JP2015010224A - Polyoxamide resin and heat-resistant component - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyoxamide resin excellent in heat resistance and color tone.SOLUTION: A polyoxamide resin contains a structural unit derived from an amine component in which a peak area fraction corresponding to 1,10-decane diamine in chromatogram by gas chromatographic analysis is 98.90% or more, and a peak area fraction corresponding to impurities having a molecular ion peak (M) in mass spectrum of 167 is less than 0.007%; and a structural unit derived from oxalic acid.

Description

  The present invention relates to a polyoxamide resin and a heat-resistant component.

  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, as well as problems such as deterioration in acids, high-temperature alcohol and hot water have been pointed out, and there is an increasing demand for polyamides with superior dimensional stability and chemical resistance. . In recent years, environmental problems such as global warming and resource depletion have become apparent, and attention has been paid to materials that are friendly to the global environment, and the demand for resin materials using plant-derived materials is also increasing.

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

  So far, polyoxamide resins using various aliphatic linear diamines as diamine components have been proposed. However, for example, a polyoxamide resin using 1,6-hexanediamine as a diamine component has a melting point (about 320 ° C.) higher than the thermal decomposition temperature (1% weight loss temperature in nitrogen; about 310 ° C.) (for example, And non-patent document 1), melt polymerization and melt molding are difficult and cannot be practically used.

  For the polyoxamide resin whose diamine component is 1,9-nonanediamine (hereinafter sometimes abbreviated as PX9), the manufacturing method and crystal structure of L. Franco et al. Using diethyl oxalate as the oxalic acid source (For example, refer nonpatent literature 2). PX9 obtained here is a polymer having an intrinsic viscosity of 0.97 dL / g and a melting point of 246 ° C. For example, Patent Document 2 shows that PX9 having an intrinsic viscosity of 0.99 dL / g and a melting point of 248 ° C. was produced when dibutyl oxalate was used as the dicarboxylic acid ester.

  Patent Documents 2 to 4 describe polyoxamide resins whose diamine components are 1,10-decanediamine (hereinafter sometimes abbreviated as PX10). The polyoxamide resin described in Patent Document 3 uses oxalic acid instead of oxalic acid diester as a raw material. In the case of a polyoxamide resin, it is known that it is not appropriate to use oxalic acid as a raw material because of its high polymerization temperature (see, for example, Non-Patent Document 3).

JP 2006-57033 A Japanese National Patent Publication No. 5-506466 U.S. Pat. No. 2,130,948 US Pat. No. 2,580,031

S. W. Shalaby., J. Polym. Sci., 11, 1 (1973) L. Franco et al., Macromolecules., 31, 3912 (1988) R.J.Gaymans et al., J. Polym. Sci. Polym. Chem. Ed., 22, 1373 (1984)

However, the polyoxamide resin (PX9) described in Non-Patent Document 2 and Patent Document 2 has a problem in that only a low molecular weight body that cannot be formed into a tough molded body is obtained. Further, the polyxamide resin (PX10) described in Patent Document 3 had a melting point as low as 229 ° C. and did not have a sufficient high molecular weight. Furthermore, the purity and impurities of 1,10-decanediamine as a raw material were not studied at all.
Furthermore, the polyoxamide resins (PX10) described in Patent Documents 2 and 4 are all manufactured by a method of mixing raw materials in a solvent such as ethanol or toluene. In this method, since the low molecular weight product before sufficiently reaching a high molecular weight is precipitated in the solvent, a mixture of unreacted raw material, solvent, and low molecular weight product is formed. When the mixture is heated to increase the molecular weight, unreacted raw materials are distilled off or pyrolyzed before the low molecular weight material is melted, so that it is difficult to achieve a sufficient high molecular weight. Furthermore, the purity and impurities of 1,10-decanediamine have not been studied at all.

  The problem to be solved by the present invention is to provide a polyoxamide resin which is a sufficiently high molecular weight polymer and has excellent heat resistance and color tone in a polyoxamide resin containing 1,10-decanediamine as a diamine component.

As a result of intensive studies in order to solve the above problems, the present inventors have determined that the peak area of the chromatogram of the main component 1,10-decanediamine among the components separated by gas chromatographic analysis as the amine component is as follows. The content of impurities whose fraction is 98.90% or more and whose molecular ion peak (M ⁺ ) in the mass spectrum is 167 is less than 0.007% in the peak area fraction of the chromatogram. When used, it was found that a polyoxamide resin having a sufficiently high molecular weight and excellent heat resistance and color tone was obtained, and the present invention was completed.

