JPH1147569A - Gas-permeable material consisting of polyamide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a gas-permeable material formed of a polyamide having an amid group in a molecular chain with nearly the same degree of ratio as that in nylon 6 or nylon 66. SOLUTION: The gas-permeable material comprises a polyamide wherein the polyamide consisting of 50-100 wt.% of dicarboxylic acid component being dicarboxylic acid component consisting of 1,6-decanedicarboxylic acid and 0-50 wt.% of diamine component and a total amount being aliphatic aminocarboxylic acid component and/or lactam component has an amid group with nearly the same degree of ratio as that in nylon 6 or nylon 66.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a gas-permeable material formed from a polyamide containing a specific ratio of units of 1,6-decanedicarboxylic acid and diamine in the molecular chain.

[Prior art]

[0002] Polyamides are excellent in mechanical properties, thermal properties, oil resistance, processability, oxygen gas barrier properties, etc., and are therefore used in the fields of automobile parts, electric parts, food packaging materials, etc. in the form of molded articles, films, fibers, and the like. It is used after being processed into monofilaments and hollow fibers. Since the gas permeability coefficient of polyamide is considerably lower than that of polyethylene, polypropylene, polybutadiene, polystyrene and the like, the use of polyamide as an oxygen gas barrier material has been increasing in recent years. The gas permeability coefficient of nylon 6, which is one of typical polyamides, is about 1/100 of that of polyethylene. It is believed that this is because nylon forms a denser molecular structure than polyethylene due to cohesion based on hydrogen bonds between amide groups.

On the other hand, when the cohesive force based on the hydrogen bond between amide groups is weakened, the gas permeability coefficient is increased, that is, the gas permeability is improved. In addition, functional properties such as hydrophilicity, hydrogen bonding property, and electron donating property based on an amide group are easily exhibited, and it is expected that a new use of polyamide is opened. For example, see JP-A-59-87154.
In the publication, the polyamide copolymer composed of a specific monomer has lower crystallinity than a homopolymer, that is,
It describes that the cohesive force based on hydrogen bonding is weakened and the gas permeability is improved. However, the structure of this copolymer is not clear, and the degree of gas permeability is not clear. As another method for improving gas permeability, there is a method in which the ratio of amide groups in the polyamide is reduced to reduce the cohesive force based on hydrogen bonds. However, the ultimate material obtained by this method is a material having no amide group, such as polyolefin, and cannot be said to be a material having the inherent characteristics of polyamide. Heretofore, there has been no specific proposal for a polyamide having an amide group ratio in a molecular chain substantially equal to that of a general-purpose polyamide such as nylon 6 or nylon 66 and having excellent gas permeability.

[Problems to be solved by the invention]

An object of the present invention is to provide a gas permeable material formed from a polyamide having an amide group in a molecular chain at substantially the same ratio as nylon 6, nylon 66, or the like.

[Means for Solving the Problems]

[0005] In order to obtain a polyamide having an excellent gas permeability, the ratio of the amide group in the polyamide is substantially the same as that of nylon 6, nylon 66, etc., various monomers are used to determine the relationship between the molecular structure and the gas permeability. It was investigated. As a result, they have found that a polyamide containing a specific proportion of a dicarboxylic acid component unit having a specific branch at a specific ratio or more has excellent gas permeability, and arrived at the present invention.

That is, the present invention relates to (A) a unit derived from a dicarboxylic acid component in which 50 to 100% by weight of the dicarboxylic acid component is 1,6-decanedicarboxylic acid;
(B) a unit derived from a diamine component, and (C)
It is a gas-permeable material formed from a polyamide consisting of units derived from an aliphatic aminocarboxylic acid component and / or units derived from a lactam component in an amount of 0 to 50% by weight based on the total amount.

[0007] A second invention of the present invention is a gas-permeable material comprising the above-mentioned polyamide, which is a molded product, a film, a fiber, a monofilament or a hollow fiber.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As the 1,6-decanedicarboxylic acid of the present invention, those produced by oxidative decomposition of cyclohexane or a method using 7-cyanoundecanoic acid as a raw material can be used. A polyamide having a specific unit or more of 1,6-decanedicarboxylic acid as a constitutional unit is a feature of the present invention. Also,
The ratio of the amide group of the polyamide having 1,6-decanedicarboxylic acid as a constitutional unit is almost the same as that of nylon 6 or nylon 66, and 1,6-decanedicarboxylic acid is a constitutional unit suitable for the purpose of the present invention. . In addition, 1,
The excellent gas permeability of the polyamide containing 6-decanedicarboxylic acid as a structural unit suggests that 1,6-decanedicarboxylic acid reduces the cohesive force based on hydrogen bonds.

