JP5975038B2 - Polyamide resin and molded product comprising the same - Google Patents

Description

  The present invention relates to a polyamide resin and a molded article comprising the same.

  Crystalline polyamides typified by nylon 6 and nylon 66 are widely used as textiles for clothing, industrial materials, or general-purpose engineering plastics because of their excellent properties and ease of melt molding. On the other hand, changes in physical properties due to water absorption, acid, high-temperature alcohol, deterioration in hot water, and the like have been pointed out, and there is an increasing demand for polyamides with better dimensional stability and chemical resistance.

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

  So far, polyoxamide resins using various aliphatic linear diamines as diamine components have been proposed. For example, Non-Patent Document 1 discloses a polyoxamide resin using 1,6-hexanediamine as a diamine component. Non-Patent Document 2 discloses a polyoxamide resin (hereinafter also referred to as PA92) whose diamine component is 1,9-nonanediamine. Non-Patent Document 3 discloses a polyoxamide resin using 1,4-butanediamine as a diamine component. Patent Document 2 discloses a polyoxamide resin using various diamine components and dibutyl oxalate as a dicarboxylic acid ester. Patent Document 3 discloses a polyoxamide resin using two kinds of diamines of 1,9-nonanediamine and 2-methyl-1,8-octanediamine as a diamine component in a specific ratio. Patent Document 4 discloses a polyoxamide resin using various diamine components and oxalic acid. Patent Document 5 discloses a polyoxamide resin using a diamine having 2 to 18 carbon atoms as a diamine component.

JP 2006-57033 A Japanese National Patent Publication No. 5-506466 WO2008-072754 U.S. Pat. No. 2,130,948 Japanese National Patent Publication No. 5-506466

S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1998) R.J.Gaymans et al., J. Polym. Sci. Polym. Chem. Ed., 22, 137 3 (1984)

  Parts around electric / electronic devices and automobile engines may be used at high temperatures. At high temperatures, oxidation degradation tends to proceed. Therefore, there is a demand for a polyamide resin having oxidation resistance.

  However, the oxidation resistant polyamide resin is not disclosed in any of Patent Documents 1 to 5 and Non-Patent Documents 1 to 3.

  The problem to be solved by the present invention is to provide a polyamide resin having oxidation resistance.

  As a result of intensive studies by the present inventors, it has been found that a polyamide resin containing a specific dicarboxylic acid component and a specific diamine component having a specific molar ratio solves the above problems.

That is, the polyamide resin according to the first aspect of the present invention is a polyamide resin using a dicarboxylic acid component and a diamine component, wherein the dicarboxylic acid component includes an oxalic acid compound, and the diamine component includes diamine (a) and diamine ( b), wherein the diamine (a) is at least one diamine selected from the group consisting of diamines having 2 to 8 carbon atoms, and the diamine (b) is from the group consisting of diamines having 10 to 18 carbon atoms. It is a polyamide resin which is at least one diamine selected and has a molar ratio of the diamine (a) to the diamine (b) of 1:99 to 99: 1.
The polyamide resin according to the second aspect of the present invention is a polyamide resin using a dicarboxylic acid component and a diamine component, wherein the dicarboxylic acid component includes an oxalic acid compound, and the diamine component includes diamine (a) and diamine (b). The diamine (a) is at least one diamine selected from the group consisting of diamines having 2 to 8 carbon atoms, and the diamine (b) is selected from the group consisting of diamines having 10 to 18 carbon atoms And a polyamide resin having a molar ratio of the diamine (a) to the diamine (b) of 50:50 to 99: 1. That is, the polyamide resin according to the second aspect of the present invention is a polyamide resin in which the molar ratio of the diamine (a) to the diamine (b) is limited to 50:50 to 99: 1 in the polyamide resin according to the first aspect. Resin.
The polyamide resin according to the third aspect of the present invention is a polyamide resin using a dicarboxylic acid component and a diamine component, wherein the dicarboxylic acid component includes an oxalic acid compound, and the diamine component includes diamine (a) and diamine (b). The diamine (a) is at least one diamine selected from the group consisting of diamines having 2 to 8 carbon atoms, and the diamine (b) is selected from the group consisting of diamines having 10 to 18 carbon atoms At least one diamine having a molar ratio of the diamine (a) to the diamine (b) of 1:99 to 50:50 (however, the diamine (a) and the diamine (b) do not contain 50 mol% each) Is a polyamide resin. That is, in the polyamide resin according to the third aspect of the present invention, in the polyamide resin according to the first aspect, the molar ratio of the diamine (a) to the diamine (b) is 1:99 to 50:50 (provided that the diamine (a ) And diamine (b) each containing 50 mol%).

The polyamide resin according to the first aspect of the present invention has lower oxidizability estimated from the amount of heat of oxidation than the conventional polyamide resin. Moreover, it is excellent in low water absorption and chemical resistance, and can be used as a molding material for industrial materials, industrial materials, household goods and the like.
The polyamide resin according to the second aspect of the present invention has a high melting point Tm and low oxidizability estimated from the amount of heat of oxidation as compared with the conventional polyamide resin. Moreover, sufficient relative viscosity (ηr) (high molecular weight) is achieved, and the moldability estimated from the temperature difference (Td−Tm) between the 1% weight loss temperature (Td) indicating the decomposition start temperature and the melting point (Tm). Wide range of moldable temperature as an index, excellent melt moldability estimated from temperature difference (Tm-Tc) between melting point (Tm) and crystallization temperature (Tc), and also excellent low water absorption and chemical resistance It can be used as a molding material for industrial materials, industrial materials, household products, etc. The molded product made of the polyamide resin according to the second aspect of the present invention can be provided as a heat-resistant component.
The polyamide resin according to the third aspect of the present invention is estimated from the temperature difference (Td−Tm) between the 1% weight loss temperature (Td) indicating the decomposition start temperature and the melting point (Tm) as compared with the conventional polyamide resin. Since the moldable temperature range, which is an index of moldability, is wide and the crystallization time is slow, it does not solidify immediately. Moreover, since the oxidation property estimated from the amount of oxidation heat is not high, and it is excellent also in low water absorption and chemical resistance, it can be used as molding materials, such as industrial material, industrial material, and household goods. In particular, since the moldable temperature range is wide, the crystallization time is slow, and the moldability is excellent, the polyamide resin according to the third aspect of the present invention can be suitably used for parts that require moldability.

[Polyamide resin according to the first aspect of the present invention]
The polyamide resin according to the first aspect of the present invention is a polyamide resin using a dicarboxylic acid component and a diamine component, wherein the dicarboxylic acid component includes an oxalic acid compound, and the diamine component includes diamine (a) and diamine (b). The diamine (a) is at least one diamine selected from the group consisting of diamines having 2 to 8 carbon atoms, and the diamine (b) is selected from the group consisting of diamines having 10 to 18 carbon atoms And a polyamide resin having a molar ratio of the diamine (a) to the diamine (b) of 1:99 to 99: 1.

(1) Dicarboxylic acid component used for polyamide resin according to the first aspect of the present invention The dicarboxylic acid component used for the polyamide resin according to the first aspect of the present invention includes an oxalic acid compound, and the oxalic acid compound includes oxalic acid itself and It is at least one selected from compounds derived from oxalic acid such as oxalic acid diester. The oxalic acid compound only needs to have reactivity with an amino group. When producing a polyamide resin at a high polymerization temperature, if oxalic acid itself is used as a raw material, oxalic acid may be thermally decomposed. Derived compounds are preferred.

  As the compound derived from oxalic acid, oxalic acid diester is preferable from the viewpoint of suppressing side reactions in the polycondensation reaction.

  Succinic acid diesters include oxalic acid diesters of aliphatic monohydric alcohols, oxalic acid diesters of alicyclic alcohols, and oxalic acid diesters of aromatic alcohols.

  The oxalic acid diester of the aliphatic monohydric alcohol is selected from dimethyl oxalate, diethyl oxalate, di-n-propyl oxalate, di-i-propyl oxalate, di-n-butyl oxalate, di-butyl oxalate and di-t-butyl oxalate. The oxalic acid diester of an aliphatic monohydric alcohol having 3 or more carbon atoms is preferable, and dibutyl oxalate is more preferable.

  Examples of oxalic acid diesters of alicyclic alcohols include dicyclohexyl oxalate.

  Succinic acid diesters of aromatic alcohols include diphenyl oxalate.

  The oxalic acid diester is preferably at least one selected from the group consisting of an aliphatic monohydric alcohol oxalic acid diester having more than 3 carbon atoms, an alicyclic alcohol oxalic acid diester, and an aromatic alcohol oxalic acid diester. And at least one selected from diphenyl oxalate, more preferably dibutyl oxalate.

  These oxalic acid compounds can be used alone or in any mixture thereof at the time of producing the polyoxamide.

  As the dicarboxylic acid component used in the polyamide resin according to the first aspect of the present invention, a dicarboxylic acid component other than the oxalic acid compound can be used as long as the effects of the present invention are not impaired.

  Examples of dicarboxylic acid components other than oxalic acid compounds include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

  Aliphatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid. Examples include acids, azelaic acid, sebacic acid, and suberic acid.