Specific means for solving the above problems are as follows.
That is, according to the present invention, in the chromatogram by gas chromatographic analysis, the peak area fraction corresponding to 1,10-decanediamine is 98.90% or more, and the molecular ion peak (M ⁺ ) in the mass spectrum is 167. There is provided a polyoxamide resin comprising a structural unit derived from an amine component having a peak area fraction corresponding to an impurity of less than 0.007% and a structural unit derived from oxalic acid.

  The present invention is also characterized in that the relative viscosity (ηr) measured at 25 ° C. using a polyoxamide resin solution having a concentration of 1.0 g / dl using 96% sulfuric acid as a solvent is 2.2 to 3.5. The above-mentioned polyoxamide resin is provided.

  The present invention also provides a heat-resistant component containing the above polyoxamide resin.

  Moreover, this invention provides said heat resistant components which are any shapes chosen from the group which consists of a sheet | seat, a film, a pipe, a tube, a monofilament, a fiber, and a container.

  Further, the present invention is any one selected from the group consisting of automobile members, computers and computer-related equipment, optical equipment members, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, and household goods. The heat-resistant component described above is used.

In the chromatogram obtained by gas chromatographic analysis, the present invention has a peak area fraction corresponding to 1,10-decanediamine of 98.90% or more and a molecular ion peak (M ⁺ ) in the mass spectrum of 167. Preparing an amine component having a peak area fraction corresponding to an impurity of less than 0.007%, and at least one acid component selected from the group consisting of the prepared amine component and oxalic acid and derivatives thereof And a method for producing a polyoxamide resin.

  ADVANTAGE OF THE INVENTION According to this invention, in the polyoxamide resin which contains 1,10-decanediamine in a diamine component, it is a sufficient high molecular weight body, and can provide the polyoxamide resin excellent in heat resistance and color tone.

  In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes. . Moreover, the numerical range shown using "to" shows the range which includes the numerical value described before and behind "to" as a minimum value and a maximum value, respectively. Further, the content of each component in the composition means the total amount of the plurality of substances present in the composition unless there is a specific notice when there are a plurality of substances corresponding to each component in the composition.

<Polyoxamide resin>
The polyoxamide resin of the present invention has a peak area fraction corresponding to 1,10-decanediamine of 98.90% or more and a molecular ion peak (M ⁺ ) in a mass spectrum in a chromatogram by gas chromatographic analysis. The structural unit derived from the amine component (henceforth a specific amine component) whose peak area fraction corresponding to the impurity which is 167 is less than 0.007%, and the structural unit derived from oxalic acid are included.
Since the polyoxamide resin of the present invention is sufficiently high molecular weight and excellent in heat resistance and color tone, it can be used as a particularly excellent heat resistant part as a molding material for industrial materials, industrial materials, household products, etc. it can. Moreover, since the plant-derived raw material is used, it can be used as a resin material in consideration of the global environment. The polyoxamide resin and heat-resistant parts having excellent heat resistance according to the present invention can be used without using a heat-resistance improving agent.

The polyoxamide resin of the present invention has a peak area fraction corresponding to 1,10-decanediamine of 98.90% or more and a molecular ion peak (M ⁺ ) in a mass spectrum in a chromatogram by gas chromatographic analysis. The structural unit derived from the amine component whose peak area fraction corresponding to the impurity which is 167 is less than 0.007% is included. Here, the structural unit derived from the amine component means a group formed by removing one hydrogen atom from the amino group of the amine component.
The structural unit derived from the amine component can be introduced into the polyoxamide resin by condensing the corresponding amine component with at least one acid component selected from the group consisting of oxalic acid and oxalic acid derivatives.

The specific amine component constituting the polyoxamide resin has a peak area fraction corresponding to 1,10-decanediamine of 98.90% or more in a chromatogram by gas chromatographic analysis, and a molecular ion peak (M ⁺ ) Has a peak area fraction corresponding to an impurity (hereinafter also referred to as a specific impurity) of 167 is less than 0.007%. By using a specific amine component having a high content of 1,10-decanediamine and a low content of specific impurities as the amine component, it is possible to obtain a polyoxamide resin that is sufficiently high in molecular weight and excellent in heat resistance and color tone. it can.
The molecular ion peak of the specific impurity is measured by chemical ionization (CI).