The proportion of 1,6-decanedicarboxylic acid in the dicarboxylic acid component used in the present invention is 50 to 100% by weight, preferably 70 to 100% by weight. If the proportion of 1,6-decanedicarboxylic acid is less than 50% by weight, the resulting polyamide may have poor gas permeability, which is not preferable.

The dicarboxylic acids other than 1,6-decanedicarboxylic acid used in the present invention include known aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. Specific examples of the aliphatic dicarboxylic acids include butanedioic acid, pentanedioic acid, hexanedioic acid, octanedioic acid, nonandioic acid, decandioic acid, undecandioic acid, dodecandionic acid, tridecandionic acid, tetradecandionic acid, and pentadecandione Acid, hexadecandioic acid and the like. Specific examples of the alicyclic dicarboxylic acid include 1,3-cyclohexanedicarboxylic acid,
Examples include 1,4-cyclohexanedicarboxylic acid. Specific examples of aromatic dicarboxylic acids include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid and 1,4
-Naphthalenedicarboxylic acid and the like. These dicarboxylic acids can be used alone or in combination of two or more.

The diamine used in the present invention includes known diamines, for example, aliphatic alkylene diamines having 2 to 8 carbon atoms, alicyclic diamines, aromatic diamines and the like. Specific examples of the aliphatic alkylenediamine having 2 to 12 carbon atoms include 1,2-diaminoethane and 1,3-diaminoethane.
Diaminoethane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-
Diaminoheptane, 1,8-diaminooctane, 1,9
-Diaminononane, 1,10-diaminodecane, 1,1
1-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotridecane, 1,15-diaminopentadecane, 1,
16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 2,2
4-, 2,4,4-trimethylhexamethylenediamine and the like. Among them, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane and 2,2,4-, 2,4,4-trimethylhexamethylenediamine are easy to handle and polymerized. It has good reactivity and is preferable.

As the alicyclic diamine, any diamine containing a cyclohexane ring can be used. Specific examples include 1,4-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, and bis (3-methyl-4-aminocyclohexyl) methane. No.

As the aromatic diamine, any diamine containing an aromatic ring can be used. Specific examples include paraxylenediamine, metaxylenediamine, paraphenylenediamine, metaphenylenediamine, and 4,4′-diaminodiphenylmethane. Of these, paraxylenediamine and metaxylenediamine are preferred because they are easy to handle and have good polymerization reactivity. These aliphatic alkylenediamines, alicyclic diamines and aromatic diamines can be used alone or in combination of two or more.

In producing the polyamide of the present invention, 1,6
A dicarboxylic acid and a diamine containing 50 to 100% by weight of decanedicarboxylic acid may be used as they are,
A nylon salt or an aqueous solution of a nylon salt synthesized by dissolving and mixing a dicarboxylic acid and a diamine in water or hot water and adjusting the pH may be used. Dicarboxylic acid and diamine are generally in a molar ratio of 1.00 / 0.9.
5 to 1.00 / 1.05, preferably 1.00 / 0.9
It is used at a ratio of 9 to 1.00 / 1.01. If the ratio is excessively out of this range, the practical strength of the obtained polyamide becomes low, and it becomes difficult to obtain a good molded product.

Specific examples of the aliphatic aminocarboxylic acid used in the present invention include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctylic acid, 9-aminononanoic acid, 10-aminocapric acid, and 11-aminocapric acid. And undecanoic acid and 12-aminododecanoic acid. Lactam is a cyclic amide compound having 4 to 12 carbon atoms, and specific examples include ε-caprolactam, ω-enantholactam, ω-undecanelactam, ω-dodecalactam, α-pyrrolidone, δ-methylpyrrolidone, and the like. . These aliphatic aminocarboxylic acids and lactams can be used alone or in an appropriate combination of two or more. Among them, 6-aminocaproic acid, 12
-Aminododecanoic acid and ε-caprolactam are preferred because they are easy to handle and have good polymerization reactivity.

