parts by weight with respect to 100 parts by weight of the polyamide resin. More preferably, it is 0.05-8 mass parts, Most preferably, it is 0.05-5 mass parts. When the proportion of layered silicate is low, the effect of layered silicate is not exhibited, and when the proportion is high, the melt viscosity becomes extremely high and the molding processability tends to deteriorate or the impact resistance tends to decrease. .

  The method for adding the layered silicate is not particularly limited as long as the layered silicate can be uniformly dispersed in the polyamide resin. For example, when the raw material of the layered silicate is a multilayered clay mineral, as disclosed in JP-A-62-74957, the layered silicate is ionized with hydrochloric acid or the like, and a swelling agent such as, for example, 1,9-nonanediamine and 2-methyl-1,8-octanediamine are added to widen the space between the layers of the 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, an organic compound may be used as a swelling agent, and the layers may be preliminarily spread to about 100 mm or more and melt-mixed with the polyamide resin to disperse each layer in the polyamide resin.

The hollow molded part of the present invention can further contain the following components as optional components.
(1) Other polymer The dicarboxylic acid component used in the present invention comprises oxalic acid, and the diamine component is a C9 diamine mixture (a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine) and 1,6- The polyamide resin composed of hexanediamine and having a molar ratio of 1:99 to 99: 1 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.

Although it will not specifically limit if it is the range which does not impair the effect of this invention as said substitution ratio by said other polymer, Preferably it is less than 50 mass%, More preferably, it is 30 mass% or less.
Hereinafter, when simply referred to as “polyamide” or “polyamide resin”, the dicarboxylic acid component is composed of oxalic acid, and the diamine component is a C9 diamine mixture (1,9-nonanediamine and 2-methyl-1,8-octane). A mixture of diamines) and 1,6-hexanediamine, and the molar ratio of these is 1:99 to 99: 1.

(2) Additive The hollow molded part of the present invention can contain other additives as long as the effects of the present invention are not impaired. Other additives include, for example, pigments, dyes, colorants, heat resistance agents, antioxidants, weathering agents, UV absorbers, light stabilizers, lubricants, crystal nucleating agents, crystallization accelerators, mold release agents, and charging agents. Examples thereof include stabilizers, plasticizers, stabilizers such as copper compounds, antistatic agents, flame retardants, glass fibers, lubricants, fillers, reinforcing fibers, reinforcing particles, and foaming agents.

  The addition method of said other polymer and additive will not be restrict | limited especially if each can be disperse | distributed to a polyamide resin, It adds to a polyamide resin at the arbitrary time which does not impair the effect. be able to. For example, the other polymers and additives can be added immediately after the post polycondensation step of the polyamide resin.

  The hollow molded part of the present invention is a part or product molded by hollow molding, such as a fuel tank, for example, a gasoline tank, an oil tank, other tanks, various bottles such as agrochemical bottles, drinking water bottles, an air duct, It can be used for various machines such as intake manifolds, automobile intake / exhaust system parts, air spoilers, fenders, bumpers, and other automotive outer plate / exterior structural members. Examples of the hollow molded part include a fuel delivery pipe, a throttle body, a resonator, an air cleaner box, a suspension boot, an air intake manifold, an air cleaner, a resonator, a fuel rail, and a hose joint.

  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) and crystallization temperature (Tc)
Tm and Tc were measured under a nitrogen atmosphere using a PYRIS Diamond DSC manufactured by PerkinELmer. The temperature was raised from 30 ° C. to 300 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 300 ° C. for 3 minutes, and then lowered to −100 ° C. at a rate of 10 ° C./min (temperature fall first). Then, the temperature was raised to 300 ° C. at a rate of 10 ° C./min (called a temperature rising second run). For the plasticizer-containing sample, the endothermic peak temperature of the temperature rising first run from the obtained DSC chart, and for the sample not containing the plasticizer, the endothermic peak temperature of the temperature rising second run is the exothermic peak temperature of the temperature decreasing first run. Temperature.

(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 Melt viscosity was measured by attaching a 25mm cone plate to a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan Co., Ltd. Measured under conditions.

(5) Film formation A film was formed from the pellets using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. Heating and melting at 290 ° C. (260 ° C. when nylon 6 is used, resin temperature 290 ° C. for PA 66, resin temperature 230 ° C. for PA 12) in a reduced pressure atmosphere of 500 to 700 Pa for 5 minutes, press at 5 MPa for 1 minute. The film was formed. 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 polyamide hot press film obtained by the present invention in the chemicals listed below for 7 days at 23 ° C., changes in the residual mass (%) and appearance of the film were observed. Concentrated hydrochloric acid, 64% sulfuric acid, and glacial acetic acid were tested.

(8) Hydrolysis resistance The hot press film of the composite material of the present invention 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 (pH) = 14), the residual weight ratio (%) and appearance change after treatment at 121 ° C. for 60 minutes were examined.

