JP2009298854A - Composite material containing polyamide resin and layered silicate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite material capable of manufacturing a rigid molded article having high mechanical strengths, heat-resistance and a liquid and vapor barrier property, being more excellent in a low water-absorption property, chemical-resistance and hydrolysis-resistance as compared with a conventional nylon-6-based composite material, having a wider moldable temperature range than a polyamide resin-based composite material using a 1,9-nonanediamine simple substance as a diamine component, being excellent in melt moldability and capable of further attainings high molecular weight. <P>SOLUTION: The composite material contains the polyamide resin and a layered silicate dispersed in the polyamide resin. A dicarboxylic acid component of the polyamide resin comprises oxalic acid, a diamine component comprises 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and a molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 1:99-99:1. <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 more molded than polyamide resin-based composite materials using 1,9-nonanediamine alone as the 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 clothing, industrial material fibers, 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 are 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.
In the prior literature, there was no specific disclosure of 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.

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

  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 and better melt moldability than polyamide resin-based composite materials using 1,9-nonanediamine alone as the diamine component. It is an object of the present invention to provide a composite material capable of producing a tough molded body capable of increasing the molecular weight.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that from oxalic acid diester as a oxalic acid source, 1,9-nonanediamine and 2-methyl-1,8-octanediamine as diamine components. The present inventors have found that the above-mentioned problems can be solved by using the resulting polyamide resin for the composite material, and have completed the invention.

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 polyamide resin has a dicarboxylic acid component comprising oxalic acid, a diamine component comprising 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2-methyl-1,8-octane. A composite material having a molar ratio with diamine 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, the diamine component is composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2-methyl- The molar ratio with 1,8-octanediamine is 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.

  As the diamine component, a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is used. The molar ratio of the 1,9-nonanediamine component to the 2-methyl-1,8-octanediamine component is 1:99 to 99: 1, preferably 5:95 to 95: 5. By copolymerizing a specific amount of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, the water absorption is low, the moldable temperature range is wide, the melt moldability is excellent, and the chemical resistance and hydrolysis resistance are high. A polyamide having excellent properties can be obtained.

Furthermore, the molar ratio of 1,9-nonanediamine to 2-methyl-1,8-octanediamine is preferably, for example, 5:95 to 40:60 or 60:40 to 95: 5, and 5: It is particularly preferred that it is 95-30: 70 or 70: 30-90: 10.
When the molar ratio is 5:95 to 40:60, particularly 5:95 to 30:70, the crystallinity is excellent, so that low water absorption and mechanical properties are excellent, and liquid and / or vapor (for example, , Alcohol) has low permeability, and more water absorption than the case where the molar content of 1,9-nonanediamine is higher than the molar content of 2-methyl-1,8-octanediamine. There is an advantage that it is low. On the other hand, when the molar ratio is 60:40 to 95: 5, particularly 70:30 to 90:10, there is an advantage that low water absorption and mechanical properties are more excellent and excellent transparency is imparted. .

  In the polyamide resin used in the present invention, 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used as diamine components, but other diamine components are blended within a range not impairing the effects of the present invention. be able to. Examples of diamine components other than 1,9-nonanediamine and 2-methyl-1,8-octanediamine include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 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 , 6-hexanediamine, aliphatic diamines such as 5-methyl-1,9-nonanediamine, cyclohexanediamine, methylcyclohexanediamine, and cycloaliphatic diamines such as 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.

[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. Let 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 that is not lower than the melting 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 is not thermally decomposed. For example, it consists of a mixture of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 1:99 to 99: In the case of a polyoxamide resin using diamine 1 and dibutyl oxalate as raw materials, the mixing temperature is preferably 15 ° C to 240 ° C. Moreover, since the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 5:95 to 90:10, it is liquid at room temperature or liquefied only by heating to about 40 ° C. It is more preferable because it is easy to handle. 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 generated by a condensation reaction, a pressure vessel is used. The charging ratio of oxalic acid diester and diamine is oxalic acid diester / diamine as described above, 0.8 to 1.2 (molar ratio), preferably 0.91 to 1.09 (molar ratio), more preferably 0.98. -1.02 (molar ratio).

  Subsequently, 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 no thermal decomposition occurs. For example, a diamine and shu comprising 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and the molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 85:15. In the case of a polyoxamide resin using dibutyl acid as a raw material, the melting point is 235 ° C., so it is preferable to raise the temperature from 240 ° C. to 280 ° 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 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 240 to 280 ° 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 moldable temperature range represented by the difference (Td−Tm) between the 1% weight loss temperature (hereinafter abbreviated as Td) and the melting point (hereinafter abbreviated as Tm), which is a substantial thermal decomposition index, is oxalic acid. And a polyamide composed of 1,9-nonanediamine, preferably 50 ° C. or higher, more preferably 60 ° C. or higher, and even 90 ° C. or higher. The polyamide resin used in the present invention has a Td of preferably 280 ° C. or higher, more preferably 300 ° C. or higher, still more preferably 320 ° C. or higher, and has high heat resistance.

[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.

  Examples of the raw material for the layered silicate include layered phyllosilicate minerals composed of magnesium silicate or aluminum silicate layers, that is, aluminum silicate phyllosilicate or magnesium silicate phyllosilicate. Specific examples include smectite clay minerals such as montmorillonite, saponite, beidellite, nontronite, hectorite, and stevensite, vermiculite, and halloysite. 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 is composed of oxalic acid, the diamine component is composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2- The polyamide resin having a molar ratio with methyl-1,8-octanediamine 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.
In the following, when simply referred to as “polyamide” or “polyamide resin”, the dicarboxylic acid component consists of oxalic acid, the diamine component consists of 1,9-nonanediamine and 2-methyl-1,8-octanediamine, And it shall refer to the polyamide resin whose molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 1: 99-99: 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 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 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, tubes or hoses for automobile fuel piping, automobile radiator hoses, brake hoses, air conditioner hoses, tubes for electric wire coating materials, optical fiber coating materials, hoses, agricultural films, linings, architectural interior materials (wallpapers) Etc.), Laminated steel plate films, sheets, automotive radiator tanks, chemical bottles, chemical tanks, bags, chemical containers, gasoline tanks, tire inner liners, tank valves, fuel delivery pipes, quick connectors, EGR parts Can be.