The amount of the aliphatic aminocarboxylic acid or lactam used is 0 to 50% by weight, preferably 0 to 30% by weight, based on the total amount of the polyamide to be produced. If the amount is more than 50% by weight, the resulting polyamide may have poor gas permeability, which is not preferable.

For the production of the polyamide of the present invention, known polymerization methods such as melt polymerization, solution polymerization, and interfacial polymerization can be used. These polymerization methods can be used alone or in an appropriate combination. Generally, melt polymerization is simple and preferred. These polymerizations can be carried out batchwise or continuously. Further, the polymerization reaction may be divided into two or more stages, and a low-molecular-weight polyamide may be produced first, and then a high-molecular-weight polyamide may be produced.

As the apparatus used for the polymerization, a known polyamide production apparatus can be used. For example, kneading reaction extruders such as batch reactors, single-tank or multi-tank continuous reactors, tubular continuous reactors, single-screw kneading extruders, twin-screw kneading extruders and multi-screw kneading extruders, and the like. There is a horizontal second polymerization tank disclosed in Japanese Patent Publication No. 4-32096.

The polyamide of the present invention is prepared from 1,6
Polymerization of a mixture of dicarboxylic acid and diamine containing 50 to 100% by weight of decanedicarboxylic acid, or a mixture of these nylon salts and, if necessary, a predetermined amount of aliphatic aminocarboxylic acid or lactam, or a mixture of these mixtures and water. 160-320 ° C, preferably 180-300 ° C, more preferably 200-280 ° C under stirring.
It is obtained by polymerizing under pressure, normal pressure or reduced pressure at the above temperature. When the polymerization temperature is low, the polymerization rate is slow,
Polymerization time becomes longer and efficiency is poor. On the other hand, when the polymerization temperature is high, side reactions and thermal decomposition reactions are likely to occur, and the resulting polyamide may be colored or gelled.

In general, the polymerization pressure is normal pressure or pressurization in the early stage of polymerization, and normal pressure or reduced pressure in the latter stage of polymerization to obtain a high molecular weight. The preferable pressure is 10 to 760 mmHg.
It is. When the pressure in the latter stage of the polymerization is higher than normal pressure, it is difficult to remove water contained in the polymerization reaction product and water produced as a result of the polymerization (condensation) reaction out of the polymerization reaction system, and it is possible to increase the molecular weight. It will be difficult. If the polymerization pressure is too low, the decompression equipment for evacuation becomes very costly. When the pressure during polymerization is reduced, at least one vent port is provided in the polymerization apparatus, and the vent port is connected to a known vacuum equipment such as a Nash pump, a mechanical booster, or a steam ejector to forcibly exhaust the gas. Done.

In the present invention, water can be added to the raw material mixture for adjusting the polymerization pressure and the viscosity of the polymerization reaction product. The water used is not particularly limited, but it is preferable to use pure water such as ion-exchanged water or distilled water, and furthermore, degassing by boiling these waters immediately before use to remove oxygen dissolved in the water. More preferably, water is used. When water is used, it is generally used in an amount of 1 to 150 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the total amount of the raw materials. If the amount of water used is too small, the melt viscosity of the polymerization reaction product may increase. Further, when the amount of water used is large, the molecular weight of the obtained polyamide becomes small.

The polyamide of the present invention can be obtained by polymerizing under the above polymerization temperature and polymerization pressure conditions, usually for about 5 minutes to 30 hours. The polyamide of the present invention has a number average molecular weight of 6,000 to 40,000, preferably 800
0 to 30,000. When the number average molecular weight is smaller than 6000, practical properties such as mechanical strength are not sufficient,
From the viewpoint of strength, it may be difficult to manufacture products such as molded products and films. On the other hand, when the number average molecular weight is more than 40,000, the viscosity at the time of melting becomes high, and it becomes difficult to mold a molded product, a film or the like. The number average molecular weight is a value determined from the reciprocal of the average value of the terminal amino group concentration and the terminal carboxyl group concentration of the obtained polyamide.

In the production of the polyamide of the present invention, phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, and their alkali metal salts and alkaline earth metals are used to promote polymerization and prevent deterioration during polymerization. Phosphorus compounds such as salts or esters can be added. Usually, the addition amount of these phosphorus compounds is preferably in the range of 50 to 3,000 ppm based on the polyamide to be obtained. If the amount is out of this range, the polymerization rate is decreased, and the resulting polyamide may be colored or gelled, which is not preferable.