The content of 1,10-decanediamine contained in the specific amine component is 98.90% or more as a peak area fraction of a chromatogram by gas chromatographic analysis, but is preferably 99.30% or more. More preferably, it is 60% or more. The content of the specific impurity contained in the amine component is less than 0.007% as a peak area fraction of chromatogram by gas chromatographic analysis, but is preferably 0.003% or less, 0.002% The following is more preferable.
The conditions for gas chromatographic analysis of the specific amine component are as follows.

Sample: A 5 mass% ethanol solution of an amine component is used at an injection volume of 1 μL.
Column: Rtx-5Amine (30 m, inner diameter 0.53 mm) (manufactured by Shimadzu LLC)
Injection temperature: 290 ° C
Detector temperature: 310 ° C
Detector: FID
Column temperature: held at 40 ° C. for 4 minutes, heated from 40 ° C. to 300 ° C. at 10 ° C./minute, and then held at 300 ° C.
Carrier gas: He
Flow rate: 10ml / min
Taking the total peak area of the obtained chromatogram as 100%, the peak area fraction (%) of the chromatogram of the main component 1,10-decanediamine and the peak area fraction (%) of the specific impurity were calculated. The peak area was calculated using software attached to the gas chromatograph apparatus.

  As for the hue of the specific amine component, the Hazen color number (APHA) is preferably 15 or less, and more preferably 11 or less. The Hazen color number (APHA) is measured using a color meter (for example, ZE6000 manufactured by Nippon Denshoku Industries Co., Ltd.).

  The specific amine component is not particularly limited as long as it satisfies the content of 1,10-decanediamine and the content of specific impurities. Among these, the specific amine component is preferably plant-derived 1,10-decanamine. Specifically, sebacic acid produced from castor oil collected from castor bean is preferably converted to 1,10-decanediamine by a conventional method.

In addition to the structural unit derived from the specific amine component, the polyoxamide resin may contain a structural unit derived from another diamine as long as the effects of the present invention are not impaired.
Other diamines include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, , 12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl Aliphatic diamines such as -1,6-hexanediamine and 5-methyl-1,9-nonanediamine; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine and isophoronediamine; p-phenylenediamine, m-phenylenediamine, p -Xylenediamine, m-xylenediamine, 4,4'-diaminodiphe Examples thereof include aromatic diamines such as nylmethane, 4,4′-diaminodiphenyl sulfone, and 4,4′-diaminodiphenyl ether. Other diamines may be used alone or in combination of two or more.

The content of the structural unit derived from 1,10-decanediamine contained in the polyoxamide resin is preferably 50 mol% or more in the total amount of the structural unit derived from the amine component contained in the polyoxamide resin, and is 80 mol. % Or more is more preferable, and 90 mol% or more is preferable.
When the polyoxamide resin contains a structural unit derived from another diamine other than 1,10-decanediamine, the content of the structural unit derived from the other diamine is a structural unit derived from the amine component contained in the polyoxamide resin. Is preferably 0.01 mol% or more and less than 50 mol%, more preferably 0.05 mol% or more and 20 mol% or less, and 0.1 mol% or more and 10 mol% or less. More preferably.
In addition, content of the structural unit derived from the amine component contained in polyoxamide resin can be calculated by hydrolyzing polyoxamide resin and quantifying the amine component to produce | generate.

  The polyoxamide resin includes a structural unit derived from oxalic acid. Here, the structural unit derived from succinic acid means a group formed by removing one hydroxy group from at least one of two carboxy groups possessed by succinic acid. The structural unit derived from succinic acid can be introduced into the polyoxamide resin by condensing, for example, at least one acid component selected from the group consisting of succinic acid and succinic acid derivatives and an amine component.