  Examples of the alicyclic dicarboxylic acid include 1,3-cyclopentane dicarboxylic acid and 1,4-cyclohexane dicarboxylic acid.

  Aromatic dicarboxylic acids include 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, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid Can be mentioned.

  Other dicarboxylic acid components other than these oxalic acid compounds can be used alone or in any mixture thereof during the production of the polyamide resin.

  Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within the range where melt molding is possible regardless of the presence or absence of dicarboxylic acid components other than oxalic acid compounds.

The total content of the dicarboxylic acid component and the polyvalent carboxylic acid component other than the oxalic acid compound is preferably less than 50 mol%, more preferably 20 mol% or less, of all the carboxylic acid components including the oxalic acid compound. More preferably, it is 10 mol% or less, More preferably, it is 5 mol% or less, More preferably, it is 1 mol% or less.
The content of the oxalic acid compound is preferably 50 mol% or more of all carboxylic acid components including the oxalic acid compound, more preferably more than 80 mol%, more preferably more than 90 mol%, Preferably it is more than 95 mol%, more preferably more than 99 mol%.

(2) Diamine component used for polyamide resin according to first aspect of the present invention The diamine component used for the polyamide resin according to the first aspect of the present invention includes diamine (a) and diamine (b).

  The molar ratio of diamine (a) to diamine (b) is 1:99 to 99: 1, preferably 1:99 to 80:20, more preferably 10:90 to 80:20, and 15:85 to 70. : 30 is more preferable, and 20:80 to 70:30 is more preferable.

  Further, from the viewpoint of having oxidation resistance and a high melting point, the content of diamine (a) and diamine (b) is more than 50 mol%, preferably 80 mol% or more, with respect to the total diamine components of the polyamide resin. Yes, more preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more.

(2-1) Diamine (a)
The diamine (a) used for the polyamide resin according to the first aspect of the present invention is at least one diamine selected from the group consisting of diamines having 2 to 8 carbon atoms.

  Examples of the diamine having 2 to 8 carbon atoms include aliphatic diamines having 2 to 8 carbon atoms, such as ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 3 -At least 1 sort (s) of aliphatic diamine selected from methyl- 1, 5- pentane diamine and 2-methyl- 1, 5- pentane diamine is mentioned.

  The diamine (a) is preferably at least one diamine selected from the group consisting of diamines having 4 to 8 carbon atoms from the viewpoint of ease of increasing the molecular weight of the obtained polyamide resin, and has 6 to 8 carbon atoms. More preferred is at least one diamine selected from the group consisting of diamines.

  Examples of the diamine having 4 to 8 carbon atoms include 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,5- Aliphatic diamines such as pentanediamine are listed.

  Examples of the diamine having 6 to 8 carbon atoms include aliphatic diamines such as 1,6-hexanediamine, 1,8-octanediamine, 3-methyl-1,5-pentanediamine, and 2-methyl-1,5-pentanediamine. Is mentioned. Among these, at least one diamine selected from the group consisting of 1,6-hexanediamine, 1,8-octanediamine, 3-methyl-1,5-pentanediamine and 2-methyl-1,5-pentanediamine. At least one selected from 1,6-hexanediamine and 1,8-octanediamine is more preferable, and 1,6-hexanediamine is more preferable.

(2-2) Diamine (b)
The diamine (b) used for the polyamide resin according to the first aspect of the present invention is at least one diamine selected from the group consisting of diamines having 10 to 18 carbon atoms.

  Examples of the diamine having 10 to 18 carbon atoms include 1,10-decanediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, , 14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,18-octadecanediamine, and the like.

  The diamine (b) is preferably at least one diamine selected from the group consisting of diamines having 10 to 16 carbon atoms and selected from the group consisting of diamines having 10 to 14 carbon atoms from the viewpoint of the melting point of the polyamide resin to be obtained. More preferred are at least one diamine.

  Examples of the diamine having 10 to 16 carbon atoms include 1,10-decanediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, , 14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine and the like.

  Examples of the diamine having 10 to 14 carbon atoms include 1,10-decanediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, And aliphatic diamines such as 14-tetradecanediamine. Among these, 1,10-decanediamine, 5-methyl-1,9-nonanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine and 1,14-tetradecanediamine are used. At least one diamine selected from the group is preferred, at least one selected from 1,10-decanediamine, 1,11-undecanediamine and 1,12-dodecanediamine is more preferred, and 1,10-decanediamine is preferred. And at least one selected from 1,12-dodecanediamine is more preferred.

(2-3) Other diamine component The diamine component used for the polyamide resin according to the first aspect of the present invention can be mixed with another diamine component within a range not impairing the effects of the present invention.

  Examples of other diamine components include aliphatic diamines, alicyclic diamines, and aromatic diamines.

  Aliphatic diamines include 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexane. Examples include diamines.

  Examples of the alicyclic diamine include cyclohexane diamine, methyl cyclohexane diamine, and isophorone diamine.

  As aromatic diamines, p-phenylenediamine, m-phenylenediamine, p-xylenediamine, m-xylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylether Is mentioned.

  These other diamine components can be used alone or in any mixture thereof during the production of polyoxamide.

The content of other diamine components is less than 50 mol%, preferably 20 mol% or less, more preferably 10 mol, based on the total diamine components including the diamine (a) and diamine (b) described above. % Or less, more preferably 5 mol% or less, and further preferably 1 mol% or less.
The polyamide resin according to the first aspect and the polyamide resins according to the second and third aspects described later include 1,6-hexanediamine as the diamine (a), 1,10-decanediamine as the diamine (b), and 1, It is preferable to contain at least one 12-dodecanediamine, more preferably dibutyl oxalate as the oxalic acid compound, and even more preferably the oxalic acid compound is butyl oxalate. The polyamide resin according to the first aspect and the polyamide resins according to the second and third aspects, which will be described later, are composed of 1,6-hexanediamine as the diamine (a) and 1,10-decanediamine as the diamine (b). It preferably comprises at least one of 1,12-dodecanediamine, more preferably contains dibutyl oxalate as the oxalate compound, and more preferably the oxalate compound is butyl oxalate.

(3) Production of polyamide resin according to the first aspect of the present invention The polyamide resin according to the first aspect of the present invention can be produced using any method known as a method for producing a polyamide resin. From the viewpoint of high molecular weight and productivity, it is preferable to obtain a diamine and oxalic acid diester by a polycondensation reaction in a batch or continuous manner. More preferably, the diamine and oxalic acid diester are obtained by (i) a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step or (ii) a pressure polymerization method described in WO2008-072754. Specifically, the synthesis is preferably performed by the polymerization method (i) or (ii) as shown by the following operation.

(I) Two-stage polymerization method: pre-polycondensation step First, after the inside of the reactor is purged with nitrogen, a diamine and an oxalic acid compound are mixed.
When mixing, a solvent in which both the diamine and the oxalic acid compound are soluble may be used. As a solvent in which both the diamine and the oxalic acid compound are soluble, 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, an oxalic acid compound is added with respect to this. At this time, the charging ratio of the oxalic acid compound and the diamine is oxalic acid compound / the diamine, preferably 0.8 to 1.5 (molar ratio), more preferably 0.91 to 1.1 (molar ratio), 0 .99 to 1.01 (molar ratio) is more preferable.

  The temperature in the reactor charged in this way is increased while stirring. The temperature is preferably controlled so that the final reached temperature is in the range of 80 to 150 ° C, and more preferably in the range of 100 to 140 ° C. The reaction time at the final temperature is preferably 3 to 6 hours.

(I) Two-stage polymerization method: post-polycondensation step In order to further increase the molecular weight, it is preferable to raise the temperature of the polymer produced in the pre-polycondensation step in the reactor. The temperature is raised from the final temperature reached in the pre-polycondensation step to a temperature range of preferably 215 ° C. or higher and 320 ° C. or lower, preferably 220 ° C. or higher and 315 ° C. or lower, more preferably 225 ° C. or higher and 310 ° C. or lower. It is preferable to hold | maintain for 1 to 8 hours including temperature rising time, and it is more preferable to hold | maintain for 2 to 6 hours. Furthermore, it can also superpose | polymerize under reduced pressure as needed. A preferable final ultimate pressure in the case of performing the vacuum polymerization is 0.1 MPa to 13.3 Pa.

(Ii) Pressurized polymerization method First, diamine is placed in a pressure vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, the oxalic acid compound is injected into the pressure vessel while maintaining the sealed pressure state at the reaction temperature, and the polycondensation reaction is started. The reaction temperature is not particularly limited as long as the polyamide resin produced by the reaction between the diamine and the oxalic acid compound can maintain a slurry state or a solution state and does not thermally decompose. For example, in the case of a polyamide resin using 1,6-hexanediamine, 1,10-decanediamine and dibutyl oxalate as raw materials, the reaction temperature is preferably 150 ° C. to 250 ° C. Here, the charging ratio of dibutyl oxalate and diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), in terms of the molar amount of dibutyl oxalate / total molar amount of diamine. More preferably, it is 0.99 to 1.01 (molar ratio).