For the purpose of controlling the molecular weight of the polyamide of the present invention and stabilizing the melt viscosity during molding, amines, carboxylic acids and the like can be added as a molecular weight regulator. The amine or carboxylic acid to be added is not particularly limited as long as it is monofunctional and / or bifunctional, and specific examples include monoamines such as laurylamine, stearylamine and benzylamine, 1,6-diaminohexane,
1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, meta-xylylenediamine, para-xylylenediamine Monocarboxylic acids such as diamines, acetic acid, benzoic acid, lauric acid, stearic acid and the like, butanedioic acid, pentanedioic acid, hexanedioic acid, octandionic acid, nonandionic acid, decandionic acid, undecandionic acid, dodecandionic acid, isophthalic acid There are acids, dicarboxylic acids such as terephthalic acid. The amount of these molecular weight regulators used depends on the reactivity of the molecular weight regulator used and the polymerization conditions, but an amount corresponding to the number average molecular weight of the polyamide to be finally obtained is used.

Further, the polyamide of the present invention may contain, if necessary, a heat-resistant agent, an antioxidant, a weathering agent, a lubricant, an antistatic agent, a pigment, a dye, an anti-blocking agent, etc. within a range that does not impair the properties of the polyamide. You can also.

The polyamide of the present invention can be used as a gas-permeable material in the form of molded articles, films, fibers, monofilaments or hollow fibers. There are no particular restrictions on the manufacture of products of these shapes, and each is manufactured by a known molding method. For example, molded articles are manufactured by injection molding, blow molding, vacuum forming, etc., and films are formed by T-die method, inflation method, tubular method, solvent casting method, compression molding method, etc. using a known extruder. Fibers, monofilaments and hollow fibers are produced by a known melt spinning method or wet spinning method. Unstretched or stretched films, fibers, monofilaments and hollow fibers can be used. When performing injection molding, melt molding such as blow molding or extrusion molding, the melting temperature of the polyamide of the present invention,
Generally, 130-300 ° C., preferably 150-250
° C.

In the polyamide of the present invention, the melting point is not observed or the heat of fusion is very small even if it is observed by the differential scanning calorimetry. Further, it has a property that the gas permeability coefficient is large. This suggests that the polyamide of the present invention has significantly reduced cohesive force based on amide groups as compared to nylon 6, nylon 66, and the like. Therefore, molded articles, films, fibers, monofilaments and hollow fibers formed from the polyamide of the present invention have excellent gas permeability, and also have functional properties such as hydrophilicity based on amide groups, hydrogen bonding properties, and electron donating properties. It can be expected that it shows a good property.

[0028]

EXAMPLES Examples and comparative examples are shown below to specifically explain the effects of the present invention. The measured values shown in the examples and comparative examples were measured by the following methods.

1) Relative viscosity (ηr) According to JIS K6810, the viscosity was measured at a temperature of 25 ° C. using 98% by weight of concentrated sulfuric acid as a solvent at a polyamide concentration of 1% by weight / volume using an Ostwald viscometer.

2) Terminal amino group concentration ([NH ₂ ]) About 1 g of polyamide was dissolved in 40 ml of a phenol / methanol mixed solvent (volume ratio: 9/1), and the obtained sample solution was treated with thymol blue as an indicator. Using 1/20
Titration with N hydrochloric acid.

3) Terminal carboxyl group concentration ([COO
H]) 40 ml of benzyl alcohol was added to about 1 g of polyamide, and the mixture was heated and dissolved in a nitrogen gas atmosphere, and the obtained sample solution was halved using phenolphthalein as an indicator.
Titration was performed with a 0N potassium hydroxide-ethanol solution.

4) Number average molecular weight (Mn) The number average molecular weight (Mn) was determined as the reciprocal of the average value of the terminal amino group concentration ([NH ₂ ]) and the terminal carboxyl group concentration ([COOH]).

5) Glass transition temperature (Tg) The glass transition temperature (Tg) was measured using a differential scanning calorimeter DSC-50 manufactured by Shimadzu Corporation, which was tested with 1-heptane and indium. After cooling the sample polymer to −50 ° C. with liquid nitrogen, it was heated to 200 ° C. at a rate of 10 ° C./min. The measurement was performed in a helium gas atmosphere supplied at a rate of 30 ml / min.