  Examples of succinic acid derivatives include oxalic acid diesters. Of these, the acid component is preferably oxalic acid diester. The oxalic acid diester is not particularly limited as long as it has reactivity with an amino group, and can be appropriately selected from commonly used oxalic acid diesters. Examples of oxalic acid diesters include dimethyl oxalate, diethyl oxalate, dipropyl oxalate, diisopropyl oxalate, dibutyl oxalate, diisobutyl oxalate, di-t-butyl oxalate, etc., oxalic acid diesters of aliphatic monohydric alcohols having 1 to 4 carbon atoms, dicyclohexyl oxalate And oxalic acid diesters of alicyclic alcohols having 3 to 6 carbon atoms, and oxalic acid diesters of aromatic alcohols such as diphenyl oxalate.

  Among the above oxalic acid diesters, selected from the group consisting of oxalic acid diesters of aliphatic monohydric alcohols having 2 to 4 carbon atoms, oxalic acid diesters of alicyclic alcohols having 5 to 6 carbon atoms, and oxalic acid diesters of aromatic alcohols And at least one selected from the group consisting of oxalic acid diesters of aliphatic monohydric alcohols having 3 to 4 carbon atoms and oxalic acid diesters of aromatic alcohols. Particularly preferred is at least one selected from the group consisting of dibutyl oxalate and diphenyl oxalate.

In addition to the structural unit derived from oxalic acid, the polyoxamide resin may contain structural units derived from other dicarboxylic acids as long as the effects of the present invention are not impaired.
Other 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. Aliphatic dicarboxylic acids such as acid, azelaic acid, sebacic acid and suberic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid; 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 And aromatic dicarboxylic acids such as 4,4'-biphenyl dicarboxylic acid.
Furthermore, the polyoxamide resin may contain a structural unit derived from a trivalent or higher polyvalent carboxylic acid as long as melt molding is possible. Examples of the trivalent or higher polyvalent carboxylic acid include trimellitic acid, trimesic acid, and pyromellitic acid.
Other dicarboxylic acids and trivalent or higher polyvalent carboxylic acids may be used singly or in combination of two or more.

The content of the structural unit derived from oxalic acid contained in the polyoxamide resin is preferably 50 mol% or more, more preferably 80 mol% or more in the total amount of structural units derived from the acid component contained in the polyoxamide resin. Is more preferable, and 90 mol% or more is preferable.
When the polyoxamide resin contains a structural unit derived from other dicarboxylic acid or polyvalent carboxylic acid other than oxalic acid, the content of the structural unit derived from other dicarboxylic acid or polyvalent carboxylic acid is included in the polyoxamide resin. The total amount of structural units derived from the acid component is preferably 0.01 mol% or more and less than 50 mol%, more preferably 0.05 mol% or more and 20 mol% or less, and more preferably 0.1 mol% More preferably, it is 10 mol% or less.

  The content ratio of the structural unit derived from oxalic acid to the structural unit derived from 1,10-decanediamine in the polyoxamide resin is preferably 0.80 to 1.50 on a molar basis from the viewpoint of practicality. It is more preferable that it is 91-1.10, and it is still more preferable that it is 0.99-1.01.

There is no particular restriction on the molecular weight of the polyoxamide resin. The polyoxamide resin preferably has a molecular weight such that the relative viscosity ηr measured at 25 ° C. is in the range of 2.2 to 3.5 using a 96 mass% concentrated sulfuric acid solution having a polyoxamide resin concentration of 1.0 g / dl. More preferably within the range of 2.3 to 3.2, still more preferably within the range of 2.3 to 3.0. If ηr is in the range of 2.2 to 3.5, in addition to the heat resistance of the molded product, it is excellent in impact resistance and in molding processability, which is desirable.
The relative viscosity is measured with an Ostwald viscometer.

In the polyoxamide resin, the rate of decrease of the relative viscosity ηr ⁴⁸ after the heat treatment at 150 ° C. for 48 hours with respect to the relative viscosity ηr ⁰ before the heat treatment is preferably 15% or less, and more preferably 10% or less. Further, the rate of decrease of the relative viscosity ηr ⁷² after the heat treatment at 150 ° C. for 72 hours with respect to the relative viscosity ηr ⁰ before the heat treatment is preferably 20% or less, and more preferably 15% or less.
The reduction rate of the relative viscosity after the heat treatment is given by the following equation when the relative viscosity after the heat treatment is ηr ¹ and the relative viscosity before the heat treatment is ηr ⁰ .
Reduction rate (%) = {(ηr ⁰ −1) − (ηr ¹ −1)} × 100 / (ηr ⁰ −1) (formula)
Moreover, the low reduction rate of relative viscosity is achieved by using a specific amine component for preparation of polyoxamide resin.