  Next, while maintaining the inside of the pressure vessel in a sealed pressure state, the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of a polyamide resin using 1,6-hexanediamine, 1,10-decanediamine and dibutyl oxalate as raw materials, the melting point is 220 to 300 ° C., so that it is 225 ° C. or higher and 330 ° C. or lower, preferably 230 ° C. or higher. The temperature is raised to 325 ° C. or lower, more preferably from 235 ° C. to 320 ° C. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. A preferable final ultimate pressure in the case of performing the vacuum polymerization is 0.1 MPa to 13.3 Pa.

(4) Relative viscosity of the polyamide resin according to the first aspect of the present invention The relative viscosity of the polyamide resin according to the first aspect of the present invention uses a 96 mass% concentrated sulfuric acid solution with a polyamide resin concentration of 1.0 g / dl. Measured at 25 ° C. From the viewpoint of avoiding the tendency of the molded product after melt molding to become brittle and lowering the physical properties, and from the viewpoint of avoiding the tendency of the melt viscosity at the time of melt molding to increase and the molding processability to deteriorate, the relative viscosity of the polyamide resin of the present invention is: 1.6-6.0 are preferable, 1.8-5.5 are more preferable, and 2.0-4.5 are more preferable. The control of the relative viscosity is achieved by the composition ratio of diamine and carboxylic acid or the reaction temperature.

(5) Thermal characteristics and water absorption of the polyamide resin according to the first aspect of the present invention The heat of oxidation of the polyamide resin according to the first aspect of the present invention is preferably 600 J / g or less from the viewpoint of ensuring heat resistance. Preferably it is 550 J / g or less.

  The melting point Tm of the polyamide resin according to the first aspect of the present invention is preferably from 200 to 320 ° C., more preferably from 210 to 320 ° C., from the viewpoint of use at high temperature and the viewpoint of securing the melt moldability by setting the solidification rate appropriately. 300 ° C.

  The 1% weight reduction temperature Td of the polyamide resin according to the first aspect of the present invention is preferably 340 to 410 ° C, more preferably 360 to 400 ° C, from the viewpoint of sufficiently ensuring the moldable temperature range and melt moldability. is there.

  The crystallization temperature Tc of the polyamide resin according to the first aspect of the present invention is preferably 180 to 270 ° C., more preferably 190 to 260 ° C., from the viewpoint of sufficiently ensuring molding cycleability and melt moldability.

  The temperature difference (Td−Tm) indicating the moldable temperature range of the polyamide resin according to the first aspect of the present invention is preferably 60 ° C. or higher, more preferably 65 ° C. or higher, and further preferably 70 ° C. or higher.

The temperature difference (Tm−Tc) indicating the melt moldability of the polyamide resin according to the first aspect of the present invention suppresses the molding cycle time, secures productivity, and suppresses the crystallization time to an appropriate size. And from a viewpoint of ensuring the physical property of a molded article, Preferably it is 10-70 degreeC, More preferably, it is 15-60 degreeC.
The crystallization time tmax that is an index of the crystallization speed according to the first aspect of the present invention is preferably 1 minute or more, more preferably 1 to 5 minutes, and more preferably 1.5 to 5 minutes.

The saturated water absorption rate of the polyamide resin according to the first aspect of the present invention is preferably less than 1.5% from the viewpoint of sufficiently ensuring low water absorption.
In addition, said oxidation calorie | heat amount, melting | fusing point Tm, 1% weight loss temperature Td, crystallization temperature Tc, crystallization time tmax, and saturated water absorption can be measured by the method as described in an Example.

(6) Blending into the polyamide resin according to the first aspect of the present invention In addition, the polyamide resin according to the first aspect of the present invention can be mixed with other polyamide resins within a range not impairing the effects of the present invention. . Specifically, it is possible to mix aromatic polyamide, aliphatic polyamide, and alicyclic polyamide. Furthermore, thermoplastic polymers other than polyamide, elastomers, fillers, reinforcing fibers, and various additives can be similarly blended.

  Further, the polyamide resin obtained according to the first aspect of the present invention may contain a stabilizer such as a copper compound, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, a crystal as necessary. Accelerators, glass fibers, plasticizers, lubricants and the like can be added during the production of the polyamide resin, and can also be added directly to the pellets of the polyoxamide resin after production or by melt kneading.

(7) Molded product comprising the polyamide resin according to the first aspect of the present invention As a molding method for the molded product comprising the polyamide resin according to the first aspect of the present invention, injection, extrusion, hollow, press, roll, foaming, vacuum・ All known molding methods applicable to polyamide resin such as compressed air and stretching are possible, and by these molding methods, it can be processed into shapes such as films, sheets, pipes, tubes, monofilaments, fibers, containers, etc. The shape of the product is preferably the shape of a film, sheet, pipe, tube, monofilament, fiber or container.

(8) Use of molded product made of polyamide resin according to the first aspect of the present invention The molded product obtained according to the first aspect of the present invention is a sheet, film, pipe, sheet of various molded products for which a polyamide molded product has been conventionally used. Used as tubes, monofilaments, fibers, containers, etc. in automotive parts, computers and computer-related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, household goods, etc. can do. Furthermore, since the polyoxamide resin of the present invention has a high melting point and a low amount of heat for oxidation, it can be suitably used, for example, for automobile members and electrical / electronic equipment.

[Polyamide resin according to the second aspect of the present invention]
The polyamide resin according to the second aspect of the present invention is a polyamide resin using a dicarboxylic acid component and a diamine component, wherein the dicarboxylic acid component includes an oxalic acid compound, and the diamine component includes diamine (a) and diamine (b). The diamine (a) is at least one diamine selected from the group consisting of diamines having 2 to 8 carbon atoms, and the diamine (b) is selected from the group consisting of diamines having 10 to 18 carbon atoms And a polyamide resin having a molar ratio of the diamine (a) to the diamine (b) of 50:50 to 99: 1.

(1) Dicarboxylic acid component used in the polyamide resin according to the second aspect of the present invention The same as the polyamide resin according to the first aspect.

(2) Diamine component used for polyamide resin according to the second aspect of the present invention The diamine component used for the polyamide resin according to the second aspect of the present invention includes diamine (a) and diamine (b).

  The molar ratio of the diamine (a) to the diamine (b) is 50:50 to 99: 1, and 50:50 to 80:20 is preferable from the viewpoint of the oxidation resistance and high melting point of the polyamide resin, and 55: 45:80:20 is more preferable, and 55: 45-70: 30 is still more preferable.

  Further, from the viewpoint of having oxidation resistance and a high melting point, the content of diamine (a) and diamine (b) is more than 50 mol%, preferably 80 mol% or more, with respect to the total diamine components of the polyamide resin. Yes, more preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more.

(2-1) Diamine (a)
This is the same as the polyamide resin according to the first aspect.

(2-2) Diamine (b)
This is the same as the polyamide resin according to the first aspect.

(2-3) Other diamine components The same as the polyamide resin according to the first aspect.

(3) Production of polyamide resin according to the second aspect of the present invention The polyamide resin according to the second aspect of the present invention can be produced using any method known as a method for producing a polyamide resin. From the viewpoint of high molecular weight and productivity, it is preferable to obtain a diamine and oxalic acid diester by a polycondensation reaction in a batch or continuous manner. More preferably, the diamine and oxalic acid diester are obtained by (i) a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step or (ii) a pressure polymerization method described in WO2008-072754. Specifically, the synthesis is preferably performed by the polymerization method (i) or (ii) as shown by the following operation.

(I) Two-stage polymerization method: pre-polycondensation step First, after the inside of the reactor is purged with nitrogen, a diamine and an oxalic acid compound are mixed.
When mixing, a solvent in which both the diamine and the oxalic acid compound are soluble may be used. As a solvent in which both the diamine and the oxalic acid compound are soluble, 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, an oxalic acid compound is added with respect to this. At this time, the charging ratio of the oxalic acid compound and the diamine is oxalic acid compound / the diamine, preferably 0.8 to 1.5 (molar ratio), more preferably 0.91 to 1.1 (molar ratio), 0 .99 to 1.01 (molar ratio) is more preferable.

  The temperature in the reactor charged in this way is increased while stirring. The temperature is preferably controlled so that the final reached temperature is in the range of 80 to 150 ° C, and more preferably in the range of 100 to 140 ° C. The reaction time at the final temperature is preferably 3 to 6 hours.

(I) Two-stage polymerization method: post-polycondensation step In order to further increase the molecular weight, it is preferable to raise the temperature of the polymer produced in the pre-polycondensation step in the reactor. The temperature is raised to a temperature range of 230 ° C. or higher and 320 ° C. or lower, preferably 235 ° C. or higher and 315 ° C. or lower, more preferably 240 ° C. or higher and 310 ° C. or lower, from the final temperature reached in the prepolycondensation step. It is preferable to hold | maintain for 1 to 8 hours including temperature rising time, and it is more preferable to hold | maintain for 2 to 6 hours. Furthermore, it can also superpose | polymerize under reduced pressure as needed. A preferable final ultimate pressure in the case of performing the vacuum polymerization is 0.1 MPa to 13.3 Pa.