6) Melting point and heat of fusion A polyamide was dried under reduced pressure at 40 ° C. for 72 hours using a differential scanning calorimeter DSC-50 manufactured by Shimadzu Corporation under a nitrogen gas atmosphere at a temperature rising rate of 10 ° C./min. The melting point was determined from the endothermic peak temperature, and the heat of fusion was determined from the endothermic area.

7) Oxygen gas permeability coefficient Compression molding machine (Model F-37, manufactured by Shinto Metal Industry Co., Ltd.)
Using the film prepared in the above as a sample, using an oxygen gas permeability measuring device OX-TRAN 2/20 manufactured by MOCON,
The measurement was performed under the conditions of a relative humidity of 0% and 23 ° C.

Example 1 Degassed water at 50 ° C. obtained by boiling high-purity ion-exchanged water 3
200 g of 1,6-decanedicarboxylic acid was dispersed in 71.4 g, and a 35% by weight aqueous solution of 1,6-diaminohexane was added thereto while stirring under a nitrogen gas atmosphere.
The addition was stopped at the time of reaching 12, and an approximately 35% by weight aqueous solution of a nylon salt composed of 1,6-diaminohexane and 1,6-decanedicarboxylic acid (hereinafter abbreviated as “6D salt”) was obtained. . This aqueous solution is concentrated to about 75% by weight,
278 g of the salt aqueous solution was charged into a 1-liter pressure vessel equipped with a stirrer, a thermometer, a pressure gauge, a nitrogen inlet, a pressure outlet, and a polymer outlet. After the pressure vessel was sufficiently purged with nitrogen, the temperature was raised in a closed state with stirring, and the temperature was 220 ° C.
Polymerization was performed at kgf / cm ² G for 3 hours. Then, while maintaining the pressure in the pressure vessel at 16 kgf / cm ² G, 2
The temperature was raised to 70 ° C. over 1 hour, and then the pressure in the pressure vessel was released at the same temperature over 30 minutes to normal pressure. Next, polymerization was performed at 270 ° C. and 760 mmHg for 2 hours while flowing nitrogen gas at a flow rate of 200 ml / min into the pressure vessel. Thereafter, stirring was stopped, and the produced polyamide was taken out in a string form from a polymer outlet at the bottom of the pressure vessel, immediately cooled in a water bath, and then made into a cylindrical polyamide chip with a pelletizer. This polyamide chip is heated at 40 ° C for 7
Vacuum dried for 2 hours. The obtained polyamide was colorless and transparent. Using a compression molding machine, this polyamide was
After preheating at 0 ° C. and 0 kgf / cm ² G for 2.5 minutes,
A film was formed under the conditions of 0 ° C., 50 kgf / cm ² G, and 2.5 minutes. The thickness of the film was 96 μm.
Table 1 shows the properties of the obtained polyamide.

Comparative Example 1 A 30% by weight aqueous solution of a nylon salt comprising equimolar amounts of 1,6-diaminohexane and octanedioic acid was prepared according to the method of Example 1. This aqueous solution was concentrated to about 90% by weight and charged in the same pressure vessel as in Example 1. After the pressure vessel is sufficiently purged with nitrogen, the temperature is raised in a sealed state with stirring,
Polymerization was performed at a temperature of 220 ° C. and a pressure of 15 kgf / cm ² G for 3 hours. Thereafter, the pressure in the pressure vessel was increased to 15 kgf / cm.
While maintaining the ² G, the temperature was raised over a period of 1 hour to 275 ° C.,
Subsequently, the pressure in the pressure vessel was released at the same temperature over 30 minutes to normal pressure. Next, 200 ml /
While flowing nitrogen gas at a flow rate of min.
Polymerization was performed at 0 mmHg for 3 hours. Thereafter, a polyamide chip was obtained in the same manner as in Example 1. This polyamide chip was vacuum dried at 40 ° C. for 72 hours. The resulting polyamide was white. The polyamide using a compression molding machine, 240 ° C., was preheated 2.5 minutes ^{0kgf / cm 2 G, 240 ℃} , to form a film under the conditions of 50kgf / cm ² G, 2.5 min. Film thickness is 65μm
Met. Table 1 shows the properties of the obtained polyamide.