The yellowness (YI) of the polyoxamide resin is preferably 30 or less, and more preferably 15 or less. The yellowness is measured according to JIS K 7373.
Low yellowness (YI) is achieved by using a specific amine component in the preparation of the polyoxamide resin.

<Method for producing polyxamide resin>
The production method of the polyoxamide resin has a peak area fraction corresponding to 1,10-decanediamine of 99.60% or more and a molecular ion peak (M ⁺ ) in the mass spectrum in a chromatogram by gas chromatographic analysis. A preparation step of preparing an amine component (specific amine component) having a peak area fraction corresponding to an impurity of 167 of less than 0.007%, and at least selected from the group consisting of the prepared amine component, oxalic acid and derivatives thereof A polycondensation step of condensing one acid component. By using a specific amine component having a specific configuration as the amine component constituting the polyoxamide resin, a polyoxamide resin excellent in heat resistance and color tone can be efficiently produced.

In the preparatory step, in the chromatogram obtained by gas chromatographic analysis, the peak area fraction corresponding to 1,10-decanediamine is 99.60% or more, and the molecular ion peak (M ⁺ ) in the mass spectrum is 167. If it is a method which can prepare the amine component whose peak area fraction corresponding to an impurity is less than 0.007%, there will be no restriction | limiting in particular. For example, even if it includes a step of converting plant-derived sebacic acid into a diamine or a step of selecting a desired amine component from commercially available 1,10-decanediamine, a commercially available 1 , 10-decanediamine may be purified to obtain a desired amine component.

  A polycondensation process can be suitably selected from the method normally used for manufacture of a polyamide resin. For example, the pressure polymerization method described in the pamphlet of International Publication No. WO2008 / 072754 can be applied. Specifically, the pressure polymerization method includes a step of mixing an amine component and oxalic acid or a derivative thereof (preferably oxalic acid diester) in a pressure-resistant vessel and performing pressure polymerization in the presence of an alcohol generated by a polycondensation reaction. It is preferable.

An example in the case of applying the pressure polymerization method to the production method of the polyoxamide resin will be described below.
First, the amine component 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 diester 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 polyoxamide produced by the reaction between the amine component and the oxalic acid diester can maintain a slurry state or a solution state in the alcohol generated at the same time and does not thermally decompose. For example, in the case of a polyoxamide resin using 1,10-decanediamine and dibutyl oxalate as raw materials, the reaction temperature is preferably 150 ° C. to 250 ° C. The charging ratio of oxalic acid diester to the amine component (oxalic acid diester / amine component) is preferably 0.80 to 1.50 (molar ratio), and preferably 0.91 to 1.10 (molar ratio). More preferably, it is 0.99 to 1.01 (molar ratio).

Next, while keeping 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 polyoxamide resin and not higher than the temperature at which it does not decompose. For example, in the case of a polyoxamide resin using 1,10-decanediamine and dibutyl oxalate as raw materials, the melting point is 251 ° C., so it is preferable to raise the temperature to 255 ° C. or more and 300 ° C. or less, and 260 ° C. or more and 290 ° C. or less. It is more preferable to raise the temperature, and it is even more preferable to raise the temperature to 265 ° C. or higher and 280 ° C. or lower.
The pressure in the pressure vessel until reaching the predetermined temperature is preferably adjusted to 0.1 MPa, more preferably from 1 MPa to 0.2 MPa from the saturated vapor pressure of the alcohol to be generated. After reaching the predetermined temperature, the pressure is released while distilling off the produced alcohol, and the polycondensation reaction is continued under normal pressure nitrogen flow or reduced pressure as necessary. A preferable final pressure in the case of carrying out the vacuum polymerization is 13.3 Pa to 0.1 MPa.

<Method of molding polyoxamide resin>
There is no restriction | limiting in particular as a shaping | molding method of polyoxamide resin, It can select suitably from the well-known shaping | molding methods applicable to polyamide, such as injection, extrusion, a hollow, a press, a roll, foaming, vacuum / pressure air, and extending | stretching. By these molding methods, a film, a sheet, a molded product, a fiber or the like can be molded into a desired shape.