(Ii) Pressurized polymerization method First, diamine is placed in a pressure vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, the oxalic acid compound is injected into the pressure vessel while maintaining the sealed pressure state at the reaction temperature, and the polycondensation reaction is started. The reaction temperature is not particularly limited as long as the polyamide resin produced by the reaction between the diamine and the oxalic acid compound can maintain a slurry state or a solution state and does not thermally decompose. For example, in the case of a polyamide resin using 1,6-hexanediamine, 1,10-decanediamine and dibutyl oxalate as raw materials, the reaction temperature is preferably 150 ° C. to 250 ° C. Here, the charging ratio of dibutyl oxalate and diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), in terms of the molar amount of dibutyl oxalate / total molar amount of diamine. More preferably, it is 0.99 to 1.01 (molar ratio).

  Next, while maintaining the inside of the pressure vessel in a sealed pressure state, the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of a polyamide resin using 1,6-hexanediamine, 1,10-decanediamine and dibutyl oxalate as raw materials, the melting point is 245 to 300 ° C., and therefore 250 ° C. or more and 330 ° C. or less, preferably 255 ° C. or more. The temperature is raised to 325 ° C. or lower, more preferably 260 ° C. or higher and 320 ° C. or lower. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. A preferable final ultimate pressure in the case of performing the vacuum polymerization is 0.1 MPa to 13.3 Pa.

(4) Relative viscosity of the polyamide resin according to the second aspect of the present invention The same as the polyamide resin according to the first aspect.

(5) Thermal characteristics and water absorption of the polyamide resin according to the second aspect of the present invention The heat of oxidation of the polyamide resin according to the second aspect of the present invention is preferably 600 J / g or less from the viewpoint of ensuring sufficient heat resistance. More preferably, it is 550 J / g or less.

  The melting point Tm of the polyamide resin according to the second aspect of the present invention is preferably 270 to 320 ° C., more preferably 280 to 320 ° C., from the viewpoint of use at high temperature and the viewpoint of securing the melt moldability by setting the solidification rate appropriately. 300 ° C.

  The 1% weight reduction temperature Td of the polyamide resin according to the second aspect of the present invention is preferably 340 to 390 ° C, more preferably 360 to 390 ° C, from the viewpoint of sufficiently ensuring the moldable temperature range and melt moldability. is there.

  The crystallization temperature Tc of the polyamide resin according to the second aspect of the present invention is preferably 210 to 270 ° C., more preferably 220 to 260 ° C., from the viewpoint of sufficiently securing molding cycle properties and melt moldability.

  The temperature difference (Td−Tm) indicating the moldable temperature range of the polyamide resin according to the second aspect of the present invention is preferably 60 to 190 ° C. from the viewpoint of sufficiently ensuring the moldable temperature range and melt moldability. Preferably it is 65-185 degreeC, More preferably, it is 70-180 degreeC.

  The temperature difference (Tm-Tc) indicating the melt moldability of the polyamide resin according to the second aspect of the present invention suppresses the molding cycle time, secures productivity, and suppresses the crystallization time to an appropriate size. And from a viewpoint of ensuring the physical property of a molded article, Preferably it is 20-70 degreeC, More preferably, it is 30-60 degreeC.

The saturated water absorption rate of the polyamide resin according to the second aspect of the present invention is preferably less than 1.5% from the viewpoint of sufficiently ensuring low water absorption.
In addition, said oxidation calorie | heat amount, melting | fusing point Tm, 1% weight loss temperature Td, crystallization temperature Tc, and saturated water absorption can be measured by the method as described in an Example.

(6) Compounding to the polyamide resin according to the second aspect of the present invention The same as the polyamide resin according to the first aspect.

(7) Molded product comprising the polyamide resin according to the second aspect of the present invention The same as the polyamide resin according to the first aspect.

(8) Use of molded product made of polyamide resin according to the second aspect of the present invention The molded product obtained by the second aspect of the present invention is a sheet, film, or pipe of various molded products for which a polyamide molded product has been conventionally used. , Tubes, monofilaments, fibers, containers, etc., in automotive parts, computers and computer-related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, household goods, etc. Can be used. Furthermore, since the polyoxamide resin of the present invention has a high melting point and a low amount of oxidation heat, it can be preferably used in applications requiring heat resistance, for example, automotive parts and electrical / electronic devices, and in particular, requires heat resistance. It can be suitably used for parts.

[Polyamide resin according to the third aspect of the present invention]
The polyamide resin according to the third aspect of the present invention is a polyamide resin using a dicarboxylic acid component and a diamine component, wherein the dicarboxylic acid component includes an oxalic acid compound, and the diamine component includes diamine (a) and diamine (b). The diamine (a) is at least one diamine selected from the group consisting of diamines having 2 to 8 carbon atoms, and the diamine (b) is selected from the group consisting of diamines having 10 to 18 carbon atoms At least one diamine having a molar ratio of the diamine (a) to the diamine (b) of 1:99 to 50:50 (however, the diamine (a) and the diamine (b) do not contain 50 mol% each) Is a polyamide resin.

(1) Dicarboxylic acid component used in the polyamide resin according to the third aspect of the present invention The same as the polyamide resin according to the first aspect.

(2) Diamine component used for polyamide resin according to the third aspect of the present invention The diamine component used for the polyamide resin according to the third aspect of the present invention includes diamine (a) and diamine (b). The molar ratio of the diamine (a) to the diamine (b) is 1:99 to 50:50 (however, each of the diamine (a) and the diamine (b) does not include 50 mol%). From the viewpoint of having a wide moldable temperature range, 1:99 to 49:51 is preferable, 10:90 to 42:58 is more preferable, 15:85 to 45:55 is further preferable, and 20:80 to 45:55 is preferable. Further preferred.

  Further, from the viewpoint of having oxidation resistance and a high melting point, the content of diamine (a) and diamine (b) is more than 50 mol%, preferably 80 mol% or more, with respect to the total diamine components of the polyamide resin. Yes, more preferably 90 mol% or more, more preferably 95 mol% or more, and even more preferably 99 mol% or more.

(2-1) Diamine (a)
This is the same as the polyamide resin according to the first aspect.
(2-2) Diamine (b)
This is the same as the polyamide resin according to the first aspect.

(2-3) Other diamine components The same as the polyamide resin according to the first aspect.

(3) Manufacture of the polyamide resin which concerns on the 3rd aspect of this invention The polyamide resin which concerns on the 3rd aspect of this invention can be manufactured using the arbitrary methods known as a method of manufacturing a polyamide resin. From the viewpoint of high molecular weight and productivity, it is preferable to obtain a diamine and oxalic acid diester by a polycondensation reaction in a batch or continuous manner. More preferably, the diamine and oxalic acid diester are obtained by (i) a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step or (ii) a pressure polymerization method described in WO2008-072754. Specifically, the synthesis is preferably performed by the polymerization method (i) or (ii) as shown by the following operation.

(I) Two-stage polymerization method: pre-polycondensation step First, after the inside of the reactor is purged with nitrogen, a diamine and an oxalic acid compound are mixed.
When mixing, a solvent in which both the diamine and the oxalic acid compound are soluble may be used. As a solvent in which both the diamine and the oxalic acid compound are soluble, 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, an oxalic acid compound is added with respect to this. At this time, the charging ratio of the oxalic acid compound and the diamine is oxalic acid compound / the diamine, preferably 0.8 to 1.5 (molar ratio), more preferably 0.91 to 1.1 (molar ratio), 0 .99 to 1.01 (molar ratio) is more preferable.

  The temperature in the reactor charged in this way is increased while stirring. The temperature is preferably controlled so that the final reached temperature is in the range of 80 to 150 ° C, and more preferably in the range of 100 to 140 ° C. The reaction time at the final temperature is preferably 3 to 6 hours.

(I) Two-stage polymerization method: post-polycondensation step In order to further increase the molecular weight, it is preferable to raise the temperature of the polymer produced in the pre-polycondensation step in the reactor. The temperature is raised from the final temperature reached in the pre-polycondensation step to a temperature range of 215 to 300 ° C., preferably 220 to 295 ° C., more preferably 225 to 290 ° C. It is preferable to hold | maintain for 1 to 8 hours including temperature rising time, and it is more preferable to hold | maintain for 2 to 6 hours. Furthermore, it can also superpose | polymerize under reduced pressure as needed. A preferable final ultimate pressure in the case of performing the vacuum polymerization is 0.1 MPa to 13.3 Pa.

(Ii) Pressurized polymerization method First, diamine is placed in a pressure vessel and purged with nitrogen, and then heated to the reaction temperature under a sealing pressure. Thereafter, the oxalic acid compound is injected into the pressure vessel while maintaining the sealed pressure state at the reaction temperature, and the polycondensation reaction is started. The reaction temperature is not particularly limited as long as the polyamide resin produced by the reaction between the diamine and the oxalic acid compound can maintain a slurry state or a solution state and does not thermally decompose. For example, in the case of a polyamide resin using 1,6-hexanediamine, 1,10-decanediamine and dibutyl oxalate as raw materials, the reaction temperature is preferably 150 ° C. to 250 ° C. Here, the charging ratio of dibutyl oxalate and diamine is 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), in terms of the molar amount of dibutyl oxalate / total molar amount of diamine. More preferably, it is 0.99 to 1.01 (molar ratio).