Example 2 In a 160 ml-capacity glass container equipped with a stirrer and a nitrogen inlet, 6.829 g of metaxylylenediamine (0.
0501 mol) and 1,6-decanedicarboxylic acid.
530 g (0.0501 mol) were charged. After sufficiently replacing the inside of the glass container with nitrogen, the glass container is immersed in a heat medium bath, and 200 ° C. while flowing a nitrogen gas at 50 ml / min with stirring.
, And then the temperature was raised to 280 ° C over 1 hour, followed by polymerization at 280 ° C for 4 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Thereafter, the glass container was cracked to take out the polyamide, pulverized, and dried under reduced pressure at 40 ° C. for 72 hours. The obtained polyamide was colorless and transparent. Using this polyamide, a film was prepared in the same manner as in Example 1. The thickness of the film is 79μm
Met. Table 1 shows the properties of the obtained polyamide.

Comparative Example 2 Meta-xylylenediamine and octane were used according to the method of Example 1.
25% by weight of nylon salt consisting of equimolar tandioic acid
An aqueous solution was obtained. This aqueous solution is concentrated to about 80% by weight,
20 g were charged in the same pressure vessel as in Example 1. This pressure
After the pressure vessel is sufficiently purged with nitrogen, the temperature is raised in a sealed state with stirring.
And temperature 210 ° C, pressure 8kgf / cm ^TwoG for 3 hours
Combined. Thereafter, the pressure in the pressure vessel was increased to 8 kgf / cm.
^TwoWhile maintaining at G, raise the temperature to 250 ° C over 1 hour,
Subsequently, the pressure in the pressure vessel is released at the same temperature for 30 minutes.
To normal pressure. Next, 200 ml /
While flowing nitrogen gas at a flow rate of min.
Polymerization was performed at 0 mmHg for 1.5 hours. Then, Example 1
A polyamide chip was obtained in the same manner as described above. This polyamide
The chip was vacuum dried at 40 ° C. for 72 hours. The obtained po
The lamide was white. Compression molding machine for this polyamide
At 240 ° C., 0 kgf / cm^Two2.5 minutes at G
After heating, 240 ℃, 50kgf / cm^TwoG, 2.5 minutes
A film was prepared under the following conditions. Film thickness is 80
μm. Table 1 shows the properties of the obtained polyamide.
You.

Example 3 15.419 g (0.1084 mol) of 1,3-bis (aminomethyl) cyclohexane and 1,6-decanedicarboxylic acid were placed in a 160 ml-capacity glass container equipped with a stirrer and a nitrogen inlet. 934g (0.1084mo
l) was charged. After the inside of the glass container was sufficiently purged with nitrogen, the glass container was immersed in a heating medium bath, and polymerization was carried out at 200 ° C. for 2 hours while flowing nitrogen gas at 50 ml / min with stirring. Subsequently, the temperature was raised to 280 ° C. over 1 hour, and polymerization was performed at the same temperature for 3 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Thereafter, the glass container was cracked to take out the polyamide, pulverized, and dried under reduced pressure at 40 ° C. for 72 hours. The obtained polyamide was colorless and transparent. This polyamide was compressed at 180 ° C. and 0 kgf / cm ² G using a compression molding machine.
After preheating for 5 minutes, 180 ° C, 50kgf · cm ² G,
A film was prepared under the conditions of 2.5 minutes. The thickness of the film was 102 μm. Table 1 shows the properties of the obtained polyamide.

Example 4 1,3-bis (aminomethyl) cyclohexane and 1,6
2,2,4-, 2, instead of decanedicarboxylic acid
4,4-trimethylhexamethylenediamine 16.42
Example 3 was carried out in the same manner as in Example 3, except that 0 g (0.1037 mol) and 23.835 g (0.1034 mol) of 1,6-decanedicarboxylic acid were used. The obtained polyamide was colorless and transparent. The polyamide using a compression molding machine, 160 ° C., was preheated 2.5 minutes ^{0kgf / cm 2 G, 160 ℃} , 50kgf / cm 2 G, 2.5
A film was formed under the conditions of minutes. Film thickness is 9
It was 6 μm. Table 1 shows the properties of the obtained polyamide.