<Polyoxamide resin composition>
The polyoxamide resin composition includes at least the polyoxamide resin, and includes other components as necessary. A polyoxamide resin composition is excellent in heat resistance and color tone by containing the said polyoxamide resin.

Other components include other polyoxamide resins other than the above polyoxamide resins, polyamide resins such as aromatic polyamides, aliphatic polyamides, and alicyclic polyamides; thermoplastic resins other than polyamides; elastomers; fillers; reinforcing fibers; And so on.
Various additives include stabilizers such as copper compounds, colorants, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, flame retardants, crystallization accelerators, glass fibers, plasticizers, and lubricants. And so on. Various additives may be added during the polycondensation reaction of the polyoxamide resin, or may be added thereafter.
Furthermore, the polyoxamide resin composition itself is excellent in heat resistance, but may further contain a heat resistance improver as necessary.

<Heat resistant parts>
The heat resistant component of the present invention contains the polyoxamide resin. The heat-resistant component can be formed into a desired shape such as various molded products, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded products have been conventionally used. The molding method of the polyoxamide resin is as described above.
The heat-resistant component may be a molded product of the polyoxamide resin composition.
Heat-resistant parts have excellent heat resistance in applications such as automobile parts, computers and computer-related equipment, optical equipment parts, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building equipment, medical supplies, and household goods. It can be used as a part having

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. Gas chromatographic analysis, mass spectral analysis, hue evaluation (APHA), relative viscosity measurement of the obtained polyoxamide resin, heat resistance evaluation test, and yellowness (YI) evaluation were performed by the following methods.

(1) Gas chromatographic analysis (GC)
A GC-2010 type gas chromatograph apparatus manufactured by Shimadzu Corporation equipped with Rtx-5Amine (30 m, inner diameter 0.53 mm) was used as a column. Each diamine was prepared as a 5% ethanol solution and measured with an injection volume of 1 μL. The injection temperature was 290 ° C., the detector temperature was 310 ° C., the column temperature was held at 40 ° C. for 4 minutes, the temperature was raised from 40 ° C. to 300 ° C. at 10 ° C./min, and then held at 300 ° C. for measurement. As the carrier gas, He was used at a flow rate of 10 ml / min. Furthermore, FID was used as a detector.
The total peak area of the obtained chromatogram is defined as 100%, the peak area fraction (%) of the chromatogram of the main component 1,10-decanediamine, and the peak area of impurities (specified by mass spectral analysis below) The fraction (%) was calculated.

(2) Mass spectrum analysis A mass spectrometry system in which a GC-mate II type manufactured by JEOL Ltd. was connected to the gas chromatograph was used. Measurement conditions are the same as in gas chromatographic analysis. For each peak, the impurity of the molecular ion peak (M ⁺ ) 167 ionized by the chemical ionization method (CI) was specified.

(3) Hue evaluation (Hazen color number; APHA)
Each diamine was prepared as a 5% ethanol solution, and the Hazen color number (APHA) was evaluated using a color meter ZE6000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the Hazen color number, the clearer the color is, and the larger the number, the lighter the color.

(4) Relative viscosity (ηr) measurement ηr was measured at 25 ° C. using an Ostwald viscometer using a 96 mass% sulfuric acid solution (concentration: 1.0 g / dl) of polyoxamide resin.

(5) Heat resistance evaluation test About 10 g of the pellets of the obtained polyoxamide resin were placed in an aluminum tray and left in a hot air oven at 150 ° C. The product was taken out after 48 hours and 72 hours, and the relative viscosity (ηr) was measured. Compared with the relative viscosity before processing in a hot air oven, it was used as an index of heat resistance.

(6) Yellowness (YI) Evaluation Based on JIS K 7373, the yellowness (YI) of the pellets of the obtained polyoxamide resin was evaluated using a color meter ZE6000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the yellowness number, the more white it is, and the larger the number, the more yellow it is to brown.

The amine component (C10D-1 to 5) containing 1,10-decanediamine shown below was prepared. The peak area fraction (%) of the main component (1,10-decanediamine) calculated by gas chromatographic analysis (GC) for the prepared amine component, the peak area fraction (%) of impurities (M ⁺ = 167), And the Hazen color number (APHA) when it was set as the 5 mass% ethanol solution was measured by said method. The results are shown in Table 1. In addition, below the detection limit in a table | surface means that a peak area fraction is less than 0.002%.