  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 270 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 270 ° 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 270 ° C. at a rate of 10 ° C./min (called a temperature raised second run). From the obtained DSC chart, the exothermic peak temperature of the temperature decrease first run was Tc, and the endothermic peak temperature of the temperature increase second run was Tm.

(3) 1% weight loss temperature (Td)
Td was measured by thermogravimetric analysis (TGA) using THERMOGRAVIMETRIC ANALYZER TGA-50 manufactured by Shimadzu Corporation. The temperature was raised from room temperature to 500 ° C. at a rate of 10 ° C./min under a nitrogen stream of 20 ml / min, and Td was measured.
(4) Melt viscosity Melt viscosity was measured by attaching a 25 mm cone plate to a melt viscoelasticity measuring device ARES manufactured by TA Instruments Japan Co., Ltd., at 250 ° C. in nitrogen and at a shear rate of 0.1 s ⁻¹ . 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. In a reduced pressure atmosphere of 500 to 700 Pa, the film was heated and melted at 260 ° C. (resin temperature 290 ° C. for PA66, resin temperature 230 ° C. for PA12) for 5 minutes, and then pressed at 5 MPa for 1 minute to form a film. 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 260 ° C. (resin temperature 290 ° C. for PA 66, resin temperature 230 ° C. for PA 12) and mold temperature 80 ° C. This was molded by injection molding using this. 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 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 60 ° C. constant temperature bath, 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 cm ² .
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: Production of PA92-1]
Oxalic acid in a pressure vessel with a volume of 150 liters equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with a diaphragm pump, nitrogen gas inlet, pressure relief port, pressure regulator and polymer outlet The operation of charging 28.40 kg (140.4 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 After repeated nitrogen substitution, the system was heated while stirring under a sealing pressure. After adjusting the temperature of dibutyl oxalate to 100 ° C. over about 30 minutes, 18.89 kg (119.3 mol) of 1,9-nonanediamine and 3.34 kg (21.1 mol) of 2-methyl-1,8-octanediamine were obtained. ) (Molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 85:15) into a reaction vessel by a diaphragm pump at a flow rate of 1.49 liters / minute for about 17 minutes. The temperature was raised simultaneously with the supply. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 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, stirring was stopped, the inside of 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 = 3.20.

[Production Example 2: Production of PA92-2]
A mixture of 17.62 kg (111.3 mol) of 1,9-nonanediamine and 4.45 kg (28.1 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 80:20). The obtained polyamide was a white tough polymer and had ηr = 3.10.

[Production Example 3: Production of PA92-3]
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 (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 50:50). The obtained polymer was a white tough polymer, and ηr = 3.35.

[Production Example 4: Production of PA92-4]
A mixture of 6.67 kg (42.1 mol) of 1,9-nonanediamine and 15.56 kg (98.3 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by reacting in the same manner as in Production Example 1 except that the octanediamine molar ratio was 30:70). The obtained polyamide was a white tough polymer, and ηr = 3.55.

[Production Example 5: Production of PA92-5]
A mixture of 1.33 kg (8.4 mol) of 1,9-nonanediamine and 20.88 kg (131.9 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -Polyamide was obtained by carrying out the reaction in the same manner as in Production Example 1 except that the molar ratio of octanediamine was 6:94). The obtained polymer was a white tough polymer, and ηr = 3.53.

[Production Example 6: Production of PA92-6]
A mixture of 1.33 kg (8.4 mol) of 1,9-nonanediamine and 20.88 kg (131.9 mol) of 2-methyl-1,8-octanediamine (1,9-nonanediamine and 2-methyl-1,8 -The octanediamine molar ratio was 6:94), and the reaction was carried out in the same manner as in Production Example 1 except that the internal pressure by extracting butanol was maintained at 0.25 MPa to obtain polyamide. The obtained polymer was a white tough polymer, and ηr = 4.00.

[Production Example 7: Production of PA-92-0]
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.

  Table 1 shows the characteristic data of polyamides prepared in Production Examples 1 to 7 and commercially available PA6 (Ube Industries, UBE nylon 1015B), PA66 (Ube Industries, UBE nylon 2020B) and PA12 (Ube Industries, UBESTA3020U). Shown in

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. Produces a tough molded body that is excellent and has a wider moldable temperature range and better melt moldability than polyamide resin (PA92-0) using 1,9-nonanediamine alone as a diamine component, and can have a higher molecular weight. I can see that
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]
To 100 parts by mass of PA92-1 produced in Production Example 1, 0.5 parts by mass of organic montmorillonite (Nanocor, Nanomer 30TC) was added, and melt kneaded at 260 ° C. using a biaxial kneader. A composite material of the present invention in the form of pellets was obtained.

[Examples 2 to 8]
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 8 and Comparative Example 1. The characteristics of PA92-0 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 goods and the like.

Claims (7)

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 1,9-nonanediamine and 2-methyl-1,8-octanediamine, and 1,9-nonanediamine and 2-methyl-1,8-octane A composite material having a molar ratio with diamine of 1:99 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 heating rate of 10 ° C./min in a nitrogen atmosphere, and differential scanning calorimetry measured at a heating 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.