Example 5 1,1,2-Diaminododecamethylene was placed in a 160 ml-capacity glass container equipped with a stirrer and a nitrogen inlet.
030 g (0.080 mol) and 18.427 g (0.080 mol) of 1,6-decanedicarboxylic acid were charged. After sufficiently replacing the inside of the glass container with nitrogen, the glass container was immersed in a heating medium bath, and polymerization was performed at 200 ° C. for 1 hour while flowing a 50 ml / min nitrogen gas with stirring. Then 280
The temperature was raised to 1 ° C. over 1 hour, and polymerization was carried out at the same temperature for 4 hours. The stirring was stopped, the glass container was taken out of the heat medium bath, and naturally cooled to room temperature while flowing nitrogen gas. Thereafter, the polyamide was taken out by breaking the glass container, crushed, and dried under reduced pressure at 30 ° C. for 72 hours. The obtained polyamide was colorless and transparent. The polyamide compression molding machine used, 160 ° C., was preheated 2.5 minutes ^{0kgf / cm 2 G, 160 ℃} , to form a film under the conditions of 50kgf · cm ² G, 2.5 min. 96 film thickness
μm. Table 1 shows the properties of the obtained polyamide.

Example 6 300 g (0.649 mol as 6D salt) of a 75% by weight aqueous solution of 6D salt obtained in the same manner as in Example 1 and ε-
70 g (0.618 mol) of caprolactam was stirred with a stirrer,
A 1-liter pressure vessel equipped with a thermometer, a pressure gauge, a nitrogen inlet, a pressure outlet, and a polymer outlet was charged. After the pressure vessel is sufficiently purged with nitrogen, the temperature is raised in a sealed state with stirring,
Polymerization was performed at a temperature of 220 ° C. and a pressure of 17 kgf / cm ² G for 4 hours. Thereafter, the pressure in the pressure vessel was increased to 17 kgf / cm.
While maintaining the ² G, the temperature was raised over a period of 1 hour to 275 ° C.,
Subsequently, the pressure in the pressure vessel was released at the same temperature over 30 minutes to normal pressure. Next, the pressure was reduced and the pressure in the pressure vessel was set to 500 mmHg, and polymerization was performed at 275 ° C. for 2 hours. After that, stirring was stopped, nitrogen gas was put in, the pressure vessel was returned to normal pressure, the produced polyamide was taken out in a string form from the polymer outlet at the bottom of the pressure vessel, and immediately cooled in a water tank, and then cylindrical with a pelletizer. Of polyamide chips. This polyamide chip was vacuum dried at 40 ° C. for 72 hours. The obtained polyamide was colorless and transparent. Using a compression molding machine, this polyamide was used at 160 ° C. and 0 kgf / c.
It was preheated 2.5 min m ² G, 160 ℃, 50kgf
/ Cm ² G for 2.5 minutes.
The thickness of the film was 65 μm. Table 1 shows the properties of the obtained polyamide.

Comparative Example 3 The same as Example 8 except that the amount of a 75% by weight aqueous solution of 6D salt was changed to 50 g (0.577 mol as 6D salt) and the amount of ε-caprolactam was changed to 150 g (1.325 mol). Polymerization and drying were performed under the following conditions to obtain a polyamide chip. The resulting polyamide was white. Using a compression molding machine, this polyamide was used at 200 ° C. and 0 kgf / cm.
After preheating at ² G for 2.5 minutes, 200 ° C, 50 kgf /
A film was formed under the conditions of cm ² G and 2.5 minutes. The thickness of this film was 76 μm. Table 1 shows the properties of the obtained polyamide.

[0045]

[Table 1]

[0046]

According to the present invention, 50 to 100% by weight of the dicarboxylic acid component is 1,6-decanedicarboxylic acid, the dicarboxylic acid component and the diamine component and 0 to 50% by weight of the total amount are the aliphatic aminocarboxylic acid component and / or Polyamide composed of lactam component is nylon 6 or nylon 66
It is a gas permeable material having amide groups in almost the same ratio. This gas permeable material can be used in moldings, films, fibers,
Used in the form of monofilaments or hollow fibers.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Takashi Amane 1-12-12 Nishihonmachi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Polymer Research Laboratory

Claims (2)

[Claims] (1) 50 to 100 in the dicarboxylic acid component (A)
A unit derived from a dicarboxylic acid component whose weight% is 1,6-decanedicarboxylic acid; a unit derived from a (B) diamine component; and (C) 0 to 50% by weight of an aliphatic amino based on the total amount. A gas permeable material formed from a polyamide comprising units derived from a carboxylic acid component and / or units derived from a lactam component. 2. The gas-permeable material according to claim 1, wherein the shape is a molded product, a film, a fiber, a monofilament or a hollow fiber.