[Example 1]
(I) Pre-polycondensation step: A raw material feed pump was directly connected by a stirrer, a thermometer, a torque meter, a pressure gauge, a nitrogen gas inlet, a pressure outlet, a polymer outlet, and a pipe made of SUS316 having a diameter of 1/8 inch. Plant-derived 1,10-decanediamine (C10D-1) 875.8 g (5.086 mol) was charged into a 5 L pressure vessel equipped with a raw material inlet, and the inside of the pressure vessel was nitrogen with a purity of 99.9999%. After pressurizing to 3.0 MPa with gas, the operation of releasing nitrogen gas to normal pressure was repeated 5 times, and then the system was heated under a sealing pressure. After the internal temperature was set to 190 ° C. over 20 minutes, 1029.9 g (5.095 mol) of dibutyl oxalate was injected into the reaction vessel at a flow rate of 65 ml / min for about 17 minutes by a raw material feed pump. The internal pressure in the pressure vessel immediately after injection of the total amount increased to 0.50 MPa by 1-butanol generated by the polycondensation reaction, and the internal temperature increased to 197 ° C.

(Ii) Post-polycondensation step: Distillation of butanol produced immediately after injection was started, and the internal temperature was kept at 250 ° C. over 3 hours while maintaining the internal pressure at 0.50 MPa. Immediately after the internal temperature reached 250 ° C., 1-butanol produced by the polycondensation reaction was extracted from the pressure release port over 20 minutes. After releasing the pressure, heating was started under a nitrogen stream of 260 ml / min, the internal temperature was set to 270 ° C. over 1 hour, and the reaction was performed at 270 ° C. for 1 hour. Thereafter, the stirring was stopped, the inside of the system was pressurized to 3 MPa with nitrogen and allowed to stand for 10 minutes, and then released to an internal pressure of 0.1 MPa, 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 obtained polymer (polyoxamide resin) was a tough polymer with excellent color tone.

[Example 2]
(I) Prepolycondensation step: 875.7 g (5.085 mol) of plant-derived 1,10-decanediamine (C10D-1) is charged, and 1027.8 g (5.085 mol) of dibutyl oxalate is a raw material feed pump. Was operated in the same manner as in Example 1 except that it was injected into the reaction vessel. By 1-butanol produced | generated by the polycondensation reaction, it rose to 0.75 Mpa and internal temperature rose to 197 degreeC.

(Ii) Post-polycondensation step: Example 1 except that distillation of butanol generated immediately after injection was started and the internal temperature was kept at 0.50 MPa and the internal temperature was 250 ° C. over 2.5 hours. The string-like polymer was pelletized with a pelletizer.
The obtained polymer (polyoxamide resin) was a tough polymer with excellent color tone.

[Comparative Example 1]
(I) Pre-polycondensation step: 875.0 g (5.081 mol) of plant-derived 1,10-decanediamine (C10D-2) is charged, and 1027.6 g (5.084 mol) of dibutyl oxalate is a raw material feed pump. Was operated in the same manner as in Example 1 except that it was injected into the reaction vessel. By 1-butanol produced | generated by polycondensation reaction, it rose to 0.62 Mpa and internal temperature rose to 198 degreeC.

(Ii) Post-polycondensation step: Example 1 except that distillation of butanol generated immediately after injection was started and the internal temperature was kept at 0.50 MPa and the internal temperature was set to 250 ° C. over 2.0 hours. The string-like polymer was pelletized with a pelletizer.
The obtained polymer (polyoxamide resin) was a brittle and poor-colored polymer.

[Comparative Example 2]
(I) Pre-polycondensation step: 875.0 g (5.081 mol) of plant-derived 1,10-decanediamine (C10D-3) is charged, and 1027.6 g (5.084 mol) of dibutyl oxalate is a raw material feed pump. Was operated in the same manner as in Example 1 except that it was injected into the reaction vessel. By 1-butanol produced | generated by polycondensation reaction, it rose to 0.62 Mpa and internal temperature rose to 198 degreeC.

(Ii) Post-polycondensation step: Example 1 except that distillation of butanol generated immediately after injection was started and the internal temperature was kept at 0.50 MPa and the internal temperature was set to 250 ° C. over 2.0 hours. The string-like polymer was pelletized with a pelletizer.
The obtained polymer (polyoxamide resin) was a tough but poor-colored polymer.