  Next, while maintaining the inside of the pressure vessel in a sealed pressure state, the temperature is raised to a temperature not lower than the melting point of the polyamide resin and not pyrolyzed. For example, in the case of a polyamide resin using 1,6-hexanediamine, 1,10-decanediamine and dibutyl oxalate as raw materials, the melting point is 220 to 280 ° C., so that it is 225 ° C. or higher and 320 ° C. or lower, preferably 230 ° C. or higher. The temperature is raised to 315 ° C. or lower, more preferably from 235 ° C. to 310 ° C. The pressure in the pressure-resistant container until reaching the predetermined temperature is adjusted to approximately 0.1 MPaG, preferably 1 MPaG to 0.2 MPaG, from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. A preferable final ultimate pressure in the case of performing the vacuum polymerization is 0.1 MPa to 13.3 Pa.

(4) Relative viscosity of the polyamide resin according to the third aspect of the present invention The same as the polyamide resin according to the first aspect.

(5) Thermal characteristics and water absorption of the polyamide resin according to the third aspect of the present invention The heat of oxidation of the polyamide resin according to the third aspect of the present invention is preferably 600 J / g or less from the viewpoint of ensuring heat resistance. Preferably it is 550 J / g or less.

  The melting point Tm ′ of the polyamide resin according to the third aspect of the present invention is preferably 200 to 280 ° C., more preferably 210 to 270 ° C. from the viewpoint of use at high temperature and the viewpoint of ensuring melt moldability.

  The 1% weight reduction temperature Td of the polyamide resin according to the third aspect of the present invention is preferably 340 to 410 ° C., more preferably 360 to 400 ° C., from the viewpoint of sufficiently ensuring the moldable temperature range and melt moldability. is there.

  The crystallization temperature Tc of the polyamide resin according to the third aspect of the present invention is preferably 180 to 250 ° C., more preferably 190 to 240 ° C., from the viewpoint of sufficiently ensuring molding cycleability and melt moldability.

  The temperature difference (Td−Tm ′) indicating the moldable temperature range according to the third aspect of the present invention is preferably 125 ° C. or higher, more preferably 128, from the viewpoint of sufficiently securing the moldable temperature range and melt moldability. It is at least 130 ° C, more preferably at least 130 ° C.

  The temperature difference (Tm′−Tc) indicating the melt moldability according to the third aspect of the present invention suppresses the molding cycle time, secures productivity, and suppresses the crystallization time to an appropriate size. From the viewpoint of securing the physical properties of the molded product, the temperature is preferably 10 to 40 ° C, more preferably 15 to 30 ° C.

  The crystallization time tmax 'that is an index of the crystallization speed according to the third aspect of the present invention is preferably 1 minute or more, more preferably 1 to 5 minutes, and more preferably 1.5 to 5 minutes.

The saturated water absorption rate of the polyamide resin according to the third aspect of the present invention is preferably less than 1.5% from the viewpoint of sufficiently ensuring low water absorption.
In addition, said oxidation calorie | heat amount, melting | fusing point Tm ', 1% weight reduction temperature Td, crystallization temperature Tc, crystallization time tmax', and saturated water absorption can be measured by the method as described in an Example.

(6) Formulation to the polyamide resin according to the third aspect of the present invention The same as the polyamide resin according to the first aspect.

(7) Molded article of polyamide resin according to the third aspect of the present invention The same as the polyamide resin according to the first aspect.

(8) Use of molded product of polyamide resin according to the third aspect of the present invention The molded product obtained by the present invention is a sheet, film, pipe, tube, monofilament, sheet of various molded products for which polyamide resin has been conventionally used. Can be used as textiles, containers, etc. in automobile parts, computers and computer-related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, household goods, etc. . Furthermore, since the polyoxamide resin of the present invention has a high melting point and a low amount of oxidation heat, it can be preferably used in applications requiring oxidation resistance, for example, automotive parts and electrical / electronic devices, and particularly requires oxidation resistance. It can be used suitably for the use of the parts to be made.

[1] Examples I-1 to I-8, Reference Examples I-1 to I-2, Comparative Examples I-1 to I-5
[Physical property measurement, molding, evaluation method]
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, relative viscosity, melting point, crystallization temperature, crystallization time evaluation, 1% weight loss temperature, film forming and oxidation resistance evaluation, measurement of saturated water absorption rate, chemical resistance, hydrolysis resistance evaluation in Examples Was carried out by the following method.

(1) Relative viscosity (ηr)
Using an Ostwald viscometer, the relative viscosity (ηr) of a solution having a polyoxamide resin concentration of 1.0 g / dl in 96% by mass sulfuric acid in warm water at 25 ° C. was measured.

(2) Melting point (Tm), crystallization temperature (Tc) and temperature difference (Tm-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 280 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 280 ° C. for 5 minutes, and then lowered to 30 ° C. at a rate of 10 ° C./min (temperature fall first run). Then, the temperature was raised to 280 ° 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-decreasing first run was the crystallization temperature (Tc), and the temperature at the high-temperature peak end of the endothermic peak of the temperature-rising second run was the melting point (Tm). A temperature difference (Tm−Tc) was determined from the obtained melting point (Tm) and crystallization temperature (Tc). From the viewpoints of durability at high temperatures and melt moldability, those having a melting point (Tm) of 270 ° C. or more and less than 320 ° C. were evaluated as A, and those having a melting point (Tm) of less than 270 ° C. or 320 ° C. or more were evaluated as B.

(3) Evaluation of crystallization time In the measurement of the crystallization time, the temperature (Tm) at the high temperature side peak end of the endothermic peak measured by the DSC temperature rising second run of (2) was used.
The crystallization time was measured under a nitrogen atmosphere using PYRIS Diamond DSC manufactured by PerkinELmer. The temperature was raised from room temperature to Tm + 20 ° C. at a rate of 100 ° C./min, held at Tm + 20 ° C. for 10 minutes to dissolve the polymer, and then cooled to Tm-20 ° C. at a rate of 500 ° C./min. Isothermal crystallization was carried out by holding at ° C. The time from reaching Tm-20 ° C. until the peak top of the exothermic peak due to crystallization was observed was defined as tmax, and this value was used as the crystallization time. From the viewpoint of moldability, the case where the value of tmax was 1 minute or more was evaluated as A, and the case where it was less than 1 minute was evaluated as B.

(4) 1% weight loss temperature (Td) and temperature difference (Td-Tm)
Td was measured by thermogravimetric analysis (TGA) using THERMOGRAVIMETRIC ANALYZER TGA-50 manufactured by Shimadzu Corporation. Under a nitrogen stream of 20 ml / min, the temperature was raised from room temperature to 500 ° C. at a rate of temperature increase of 10 ° C./min, and 1% weight loss temperature (Td) was measured. A temperature difference (Td−Tm) was determined from the obtained 1% weight loss temperature (Td) and the melting point (Tm) obtained in (2).
From the viewpoint of melt moldability, AA having a temperature difference (Td-Tm) of 125 ° C. or higher, A being 60 ° C. or higher and lower than 125 ° C., B being 50 ° C. or higher and lower than 60 ° C., B, lower than 50 ° C. Was rated C.

(5) Film formation Film formation was performed using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. After being melted by heating at 245 to 295 ° C. for 5 minutes under a reduced pressure atmosphere of 500 to 700 Pa, the film was formed by pressing at 10 MPa for 1 minute. Next, after returning the reduced-pressure atmosphere to normal pressure, the film was crystallized by cooling at room temperature of 5 MPa for 1 minute to obtain a film.

(6) Oxidation resistance The film obtained by the film forming of (5) was evaluated for oxidation resistance using RDC220 manufactured by Seiko Instruments Inc. Set the film obtained on RDC220 manufactured by Seiko Instruments Inc., raise the temperature from room temperature to 190 ° C at a temperature increase rate of 20 ° C / min under a nitrogen flow of 100 ml / min, hold at 190 ° C, and start the temperature increase 60 minutes later, the temperature was switched to an oxygen stream of 100 ml / min, and the calorific value of the film was measured. The calorific value measured was taken as the calorific value of oxidation and used as an index of oxidation resistance. Since the amount of heat of oxidation is generated by oxidation, the smaller the amount of heat of oxidation, the better the oxidation resistance. From the viewpoint of heat resistance, the heat of oxidation was evaluated as A when the heat of oxidation was less than 600 J / g and B as 600 J / g or more.

(7) Saturated water absorption (5) Film obtained by film formation (dimensions: 20 mm × 10 mm, thickness 0.25 mm; weight about 0.05 g) is immersed in ion exchange water at 23 ° C. for a predetermined time ( Every 30 days), the film was taken out, the film weight was measured, and the rate of increase in the film weight was calculated. When the rate of increase in film weight is within the range of 0.2% for 3 consecutive times, it is determined that the absorption of water into the polyamide resin film has reached saturation, and the weight of the film before being immersed in water Saturated water absorption (%) was calculated from formula (1) from (Xg) and the weight (Yg) of the film when saturation was reached.

(8) Chemical resistance After immersing the film obtained by film forming of (5) at the following chemicals and its temperature for 7 days, the weight residual ratio (%) and changes in the appearance of the film were observed. The chemicals used and their temperatures were 37 mass% concentrated hydrochloric acid, 64 mass% sulfuric acid, 30 g / dl sodium hydroxide aqueous solution, 5 g / dl potassium permanganate aqueous solution at 23 ° C, and benzyl alcohol at 50 ° C.

(9) Hydrolysis resistance The film obtained by the film formation of (5) was put in an autoclave and treated in water, 0.5 mol / l sulfuric acid, and 1 mol / l sodium hydroxide aqueous solution at 121 ° C. for 60 minutes, respectively. After that, the residual weight ratio (%) and the appearance change were examined.

[Example I-1]
5L equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure outlet, polymer outlet, and raw material inlet with a raw material feed pump directly connected by SUS316 piping of 1/8 inch diameter A pressure vessel was charged with 290 g (2.5 mol) of 1,6-hexanediamine and 430 g (2.5 mol) of 1,10-decanediamine, and the pressure vessel was pressurized to 3.0 MPaG with nitrogen gas, Next, nitrogen gas was released to normal pressure, and the system was heated up under sealing pressure. After the internal temperature was set to 190 ° C. over 20 minutes, 1011 g (5.0 mol) of dibutyl oxalate was injected into the reaction vessel at a flow rate of 65 ml / min by a raw material feed pump. The internal pressure in the pressure vessel immediately after injection of the entire amount increased to 0.65 MPaG by 1-butanol generated by the polycondensation reaction, and the internal temperature increased to 197 ° C.
Distillation of butanol produced immediately after injection was started, and the internal temperature was raised to 260 ° C. over 2 hours while maintaining the internal pressure at 0.50 MPaG (first temperature raising step). Immediately after the internal temperature reached 260 ° C., 1-butanol produced by the polycondensation reaction was extracted from the pressure release port over 20 minutes (extraction process). After releasing the pressure, heating was started under a nitrogen stream of 260 ml / min, the internal temperature was raised to 275 ° C. over 1 hour, and held at 275 ° C. for 1 hour (second heating step). Thereafter, stirring was stopped, the inside of the system was pressurized to 3 MPaG with nitrogen and allowed to stand for 10 minutes, and then released to an internal pressure of 0.5 MPaG, and the polymer was extracted from the lower part of the pressure vessel in a string shape. The string-like polymer was immediately cooled with water, and the water-cooled string-like polymer was pelletized with a pelletizer. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 50:50.

[Example I-2]
(I) Prepolymerization step: The inside of a 1 L separable flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, and raw material inlet is replaced with nitrogen gas, and 500 ml of dehydrated toluene, 1,6- Hexanediamine 35.2 g (0.30 mol) and 1,10-decanediamine 34.7 g (0.20 mol) were charged. This separable flask was placed in an oil bath and heated to 50 ° C., and then charged with 102 g (0.50 mol) of dibutyl oxalate.
Next, the temperature of the oil bath was raised to 130 ° C. and kept under reflux for 5 hours. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 50 ml / min.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is kept under a reduced pressure of 13 Pa or less. Then, after performing an operation of introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 240 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. After the temperature of the salt bath was raised to 290 ° C. over 1 hour, the inside of the container was depressurized to about 66.5 Pa and held for another 2 hours. Subsequently, nitrogen gas was introduced to normal pressure, then taken out from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a white polyoxamide resin. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 60:40.

[Example I-3]
406 g (3.5 mol) of 1,6-hexanediamine, 258 g (1.5 mol) of 1,10-decanediamine, and 1012 g (5.0 mol) of dibutyl oxalate were used at 0.05 MPaG under the first heating step. The temperature was raised to 280 ° C. in the same manner as in Example I-1, except that the temperature was raised to 300 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 70:30.

[Example I-4]
In the first heating step, 465 g (4.0 mol) of 1,6-hexanediamine, 172 g (1.0 mol) of 1,10-decanediamine, and 1012 g (5.0 mol) of dibutyl oxalate The temperature was raised to 295 ° C. in the same manner as in Example I-1, except that the temperature was raised to 310 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 80:20.

[Example I-5]
290 g (2.5 mol) of 1,6-hexanediamine, 501 g (2.5 mol) of 1,12-dodecanediamine and 1012 g (5.0 mol) of dibutyl oxalate were used, and the pressure was reduced to 0.05 MPaG in the first heating step. The temperature was raised to 260 ° C., and the same procedure as in Example I-1 was performed except that the temperature was raised to 280 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,12-decanediamine in the obtained polyoxamide resin is 50:50.

[Example I-6]
(I) Pre-polycondensation step: 40.7 g (0.35 mol) of 1,6-hexanediamine, 30.1 g (0.15 mol) of 1,12-dodecanediamine, and 102 g (0.50 mol) of dibutyl oxalate The same procedure as in Example I-2 was performed except for the preparation.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 240 ° C. under a nitrogen stream of 50 ml / min, and the temperature was immediately raised. After the temperature of the salt bath was adjusted to 310 ° C. over 1 hour, the inside of the container was depressurized to about 66.5 Pa and held for another 2 hours. Subsequently, after introducing nitrogen gas to normal pressure, it was removed from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide resin. The molar ratio of 1,6-hexanediamine and 1,12-dodecanediamine in the obtained polyoxamide resin is 70:30.

[Example I-7]
In the first heating step, 232 g (2.0 mol) of 1,6-hexanediamine, 517 g (3.0 mol) of 1,10-decanediamine, and 1012 g (5.0 mol) of dibutyl oxalate were used at 0.05 MPaG. The temperature was raised to 220 ° C. and the temperature was raised to 240 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 40:60.

[Example I-8]
Using 232 g (2.0 mol) of 1,6-hexanediamine, 601 g (3.0 mol) of 1,12-dodecanediamine, and 1012 g (5.0 mol) of dibutyl oxalate, The temperature was raised to 215 ° C. in the same manner as in Example I-1 except that the temperature was raised to 235 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,12-dodecanediamine in the obtained polyoxamide resin is 40:60.

[Comparative Example I-1]
(I) Pre-polycondensation step: using a separable flask having an internal volume of 300 ml, dehydrated toluene 100 ml, 1,6-hexanediamine 15.5 g (0.13 mol), dibutyl oxalate 27.1 g (0.13 mol) ) Was carried out in the same manner as in Example I-2.
(Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. The temperature of the salt bath was adjusted to 340 ° C. over 1 hour, and then kept for 2 hours. Then, it took out from the salt bath and cooled to room temperature under a nitrogen stream to obtain a white powdery polyamide. This powder was difficult to produce a film by press molding and could not be evaluated for oxidation. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 100: 0.

[Reference Example I-1]
(I) Pre-polycondensation step: Using a separable flask having an internal volume of 500 ml, dehydrated toluene 200 ml, 1,10-decanediamine 36.2 g (0.21 mol), dibutyl oxalate 42.5 g (0.21 mol) ) Was carried out in the same manner as in Example I-2.
(Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. The temperature of the salt bath was brought to 285 ° C. over 1 hour and held for another 2 hours. The polyoxamide resin was obtained by removing from the salt bath and cooling to room temperature under a nitrogen stream of 50 ml / min. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 0: 100.

[Reference Example I-2]
(I) Pre-polycondensation step: Using a separable flask having an internal volume of 500 ml, 200 ml of dehydrated toluene, 42.1 g (0.21 mol) of 1,12-dodecanediamine, 42.5 g (0.21 mol) of dibutyl oxalate ) Was carried out in the same manner as in Example I-2.
(Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. The salt bath temperature was 265 ° C. over 1 hour and held for another 2 hours. The polyoxamide resin was obtained by removing from the salt bath and cooling to room temperature under a nitrogen stream of 50 ml / min. The molar ratio of 1,6-hexanediamine and 1,12-dodecanediamine in the obtained polyoxamide resin is 0: 100.

[Comparative Example I-2]
(I) Prepolycondensation step: 1,9-nonanediamine 4.8 g (0.03 mol), 2-methyl-1,8-octanediamine 75.4 g (0.47 mol), dibutyl oxalate 102 g (0.50) Mol) was carried out in the same manner as in Example I-2.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. After the temperature of the salt bath was adjusted to 260 ° C. over 1 hour, the inside of the container was depressurized to about 66.5 Pa and held for another 2 hours. Subsequently, after introducing nitrogen gas to normal pressure, it was removed from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide resin.

  The diamine composition, relative viscosity (ηr), melting point (Tm) of polyamide resins obtained from Examples I-1 to I-8, Reference Examples I-1 to I-2 and Comparative Examples I-1 to I-2, Tables I-1 and I-2 show the crystallization temperature (Tc), 1% weight loss temperature (Td), temperature difference (Tm-Tc), moldable temperature range (Td-Tm), and oxidation heat amount. Further, the saturated water absorption of the polyamide resins obtained from Examples I-1 to I-6 is shown in Table I-3. Furthermore, the chemical resistance of the polyamide resin obtained from Example I-1 is shown in Table I-4, and the hydrolysis resistance is shown in Table I-5.

  From Table I-1 and Table I-2, the polyamide resins obtained in Examples I-1 to I-6 are Example I-7, Example I-8, Reference Example I-1, and Reference Example I-. 2. The melting point is higher than that of Comparative Example I-2. Moreover, since the polyamide resin obtained by Example I-1 to I-6 shows the oxidation calorie | heat amount small compared with Comparative Example I-2, oxidation resistance is excellent. The polyamide resin according to the second aspect of the present invention has a high melting point, excellent oxidation resistance, and excellent heat resistance.

[Comparative Example I-3]
A film was molded using nylon 6 (UBE Nylon 1015B, manufactured by Ube Industries) instead of the polyamide resin obtained in the present invention. The obtained nylon 6 film was a colorless and transparent film. The film was evaluated for saturated water absorption, chemical resistance, and hydrolysis resistance. The results are shown in Tables I-3, I-4 and I-5, respectively.

[Comparative Example I-4]
A film was formed using nylon 66 (UBE Nylon 2020B, manufactured by Ube Industries) instead of the polyamide resin obtained in the present invention. The obtained nylon 66 film was a colorless and transparent film. The saturated water absorption of this film was evaluated. The results are shown in Table I-3.

[Comparative Example I-5]
Instead of the polyamide resin obtained in the present invention, a film was formed using nylon 12 (UBE Kosan, UBESTA 3014U). The obtained nylon 12 film was a colorless and transparent film. The film was evaluated for saturated water absorption and chemical resistance. The results are shown in Tables I-3 and I-4, respectively.

  From Tables I-3, I-4, and I-5, the polyamide resin according to the second aspect of the present invention has low water absorption compared to nylon 6, nylon 66, and 12, and is resistant to chemicals and hydrolysis. Excellent.

[2] Examples II-1 to II-7, Reference Examples II-1 to II-2, Comparative Examples II-1 to II-5
[Physical property measurement, molding, evaluation method]
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, relative viscosity, melting point, crystallization temperature, crystallization time evaluation, 1% weight loss temperature, film forming and oxidation resistance evaluation, measurement of saturated water absorption rate, chemical resistance, hydrolysis resistance evaluation in Examples Was carried out by the following method.

(1) Relative viscosity (ηr)
Measurement was performed in the same manner as in the above [1].

(2) Melting point (Tm ′), crystallization temperature (Tc) and temperature difference (Tm′−Tc)
Tm ′ and Tc were measured in a nitrogen atmosphere using PYRIS Diamond DSC manufactured by PerkinELmer. The temperature was raised from 30 ° C. to 280 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run), held at 280 ° C. for 5 minutes, and then lowered to 30 ° C. at a rate of 10 ° C./min (temperature fall first run). Then, the temperature was raised to 280 ° 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-fall first run was defined as the crystallization temperature (Tc), and the endothermic peak temperature of the temperature-increased second run as the melting point (Tm ′). A temperature difference (Tm′−Tc) was determined from the obtained melting point (Tm ′) and crystallization temperature (Tc). From the viewpoints of durability at high temperatures and melt moldability, those having a melting point (Tm ′) of 270 ° C. or more and less than 320 ° C. were evaluated as A, and those having a melting point (Tm ′) of less than 270 ° C. or 320 ° C. or more were evaluated as B.

(3) Evaluation of crystallization time In the measurement of the following crystallization time, the temperature increase second run endothermic peak temperature (Tm ′) of DSC in (2) was used.
The crystallization time was measured under a nitrogen atmosphere using PYRIS Diamond DSC manufactured by PerkinELmer. The temperature was raised from room temperature to Tm ′ + 20 ° C. at a rate of 100 ° C./min, held at Tm ′ + 20 ° C. for 10 minutes to dissolve the polymer, and then cooled to Tm′-20 ° C. at a rate of 500 ° C./min. And kept at Tm′−20 ° C. for isothermal crystallization. The time from reaching Tm′-20 ° C. until the peak top of the exothermic peak due to crystallization was observed was defined as tmax ′, and this value was used as the crystallization time. From the viewpoint of moldability, the case where the value of tmax 'was 1 minute or more was evaluated as A, and the case where it was less than 1 minute was evaluated as B.

(4) 1% weight loss temperature (Td) and temperature difference (Td−Tm ′)
Td was measured by thermogravimetric analysis (TGA) using THERMOGRAVIMETRIC ANALYZER TGA-50 manufactured by Shimadzu Corporation. Under a nitrogen stream of 20 ml / min, the temperature was raised from room temperature to 500 ° C. at a rate of temperature increase of 10 ° C./min, and 1% weight loss temperature (Td) was measured. The temperature difference (Td−Tm ′) was determined from the obtained 1% weight loss temperature (Td) and the melting point (Tm ′) obtained in (2).
From the viewpoint of melt moldability, AA has a temperature difference (Td−Tm ′) of 125 ° C. or more, A is 60 ° C. or more and less than 125 ° C., B is 50 ° C. or more and less than 60 ° C., 50 ° C. Less than that was evaluated as C.

(5) Film formation It measured similarly to said [1].
(6) Oxidation resistance It measured similarly to said [1].
(7) Saturated water absorption Measured in the same manner as in [1] above.
(8) Chemical resistance Measured in the same manner as in [1] above.
(9) Hydrolysis resistance Measured in the same manner as in [1] above.

[Example II-1]
5L equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet, pressure outlet, polymer outlet, and raw material inlet with a raw material feed pump directly connected by SUS316 piping of 1/8 inch diameter A pressure vessel was charged with 232 g (2.0 mol) of 1,6-hexanediamine and 517 g (3.0 mol) of 1,10-decanediamine, and the pressure vessel was pressurized to 3.0 MPaG with nitrogen gas, Next, nitrogen gas was released to normal pressure, and the system was heated up under sealing pressure. After the internal temperature was set to 190 ° C. over 20 minutes, 1011 g (5.0 mol) of dibutyl oxalate was injected into the reaction vessel at a flow rate of 65 ml / min by a raw material feed pump. The internal pressure in the pressure vessel immediately after injection of the entire amount increased to 0.65 MPaG by 1-butanol generated by the polycondensation reaction, and the internal temperature increased to 197 ° C.

  Distillation of butanol produced immediately after injection was started, and the internal temperature was raised to 260 ° C. over 2 hours while maintaining the internal pressure at 0.50 MPaG (first temperature raising step). Immediately after the internal temperature reached 260 ° C., 1-butanol produced by the polycondensation reaction was extracted from the pressure release port over 20 minutes (extraction process). After releasing the pressure, heating was started under a nitrogen stream of 260 ml / min, the internal temperature was raised to 245 ° C. over 1 hour, and held at 245 ° C. for 1 hour (second heating step). Thereafter, stirring was stopped, the inside of the system was pressurized to 3 MPaG with nitrogen and allowed to stand for 10 minutes, and then released to an internal pressure of 0.5 MPaG, and the polymer was extracted from the lower part of the pressure vessel in a string shape. The string-like polymer was immediately cooled with water, and the water-cooled string-like polymer was pelletized with a pelletizer. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 40:60.

[Example II-2]
(I) Prepolymerization step: The inside of a 1 L separable flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, and raw material inlet is replaced with nitrogen gas, and 500 ml of dehydrated toluene, 1,6- Hexanediamine 11.6 g (0.10 mol) and 1,10-decanediamine 68.9 g (0.40 mol) were charged. This separable flask was placed in an oil bath and heated to 50 ° C., and then charged with 101 g (0.50 mol) of dibutyl oxalate.

  Next, the temperature of the oil bath was raised to 130 ° C. and kept under reflux for 5 hours. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 50 ml / min.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is kept under a reduced pressure of 13 Pa or less. Then, after performing an operation of introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. After the temperature of the salt bath was raised to 250 ° C. over 1 hour, the inside of the container was depressurized to about 66.5 Pa and held for another 2 hours. Subsequently, nitrogen gas was introduced to normal pressure, then taken out from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a white polyoxamide resin. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 20:80.

[Example II-3]
In the first temperature raising step, 29.1 g (0.25 mol) of 1,6-hexanediamine, 818 g (4.75 mol) of 1,10-decanediamine and 1011 g (5.0 mol) of dibutyl oxalate were used. The procedure was the same as Example II-1 except that the temperature was raised to 260 ° C. under 05 MPaG and the temperature was raised to 275 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 5:95.

[Example II-4]
Using 232 g (2.0 mol) of 1,6-hexanediamine, 601 g (3.0 mol) of 1,12-dodecanediamine, and 1012 g (5.0 mol) of dibutyl oxalate, The temperature was raised to 215 ° C. in the same manner as in Example II-1 except that the temperature was raised to 235 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,12-decanediamine in the obtained polyoxamide resin is 40:60.

[Example II-5]
(I) Pre-polycondensation step: 11.6 g (0.1 mol) of 1,6-hexanediamine, 80.1 g (0.4 mol) of 1,12-dodecanediamine, and 101 g (0.50 mol) of dibutyl oxalate The same procedure as in Example II-2 was carried out except for the preparation.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. After the temperature of the salt bath was adjusted to 245 ° C. over 1 hour, the inside of the container was depressurized to about 66.5 Pa and held for another 2 hours. Subsequently, after introducing nitrogen gas to normal pressure, it was removed from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide resin. The molar ratio of 1,6-hexanediamine and 1,12-dodecanediamine in the obtained polyoxamide resin is 20:80.

[Example II-6]
Using 291 g (2.5 mol) of 1,6-hexanediamine, 431 g (2.5 mol) of 1,10-decanediamine and 1011 g (5.0 mol) of dibutyl oxalate, The temperature was raised to 260 ° C. and the temperature was raised to 280 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 50:50.

[Example II-7]
291 g (2.5 mol) of 1,6-hexanediamine, 501 g (2.5 mol) of 1,12-dodecanediamine and 1012 g (5.0 mol) of dibutyl oxalate were used, and the pressure was reduced to 0.05 MPaG in the first heating step. The temperature was raised to 260 ° C. and the temperature was raised to 275 ° C. under a nitrogen stream in the second temperature raising step. The molar ratio of 1,6-hexanediamine and 1,12-dodecanediamine in the obtained polyoxamide resin is 50:50.

[Comparative Example II-1]
(I) Pre-polycondensation step: using a separable flask having an internal volume of 300 ml, dehydrated toluene 100 ml, 1,6-hexanediamine 15.5 g (0.13 mol), dibutyl oxalate 27.1 g (0.13 mol) ) Was carried out in the same manner as in Example II-2.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. The temperature of the salt bath was adjusted to 340 ° C. over 1 hour, and then kept for 2 hours. Then, it took out from the salt bath and cooled to room temperature under a nitrogen stream to obtain a white powdered polyamide resin. This powder was difficult to produce a film by press molding and could not be evaluated for oxidation. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 100: 0.

[Reference Example II-1]
(I) Pre-polycondensation step: Using a separable flask having an internal volume of 500 ml, dehydrated toluene 200 ml, 1,10-decanediamine 36.2 g (0.21 mol), dibutyl oxalate 42.5 g (0.21 mol) ) Was carried out in the same manner as in Example II-2.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. The temperature of the salt bath was brought to 285 ° C. over 1 hour and held for another 2 hours. The polyoxamide resin was obtained by removing from the salt bath and cooling to room temperature under a nitrogen stream of 50 ml / min. The molar ratio of 1,6-hexanediamine and 1,10-decanediamine in the obtained polyoxamide resin is 0: 100.

[Reference Example II-2]
(I) Pre-polycondensation step: Using a separable flask having an internal volume of 500 ml, 200 ml of dehydrated toluene, 42.1 g (0.21 mol) of 1,12-dodecanediamine, 42.5 g (0.21 mol) of dibutyl oxalate ) Was carried out in the same manner as in Example II-2.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. The salt bath temperature was 265 ° C. over 1 hour and held for another 2 hours. The polyoxamide resin was obtained by removing from the salt bath and cooling to room temperature under a nitrogen stream of 50 ml / min. The molar ratio of 1,6-hexanediamine and 1,12-dodecanediamine in the obtained polyoxamide resin is 0: 100.

[Comparative Example II-2]
(I) Prepolycondensation step: 1,9-nonanediamine 4.8 g (0.03 mol), 2-methyl-1,8-octanediamine 75.4 g (0.47 mol), dibutyl oxalate 102 g (0.50) Mol) was carried out in the same manner as in Example II-2.

  (Ii) Post-polycondensation step: The polymer obtained by the above operation is charged into a glass reaction tube having a diameter of about 35 mmφ equipped with a stirrer, an air cooling tube, and a nitrogen introduction tube, and the inside of the reaction tube is subjected to reduced pressure of 13.3 Pa or less. Then, after introducing nitrogen gas to normal pressure, it was transferred to a salt bath maintained at 210 ° C. under a nitrogen stream of 50 ml / min, and temperature increase was immediately started. After the temperature of the salt bath was adjusted to 260 ° C. over 1 hour, the inside of the container was depressurized to about 66.5 Pa and held for another 2 hours. Subsequently, after introducing nitrogen gas to normal pressure, it was removed from the salt bath and cooled to room temperature under a nitrogen stream of 50 ml / min to obtain a polyamide resin.

  Diamine composition, relative viscosity (ηr), melting point (Tm ′) of polyamide resins obtained from Examples II-1 to II-7, Reference Examples II-1 to II-2 and Comparative Examples II-1 to II-2 Table II-1 and Table II-2 show the crystallization temperature (Tc), 1% weight loss temperature (Td), temperature difference (Tm′−Tc), moldable temperature range (Td−Tm ′), and oxidation heat amount. Show. Moreover, the saturated water absorption of the polyamide resins obtained from Examples II-1 to II-5 is shown in Table II-3. Furthermore, the chemical resistance of the polyamide resin obtained from Example II-1 is shown in Table II-4, and the hydrolysis resistance is shown in Table II-5.

  From Table II-1 and Table II-2, the polyamide resins obtained in Examples II-1 to II-5 are Example II-6, Example II-7, Comparative Example I-1, and Comparative Example I-. Compared to 2, the moldable temperature range is wide. The polyamide resins obtained in Examples II-1 to II-5 have a longer crystallization time than Comparative Example II-1, Reference Example II-1, and Reference Example II-2. Moreover, since the polyamide resin obtained by Example II-1 to II-5 shows the oxidation calorie | heat amount small compared with Comparative Example II-2, oxidation resistance is excellent. The polyamide resin according to the third aspect of the present invention has oxidation resistance and is excellent in moldability.

[Comparative Example II-3]
A film was molded using nylon 6 (UBE Nylon 1015B, manufactured by Ube Industries) instead of the polyamide resin obtained in the present invention. The obtained nylon 6 film was a colorless and transparent film. The film was evaluated for saturated water absorption, chemical resistance, and hydrolysis resistance. The results are shown in Tables II-3, II-4 and II-5, respectively.

[Comparative Example II-4]
A film was formed using nylon 66 (UBE Nylon 2020B, manufactured by Ube Industries) instead of the polyamide resin obtained in the present invention. The obtained nylon 66 film was a colorless and transparent film. The saturated water absorption of this film was evaluated. The results are shown in Table II-3.

[Comparative Example II-5]
Instead of the polyamide resin obtained in the present invention, a film was formed using nylon 12 (UBE Kosan, UBESTA 3014U). The obtained nylon 12 film was a colorless and transparent film. The film was evaluated for saturated water absorption and chemical resistance. The results are shown in Tables II-3 and II-4, respectively.

  From Tables II-3, II-4, and II-5, the polyamide resin of the present invention has low water absorption compared to nylon 6, nylon 66, and 12, and is excellent in chemical resistance and hydrolysis resistance.

The polyamide resin of the present invention can be suitably used as a molding material for industrial materials, industrial materials, household products and the like. For example, various molded products such as sheets, films, pipes, tubes, monofilaments, fibers, etc., automobile parts, computers and computer-related equipment, optical equipment members, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / architecture It can be used as a molding material for supplies, medical supplies, household items, etc.
Among them, the polyamide resin according to the second aspect is excellent in heat resistance, and therefore requires heat resistance, packaging materials that require heat sterilization, molding materials around automobile engines, electrical / electronic materials having solder heat resistance, etc. It can be suitably used as a molding material.
In particular, the polyamide resin according to the third aspect can be suitably used as a molding material for an extrusion-molded product, taking advantage of the slow crystallization time.

Claims (13)

A polyamide resin using a dicarboxylic acid component and a diamine component,
The dicarboxylic acid component includes an oxalic acid compound,
The diamine component includes diamine (a) and diamine (b),
The diamine (a) is at least one diamine selected from the group consisting of aliphatic diamines having 2 to 8 carbon atoms, and the diamine (b) is selected from the group consisting of aliphatic diamines having 10 to 18 carbon atoms At least one diamine,
The polyamide resin whose molar ratio of the said diamine (a) and the said diamine (b) is 1: 99-99: 1.   2. The polyamide resin according to claim 1, which has a relative viscosity of 1.6 to 6.0 measured at 25 ° C. using a solution having a polyamide resin concentration of 1.0 g / dl using 96 mass% sulfuric acid as a solvent.   The polyamide resin according to claim 1 or 2, wherein the heat of oxidation is 600 J / g or less.   The polyamide resin according to any one of claims 1 to 3, wherein a molar ratio of the diamine (a) to the diamine (b) is 50:50 to 99: 1.   The polyamide resin according to claim 4, wherein the molar ratio of the diamine (a) to the diamine (b) is 50:50 to 80:20.   The polyamide resin according to claim 4 or 5, which has a melting point of 270 to 320 ° C.   The molar ratio of the diamine (a) to the diamine (b) is 1:99 to 50:50 (however, each of the diamine (a) and the diamine (b) does not include 50 mol%). The polyamide resin according to any one of the above.   The polyamide resin according to claim 7, wherein a molar ratio of the diamine (a) to the diamine (b) is 15:85 to 45:55.   The polyamide resin according to claim 7 or 8, wherein a moldable temperature range (temperature difference: Td-Tm), which is a value obtained by subtracting the melting point Tm 'of the polyamide resin from the 1% weight phenomenon temperature Td of the polyamide resin, is 125 ° C or more. .   The polyamide resin according to any one of claims 7 to 9, wherein tmax 'as an index of crystallization time is 1 minute or more.   The molded article which consists of a polyamide resin of any one of Claims 1-10.   The molded article according to claim 11, wherein the molded article is used for a part requiring heat resistance.   The molded article according to claim 11 or 12, wherein the molded article has a shape of a sheet, a film, a pipe, a tube, a monofilament, a fiber, or a container.