(9) Mechanical properties [1] to [4] shown below are measured using a resin temperature of 290 ° C. (260 ° C. when nylon 6 is used, resin temperature 290 ° C. for PA 66, resin for PA 12) The temperature was 230 ° C.) and the mold temperature was 80 ° C., and this was used for molding. The data measured at 23 ° C. after the molding was shown in the table as dry, the moisture was adjusted at a humidity of 65% RH after molding, and the data measured at 23 ° C. was shown in the table.
[1] Tensile yield strength or tensile strength: Measured according to ASTM D638 using a Type I test piece described in ASTM D638.
[2] Flexural modulus: Measured according to ASTM D790 using a test piece with a test piece size of 3.2 mm × 12.7 mm × 127 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 mm.
[4] Deflection temperature under load (thermal deformation temperature): Measured at a load of 1.82 MPa in accordance with ASTM D648 using a test piece having a test piece size of 3.2 mm × 12.7 mm × 127 mm.

(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.

(12) Ethanol vapor transmission coefficient 50 ml of ethanol was put into a stainless steel container, and the container formed with the PTFE gasket was covered with a film molded under the conditions of (5) and tightened with screw pressure. . The cup was placed in a constant temperature bath at 60 ° C., and nitrogen was allowed to flow at 50 ml / min in the bath. 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 cm2.
Ethanol permeability coefficient (g · mm / m 2 · day) = [permeation weight (g) × film thickness (mm)] / [permeation area (mm 2) × days (day) × pressure (atom)]

[Production Example 1: PA92 / 62T-1]
Oxalic acid 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 to the diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator and polymer outlet The operation of charging 28.230 kg (139.56 mol) of dibutyl, pressurizing the inside of the pressure vessel to 0.5 MPa with nitrogen gas having a purity of 99.9999%, and then releasing nitrogen gas to normal pressure is performed 5 times. After repeated nitrogen substitution, the system was heated while stirring under a sealing pressure. After the temperature of dibutyl oxalate was raised to 100 ° C. over about 30 minutes, 1.241 kg (7.84 mol) of 1,9-nonanediamine and 19.639 kg (124.04 mol) of 2-methyl-1,8-octanediamine were obtained. And a mixture of 0.893 kg (7.68 mol) of 1,6-hexanediamine (molar ratio of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine is 5.62: 88.88: 5.50) was supplied into the reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes, and at the same time 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 235 ° C. over 1 hour. 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 235 ° 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 brought to 260 ° C. over about 1 hour, and the reaction was carried out at 260 ° C. 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 released to an internal pressure of 0.5 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 = 3.13.

[Production Example 2: PA92 / 62T-2]
28.462 kg (140.71 mol) of dibutyl oxalate was charged, 16.448 kg (103.88 mol) of 1,9-nonanediamine, 2.903 kg (18.34 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 2.150 kg (18.50 mol) (mixture ratio of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine is 73.83: 13.13. 03: 13.14) was reacted in the same manner as in Production Example 1 to obtain polyamide. The obtained polyamide was a white tough polymer with ηr = 2.97.

[Production Example 3: PA92 / 62T-3]
30.238 kg (149.49 mol) of dibutyl oxalate was charged, 4.486 kg (28.33 mol) of 1,9-nonanediamine, 4.486 kg (28.33 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 10.79 kg (92.85 mol) (1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine molar ratio of 18.95: 18. 95: 62.10) was supplied into the reaction vessel with a diaphragm pump at a flow rate of 1.49 liters / minute over about 17 minutes, and at the same time 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 270 ° C. over 1.5 hours. Meanwhile, the internal pressure was adjusted to 1.00 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 285 ° C. over about 1 hour, and the reaction was carried out at 285 ° 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 released to an internal pressure of 0.5 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 = 2.88.

[Production Example 4: PA92 / 62T-4]
29.864 kg (147.64 mol) of dibutyl oxalate was charged, and 5.598 kg (35.36 mol) of 1,9-nonanediamine, 5.598 kg (35.36 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 8.941 kg (76.92 mol) of a mixture (the molar ratio of 1,9-nonanediamine, 2-methyl-1,8-octanediamine and 1,6-hexanediamine was 23.95: 23. 95: 52.10) was supplied to the reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute over about 17 minutes, and at the same time 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 250 ° C. over 1 hour. Meanwhile, the internal pressure was adjusted to 1.00 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 250 ° 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 increased to 270 ° C. over about 1 hour and reacted at 270 ° 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 released to an internal pressure of 0.5 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 = 2.83.

[Production Example 5: PA92 / 62T-5]
29.107 kg (143.89 mol) of dibutyl oxalate were charged, 5.641 kg (35.63 mol) of 1,9-nonanediamine, 10.028 kg (63.34 mol) of 2-methyl-1,8-octanediamine and 1 , 6-hexanediamine 5.223 kg (44.93 mol) (1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,6-hexanediamine molar ratio 24.76: 44. 02: 31.22) 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, 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 250 ° C. over 1 hour. 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 240 ° 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 adjusted to 265 ° C. over about 1 hour, and the reaction was carried out at 265 ° 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 released to an internal pressure of 0.5 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 = 3.11.

[Reference Production Example 1: PA92C]
A mixture of 11.11 kg (70.2 mol) of 1,9-nonanediamine and 11.11 kg (70.2 mol) of 2-methyl-1,8-octanediamine was charged with 28.40 kg (140.4 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, and at the same time 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 235 ° C. over 1 hour. 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 235 ° 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 brought to 260 ° C. over about 1 hour, and the reaction was carried out at 260 ° C. 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 released to an internal pressure of 0.5 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 = 3.35.

[Comparative Production Example 1: Production of PA92]
Using only 22.25 kg (140.4 mol) of 1,9-nonanediamine as a diamine raw material, a reaction was carried out in the same manner as in Production Example 1 to obtain a polyamide. The obtained polymer was a yellowish white polymer, and ηr = 2.78.

  Polyamide PA92 / 62T-1 to PA92 / 62T-5, PA92C, PA92, and nylon 6 (manufactured by Ube Industries, UBE nylon 1015B: PA6) produced in Production Examples 1-5, Reference Production Example 1 and Comparative Production Example 1. For nylon 66 (Ube Industries, UBE nylon 2020B: PA66) and nylon 12 (Ube Industries, UBESTA3020U: PA12), relative viscosity, melting point, crystallization temperature, 1% weight loss temperature, melt viscosity, saturated water absorption, resistance to water Chemical properties, hydrolysis resistance, 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, nylon 66 and nylon 12, has excellent chemical resistance and hydrolysis resistance, and has excellent mechanical properties under wet conditions. It is excellent in producing a tough molded body having a wider moldable temperature range and excellent melt moldability than that of a polyamide resin (PA92) using 1,9-nonanediamine alone as a diamine component, and capable of increasing the molecular weight. I understand that I can do it.
The composite material of the present invention includes a layered silicate dispersed in a polyamide resin, but the composite material basically retains the characteristics of the above-described polyamide resin.

[Example 1]
0.5 parts by mass of organic montmorillonite (Nanocor, Nanomer 30TC) is added to 100 parts by mass of PA92 / 62T-1 produced in Production Example 1, and melt kneaded at 290 ° C. using a biaxial kneader. Thus, a composite material of the present invention in the form of pellets was obtained.

[Examples 2 to 7]
A composite material of the present invention in the form of pellets was obtained in the same manner as in Example 1 except that the composition in Table 2 was followed.

[Comparative Example 1]
A composite material was obtained in the same manner as in Example 1 using PA6 (manufactured by Ube Industries, UBE nylon 1015B) instead of the polyamide resin.

  Table 2 shows the characteristics of the composite materials of Examples 1 to 7 and Comparative Example 1. The characteristics of PA92 produced in Production Example 7 are shown in Table 2 as Reference Example 1.

  The composite material comprising the polyamide resin and the layered silicate of the present invention has high mechanical strength, heat resistance, and barrier property against liquid or vapor, and has low water absorption, resistance to resistance compared to conventional nylon 6-based composite materials. Excellent chemical properties and hydrolysis resistance, and has a wider moldable temperature range than polyamide resin composites using 1,9-nonanediamine alone as the diamine component. It is industrially useful because it can be used as a molding material for industrial materials, industrial materials, household products and the like.

Claims (9)

  A composite material comprising a polyamide resin and a layered silicate dispersed in the polyamide resin, wherein the dicarboxylic acid component of the polyamide resin is composed of oxalic acid, and the diamine component is 1,9-nonanediamine and 2-methyl- It consists of a mixture of 1,8-octanediamine (hereinafter referred to as “C9 diamine mixture”) and 1,6-hexanediamine (hereinafter referred to as “C6 diamine”), and the molar ratio of C9 diamine mixture to C6 diamine is 1. A composite material which is a polyamide resin which is 99 to 99: 1.   The relative viscosity (ηr) of the polyamide resin measured at 25 ° C. using a polyamide resin solution having a concentration of 1.0 g / dl using 96% sulfuric acid as a solvent is 1.8 to 6.0. The composite material described in 1.   1% weight loss temperature in thermogravimetric analysis of the polyamide resin measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere, and differential scanning calorimetry measured at a temperature rising rate of 10 ° C./min in a nitrogen atmosphere. The composite material according to claim 1, wherein the temperature difference from the melting point measured by the step is 50 ° C. or more.   The composite material according to any one of claims 1 to 3, wherein a molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is 5:95 to 95: 5.   The composite material according to any one of claims 1 to 4, wherein a content of the layered silicate is 0.05 to 10 parts by mass with respect to 100 parts by mass of the polyamide resin.   The composite material according to any one of claims 1 to 5, wherein 50% by mass or more of the layered silicate is dispersed in a single layer in the polyamide resin.   The composite material according to any one of claims 1 to 6, wherein the layered silicate is an aluminum silicate phyllosilicate or a magnesium silicate phyllosilicate.   The polyamide resin composition for engine cooling water system components which uses the composite material as described in any one of the said Claims 1-7.   A hollow molded part using the composite material according to any one of claims 1 to 7.