[Comparative Example 3]
(I) Pre-polycondensation step: 877.1 g (5.093 mol) of plant-derived 1,10-decanediamine (C10D-4) is charged, and 1029.6 g (5.094 mol) of dibutyl oxalate is a raw material feed pump. Was operated in the same manner as in Example 1 except that it was injected into the reaction vessel. By 1-butanol produced | generated by the polycondensation reaction, it rose to 0.61 Mpa and internal temperature rose to 198 degreeC.

(Ii) Post-polycondensation step: Example 1 except that distillation of butanol generated immediately after injection was started and the internal temperature was kept at 0.50 MPa and the internal temperature was set to 250 ° C. over 2.0 hours. The string-like polymer was pelletized with a pelletizer.
The obtained polymer (polyoxamide resin) was a tough but poor-colored polymer.

[Comparative Example 4]
(I) Pre-polycondensation step: 825.9 g (4.796 mol) of plant-derived 1,10-decanediamine (C10D-5) is charged, and 969.4 g (4.796 mol) of dibutyl oxalate is a raw material feed pump. Was operated in the same manner as in Example 1 except that it was injected into the reaction vessel. By 1-butanol produced | generated by polycondensation reaction, it rose to 0.60 Mpa and internal temperature rose to 198 degreeC.

(Ii) Post-polycondensation step: Example 1 except that distillation of butanol generated immediately after injection was started and the internal temperature was kept at 0.50 MPa and the internal temperature was set to 250 ° C. over 2.0 hours. The string-like polymer was pelletized with a pelletizer.
The obtained polymer (polyoxamide resin) was a tough but poor-colored polymer.

About each polyoxamide resin obtained in Example 1, Example 2, and Comparative Examples 1 to 4, the yellowness (YI) of the pellet, the relative viscosity before heat treatment (ηr ⁰ ), and in a hot air oven at 150 ° C. Table 2 shows the relative viscosities (ηr ⁴⁸ and ηr ⁷² ) after standing for 48 hours or 72 hours and heat treatment. Furthermore, the rate of decrease (%) in relative viscosity after heat treatment is also shown. The reduction rate (%) of the relative viscosity was calculated by the method described above.

  From Table 2, it can be seen that the polyoxamide resin of the present invention is excellent in heat resistance since the decrease rate of the relative viscosity is small. Moreover, it turns out that the polyoxamide resin of this invention is excellent in a color tone from yellowness being small.

  The polyoxamide resin of the present invention is a polyoxamide resin excellent in heat resistance and color tone, and provides a heat-resistant component. Moreover, it can use suitably as molding materials, such as industrial material, industrial material, and household goods. For example, various injection-molded products, sheets, films, pipes, tubes, monofilaments, fibers, etc., automobile members, optical equipment members, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, households It can be used as heat-resistant parts for applications such as goods.

Claims (6)

In the chromatogram by gas chromatographic analysis, it corresponds to an impurity having a peak area fraction corresponding to 1,10-decanediamine of 98.90% or more and a molecular ion peak (M ⁺ ) in the mass spectrum of 167. A structural unit derived from an amine component having a peak area fraction of less than 0.007%;
And a structural unit derived from oxalic acid.   The relative viscosity (ηr) measured at 25 ° C. using a polyoxamide resin solution having a concentration of 1.0 g / dl in 96% sulfuric acid is 2.2 to 3.5. The polyoxamide resin described in 1.   A heat-resistant component comprising the polyoxamide resin according to claim 1.   The heat-resistant component according to claim 3, wherein the heat-resistant component has any shape selected from the group consisting of a sheet, a film, a pipe, a tube, a monofilament, a fiber, and a container.   It is used in any one selected from the group consisting of automobile members, computers and computer-related equipment, optical equipment members, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, and household goods. The heat resistant component according to claim 3 or claim 4. In the chromatogram by gas chromatographic analysis, it corresponds to an impurity having a peak area fraction corresponding to 1,10-decanediamine of 98.90% or more and a molecular ion peak (M ⁺ ) in the mass spectrum of 167. Providing an amine component having a peak area fraction of less than 0.007%;
Condensing the prepared amine component with at least one acid component selected from the group consisting of oxalic acid and its derivatives;
A process for producing a polyoxamide resin comprising: