JP2015007223A - Polyamide resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyamide resin capable of sufficiently securing all of heat resistance estimated from melting point Tm, melt moldability estimated from the temperature difference (Tm-Tc), dimensional stability at a high temperature, estimated from the glass-transition temperature (Tg), low water absorption and ethanol barrier properties.SOLUTION: Th polyamide resin includes a unit derived from a dicarboxylic acid and a unit derived from a diamine. The dicarboxylic acid contains an oxalic acid compound (compound A) and the diamine contains an amine (compound B) having a structure represented by formula (1) mentioned below. In the formula (1), Rand Rare the same or different and each represent a divalent single bond or a divalent linking group including a hydrocarbon chain.

Description

  The present invention relates to a novel polyamide resin.

  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. Of course, it is also used for parts that are easily exposed to high temperatures, such as around automobile engines.

WO2008 / 072754 WO2008 / 123534 WO2011-136263

  When crystalline polyamide is used in parts that are easily exposed to high temperatures such as around automobile engines, dimensional stability at high temperatures is more demanded.

The problem to be solved by the present invention is to provide a polyamide resin excellent in dimensional stability at a high temperature estimated from the peak of E ″ (glass transition temperature Tg) of solid viscoelasticity measurement.
In addition, biofuels have been used in recent years from the viewpoint of suppressing carbon dioxide emissions, and in order to prevent the ethanol contained therein from escaping to the outside air, it is more desirable to provide a polyamide resin having excellent ethanol barrier properties. preferable.

The present invention is a polyamide resin comprising a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid includes oxalic acid compound A (hereinafter also referred to as “compound A”),
The diamine is a polyamide resin containing diamine B having a structure of the following formula (1) (hereinafter also referred to as “compound B”).

  According to the present invention, (b) excellent heat resistance estimated from melting point Tm, (b) excellent melt formability estimated from temperature difference (Tm-Tc), and (c) glass transition temperature (Tg). It is possible to provide a polyamide resin excellent in dimensional stability at a high temperature estimated from (ii) low water absorption and (e) ethanol barrier properties.

The polyamide resin of the present invention is
A polyamide resin comprising a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid compound A (compound A);
The diamine is a polyamide resin containing diamine B (compound B) having the structure of the above formula (1),
Preferably, a polyamide resin containing a diamine other than the compound B (hereinafter also referred to as “compound C”),
Preferably, the compound B is a polyamide resin which is 1,3-bisaminomethylcyclohexane,
Preferably, it is a polyamide resin containing 50 mol% or more of the unit derived from the compound B with respect to all units derived from the diamine,
Preferably, a polyamide resin having a glass transition temperature of 104 ° C. or higher,
Preferably, it is a polyamide resin in which the temperature difference between the melting point and the crystallization temperature is 34 ° C. or higher, preferably a polyamide resin in which the molar ratio of the compound B to the compound C is 100: 0 to 60:40,
A polyamide resin having a molar ratio of the compound B to the compound C of 90:10 to 60:40 is preferable.

  Below, the detail of the polyamide resin of this invention is demonstrated.

(1) Compounds A, B and C
Compound A used as a raw material for the polyamide resin of the present invention is a compound that provides a unit derived from oxalic acid to the polyamide resin, and is a compound derived from oxalic acid such as oxalic acid and / or oxalic acid diester. Compound A may be any compound having reactivity with an amino group. In the case of producing a polyamide at a high polymerization temperature, if oxalic acid itself is used as a raw material, oxalic acid may be thermally decomposed. Therefore, Compound A in the case of producing at a high polymerization temperature was derived from oxalic acid. 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.

Examples of oxalic acid diesters of aliphatic monohydric alcohols include dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) butyl oxalate, An oxalic acid diester of an aliphatic monohydric alcohol having 3 or more carbon atoms is preferable, di-n-butyl oxalate, di-butyl oxalate and / or di-t-butyl oxalate is more preferable, and di-n-butyl oxalate is still more preferable. The two alcohol residues in the succinic acid diester may be the same or different.
Examples of oxalic acid diesters of alicyclic alcohols include dicyclohexyl oxalate.
Examples of oxalic 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. n-Butyl, di-i-butyl oxalate and / or di-t-butyl oxalate are more preferred, and di-n-butyl oxalate is more preferred.

  These compounds A may be used alone or in combination of two or more at the time of producing the polyamide resin.

Examples of raw materials other than Compound A include dicarboxylic acids other than Compound A, diamines, lactams, aminocarboxylic acids, and the like.
Examples of dicarboxylic acids other than oxalic acid compounds include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, aromatic dicarboxylic acids, and compounds derived therefrom.
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.
Dicarboxylic acids other than these compounds A can be used alone or in combination of two or more, and can be added 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 acids other than Compound A.

  Compound A is preferably 50 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more, from the viewpoint of water absorption of the resulting polymer in all dicarboxylic acids used in the polyamide resin. More preferably, it is 95 mol% or more, more preferably 99 mol% or more. When the ratio of compound A is large, the water absorption tends to be low.

  Compound A is preferably 10 mol% or more, more preferably 30 mol% or more, and even more preferably 49 mol%, from the viewpoint of water absorption of the obtained polymer in all raw materials used for the polyamide resin. That's it.

As the diamine component, a diamine (compound B) having the structure of the above formula (1) is used. R ₁ and R _{2 in} formula (1) are, for example, preferably a divalent single bond or a hydrocarbon chain having 1 to 3 carbon atoms, and a hydrocarbon chain having 1 to 2 carbon atoms. More preferably. The carbon number of the hydrocarbon chain in R ₁ and R ₂ may be the same or different. From the viewpoint of increasing the molecular weight and increasing the melting point, bisaminomethylcyclohexane in which R ₁ and R ₂ in the formula (1) are both methylene groups is preferable. Among bisaminomethylcyclohexane, 1,3-bisaminomethylcyclohexane and 1,4-bisaminomethylcyclohexane are more preferable, and 1,3-bisaminomethylcyclohexane is more preferable.

  The polyamide resin of the present invention may contain a diamine other than Compound B (Compound C) as a diamine component. Examples of the diamine of Compound C include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexamethylenediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8- Octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl -1,6-hexanediamine, aliphatic diamines such as 5-methyl-1,9-nonanediamine, cyclohexanediamine, alicyclic diamines such as methylcyclohexanediamine, isophoronediamine, p-phenylenediamine, m-phenylenediamine, p -Xylenediamine, m-xylenediamine, 4,4'-diamy Diphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-aromatic diamines diaminodiphenyl ether, etc., and the like, these alone, or in two or more may be added during manufacturing. As the diamine of Compound C, an aliphatic diamine is preferable, and a linear or branched aliphatic diamine having 4 to 12 carbon atoms is more preferable.

  Among these, 1,6-hexamethylenediamine, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1,10 from the viewpoints of increasing the molecular weight of the polyamide resin and supply stability of the raw material -At least 1 sort (s) chosen from the group which consists of decanediamine is preferable, and 1,6-hexamethylenediamine is more preferable from the balance of melting | fusing point of the polymer obtained, water absorption, and ethanol barrier property.

  Examples of the lactam described above include ε-caprolactam, ω-enantolactam, ω-laurolactam, α-pyrrolidone, α-piperidone and the like. These can use 1 type (s) or 2 or more types. Among these, ε-caprolactam and / or ω-laurolactam are preferable.

  Examples of aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. These can use 1 type (s) or 2 or more types. Among these, 6-aminocaproic acid, 11-aminoundecanoic acid and / or 12-aminododecanoic acid are preferable.

  The polyamide resin used in the present invention can be produced using any method known as a method for producing polyamide. From the viewpoint of increasing the molecular weight and productivity, the raw material is preferably produced by a polycondensation reaction in a batch or continuous manner. More preferably, the raw material is produced by a two-stage polymerization method comprising a pre-polycondensation step and a post-polycondensation step or a pressure polymerization method described in WO2008-072754.

  In order to obtain a polyamide having excellent melt moldability, heat resistance, dimensional stability at high temperature, low water absorption, and ethanol barrier properties, the molar ratio of Compound B to Compound C is a molar ratio of Compound B: Expressed as Compound C, it is preferably 100: 0 to 50:50, more preferably 97: 3 to 50:50, still more preferably 95: 5 to 55:45, 90:10 More preferably, it is -55: 45, and it is still more preferable that it is 85: 15-60: 40. Hereinafter, the molar ratio of compound B to compound C also means the molar ratio of the unit derived from compound B to the unit derived from compound C in the polyamide resin.

(2) Thermal characteristics and low water absorption of polyamide resin The polyamide resin of the present invention further has a melting point Tm, compound A, 1,9-nonanediamine and 2 by changing the polycondensation ratio of compounds B and C. -Polyamide resin obtained by polycondensation with methyl-1,8-octanediamine (hereinafter also referred to as Comparative polyamide resin 1), Compound A, hexamethylenediamine, 1,9-nonanediamine and 2-methyl- It can be made higher than a polyamide resin obtained by polycondensation with 1,8-octanediamine (hereinafter also referred to as comparative polyamide resin 2). Further, the polyamide resin of the present invention changes the polycondensation ratio of the compounds B and C to change the melting point Tm, the compound A, 1,6-hexanediamine and 2-methyl-1,5-pentanediamine. It can be made equal to or higher than the polyamide resin obtained by polycondensation (hereinafter also referred to as comparative polyamide resin 3).

  Further, the polyamide resin of the present invention can be obtained by changing the polycondensation ratio of the compounds B and C to obtain the temperature difference between the melting point Tm and the crystallization temperature Tc (Tm−Tc), the comparative polyamide resins 1, 2 and It can be made larger than 3. Further, the glass transition temperature (Tg) can be made higher than those of the comparative polyamide resins 1, 2 and 3. Furthermore, the saturated water absorption can be increased as compared with the comparative polyamide resins 1 and 2, and can be decreased as compared with the comparative polyamide resin 3. Furthermore, the ethanol permeability coefficient can be made smaller than those of the comparative polyamide resins 1 to 3.

  That is, the polyamide resin of the present invention is estimated from (i) the heat resistance estimated from the melting point Tm, and (b) the temperature difference (Tm−Tc) between the melting point Tm and the crystallization temperature Tc, as compared with the conventional polyoxamide resin. It is possible to sufficiently ensure all of melt formability, (c) dimensional stability at high temperatures estimated from the glass transition temperature (Tg), (d) low water absorption, and (e) ethanol barrier properties.

In the polyamide resin of the present invention, Tm is preferably 250 to 318 ° C., from the viewpoint of sufficiently ensuring all of heat resistance, melt moldability, dimensional stability at high temperature, low water absorption, and ethanol barrier properties. More preferably, it is 260-300 degreeC. Tc is preferably 210 to 271 ° C, more preferably 215 to 260 ° C. The temperature difference (Tm−Tc) is preferably 34 to 47 ° C., more preferably 35 to 47 ° C. Tg is preferably 120 to 138 ° C, more preferably 122 to 135 ° C. The saturated water absorption is preferably 1.7 to 2.2. Ethanol permeability coefficient is preferably ^{0.001~0.02g · mm · m -2 · d} -1 · atm -1, particularly ^-1 preferably 0.003~0.018g ^· mm · ^m -2 · ^d atm ⁻¹

  The outline of the measuring method of the melting point Tm and the crystallization temperature Tc is as described above, and the details thereof and the detailed measuring methods of the glass transition temperature Tg, the saturated water absorption rate and the ethanol permeability coefficient are described in Examples described later. Will be described in the next section.

  Tc is also preferably within the above range from the viewpoint of securing the melt moldability by appropriately setting the solidification rate. The temperature difference (Tm−Tc) is preferably in the above range from the viewpoint of suppressing the crystallization rate to an appropriate level and ensuring the physical properties of the molded product.

(3) Manufacture of polyamide resin The polyamide resin of the present invention can be manufactured using any method known as a method of manufacturing polyamide. From the viewpoint of high molecular weight and productivity, preferably, Diamine and oxalic acid diester can be obtained by subjecting polycondensation reaction in a batch or continuous manner.
Specifically, it is more preferable to carry out in the order of (i) pre-polycondensation step and (ii) post-polycondensation step as shown by the following operations.

(I) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then diamine (compound B or compounds B and C) and compound A are mixed. When mixing, a solvent in which both the diamine and the compound A are soluble may be used. As a solvent in which both the diamine component and compound A are soluble, for example, toluene, xylene, trichlorobenzene, phenol, trifluoroethanol and the like can be used. In particular, toluene can be preferably used. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid source components, such as a oxalic acid diester, are added with respect to this.
At this time, the charging ratio of the compound A and the diamine is preferably 0.8 to 1.5 (molar ratio), preferably 0.91 to 1.1 (molar ratio), from the viewpoint of increasing the molecular weight. Ratio) is more preferable, and 0.99 to 1.01 (molar ratio) is more preferable.

  The temperature in the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The reaction temperature is preferably controlled so that the final temperature reaches 80 to 150 ° C, particularly 100 to 140 ° C. The reaction time at the final temperature reached is preferably 3 to 6 hours.

(Ii) Post-polycondensation step: In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. In the temperature raising process, the final reached temperature of the pre-polycondensation step, that is, preferably from 80 to 150 ° C, is finally preferably 265 ° C to 350 ° C, more preferably 265 ° C to 345 ° C, and further preferably 270 ° C. The temperature is made 340 ° C. or lower, more preferably 270 ° C. or higher and 335 ° C. or lower. It is preferable to carry out the reaction while keeping the temperature rising time preferably 1 to 8 hours, more preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. The preferable final ultimate pressure in the case of performing the vacuum polymerization is less than 0.1 MPa to 13.3 Pa.

(4) Component that can be used as dicarboxylic acid in polyamide resin In the polyamide resin of the present invention, other dicarboxylic acid components other than Compound A can be used within a range not impairing the effects of the present invention.
As other dicarboxylic acid components other than Compound A (oxalic acid), for example, aliphatic dicarboxylic acid, alicyclic dicarboxylic acid, aromatic dicarboxylic acid, etc. are used alone or in any mixture thereof and added during the polycondensation reaction. can do.
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, etc. Is mentioned.
In addition to the other dicarboxylic acid components described above, polyvalent carboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can also be used as long as melt molding is possible.

  When other dicarboxylic acid components are used, the proportion thereof is preferably 25 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, and more preferably 5 mol% or less, relative to Compound A (oxalic acid). Is even more preferable, and 0 mol% (that is, the dicarboxylic acid component consists only of Compound A) is particularly preferable. The molar ratio of the other dicarboxylic acid component to the compound A (oxalic acid) also means the molar ratio of the unit derived from the compound A and the unit derived from the other dicarboxylic acid component in the polyamide resin.

In the polyamide resin of the present invention, other diamine components other than the compounds B and C can be used as long as the effects of the present invention are not impaired.
As other diamine components, aliphatic diamines, alicyclic diamines, aromatic diamines and the like can be added alone or in an arbitrary mixture thereof during the polycondensation reaction.
Aliphatic diamines include ethylenediamine, propylenediamine, 1,4-butanediamine, 1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2-methyl-1,5-pentanediamine, and 3-methyl. -1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, etc. It is done.
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 Etc.

  When other diamine components are used, the proportion is preferably 25 mol% or less, more preferably 15 mol% or less, still more preferably 10 mol% or less, and even more preferably 5 mol% or less with respect to compounds B and C. Even more preferred is 0 mol% (ie, the diamine component consists solely of compounds B and C). In addition, the molar ratio of the other diamine component with respect to the compounds B and C also means the molar ratio of the unit derived from the compound B and C and the unit derived from another diamine component in the polyamide resin.

  The polyamide resin of the present invention can be mixed with other polyoxamides, polyamides such as aromatic polyamides, aliphatic polyamides, and alicyclic polyamides within a range that does not impair the effects of the present invention.

  The polyamide resin of the present invention can be further blended with thermoplastic polymers other than polyamide, elastomers, fillers, reinforcing fibers, and various additives.

  Furthermore, the polyamide resin 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 crystallization accelerator, glass, if necessary. Fibers, plasticizers, lubricants and the like can be added during or after the polycondensation reaction.

(6) Polyamide resin molding The polyamide resin molding method of the present invention can be any known molding processing method applicable to polyamide, such as injection, extrusion, hollow, press, roll, foaming, vacuum / compression, stretching. is there. By these molding methods, the polyamide resin of the present invention can be processed into films, sheets, molded articles, fibers and the like.

(7) Use of polyamide molded product The molded product obtained from the polyamide resin of the present invention is an automobile member as various molded products, sheets, films, pipes, tubes, monofilaments, fibers, containers, etc. for which polyamide molded products have been conventionally used. , Computers and related equipment, optical equipment members, electrical / electronic equipment, information / communication equipment, precision equipment, civil engineering / building supplies, medical supplies, household goods, etc.

[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. The relative viscosity, number average molecular weight, melting point, crystallization temperature, 1% weight loss temperature, glass transition temperature, saturated water absorption rate and ethanol permeability coefficient in the examples were measured by the following methods.

(1) Relative viscosity ηr
ηr was measured at 25 ° C. using an Ostwald viscometer using a sulfuric acid solution (sulfuric acid concentration: 96% by weight) having a polyamide concentration of 1.0 g / dl.

(2) Number average molecular weight (Mn)
The number average molecular weight (Mn) is based on the signal intensity obtained from the ¹ H-NMR spectrum, for example, dibutyl oxalate as the oxalic acid source, 1,3-bisaminomethylcyclohexane (compound B) and 1,6 as the diamine component. -In the case of a polyamide produced by using hexanediamine (compound C) at a molar ratio of 90:10 [hereinafter abbreviated as PA-BAC / 6 (compound B / compound C = 90/10)], Calculated.
Mn = np × 193.65 + n (NH ₂ ) × 138.63 + n (OBu) × 129.13 + n (NHCHO) × 29.14

In addition, the measurement conditions of ¹ H-NMR are as follows.
・ Model used: Bruker Biospin AVANCE500
・ Solvent: Bisulfuric acid ・ Accumulated times: 1024 times

Moreover, each term in the said formula is prescribed | regulated as follows.
Np = Np / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
N (NH ₂ ) = N (NH ₂ ) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
N (NHCHO) = N (NHCHO) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
N (OBu) = N (OBu) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
Np = Sp / sp-N (NHCHO)
N (NH ₂ ) = S (NH ₂ ) / s (NH ₂ )
N (NHCHO) = S (NHCHO) / s (NHCHO)
N (OBu) = S (OBu) / s (OBu)

However, each term has the following meaning.
Np: Total number of repeating units in the molecular chain excluding terminal units of PA-BAC / 6 (compound B / compound C = 90/10).
Np: the number of repeating units in the molecular chain per molecule.
Sp: Signal based on proton of methylene group adjacent to oxamide group in repeating unit in molecular chain excluding terminal of PA-BAC / 6 (compound B / compound C = 90/10) (around 3.1 ppm) ) Integral value.
Sp: The number of hydrogens (4) counted in the integral value Sp.
· _N (NH 2): The total number of terminal amino groups of the PA-BAC / 6 (Compound B / Compound C = 90/10).
N (NH ₂ ): number of terminal amino groups per molecule.
· _S (NH 2): integrated value of the PA-BAC / 6 signals based on (Compound B / Compound C = 90/10) protons of the methylene group adjacent to the terminal amino group of (around 2.6 ppm).
S (NH ₂ ): The number of hydrogens (2) counted in the integrated value S (NH ₂ ).
N (NHCHO): total number of terminal formamide groups of PA-BAC / 6 (compound B / compound C = 90/10).
N (NHCHO): number of terminal formamide groups per molecule.
-S (NHCHO): The integrated value of the signal (7.8 ppm) based on the proton of the formamide group of PA-BAC / 6 (compound B / compound C = 90/10).
S (NHCHO): The number of hydrogens (one) counted in the integral value S (NHCHO).
N (OBu): total number of terminal butoxy groups of PA-BAC / 6 (compound B / compound C = 90/10).
N (OBu): number of terminal butoxy groups per molecule.
S (OBu): integral value of a signal (around 4.1 ppm) based on the proton of the methylene group adjacent to the oxygen atom of the terminal butoxy group of PA-BAC / 6 (compound B / compound C = 90/10).
S (OBu): The number of hydrogens (two) counted in the integral value S (OBu).

(3) Melting point Tm and crystallization temperature Tc
Tm and Tc were measured in a nitrogen atmosphere using a PYRIS Diamond DSC manufactured by PerkinELmer.
Tm and Tc were measured by the following procedure.
The temperature is raised from 30 ° C. to 330 ° C. at a rate of 10 ° C./min (referred to as a temperature rise first run).
After holding at 340 ° C. for 3 minutes, the temperature is decreased to 30 ° C. at a rate of 10 ° C./min (referred to as a temperature decrease first run)
Next, the temperature is raised to 330 ° C. at a rate of 10 ° C./min (referred to as a temperature rising second run).
From the obtained DSC chart, the exothermic peak temperature of the temperature-decreasing first run was Tc, and the endothermic peak temperature of the temperature-rising second run was Tm.

(4) Glass transition temperature Tg
Tg is T.W. The measurement was performed using a solid viscoelasticity analyzer RSAIII manufactured by A Instruments Inc. Measurement of solid viscoelasticity is dynamic measurement in tensile mode, temperature scan is 2 ° C / step, holding time is 30 seconds, frequency is 1.0Hz, strain is automatically set to 0.2 to 2%, temperature range is -110 ° C, measurement limit Until, it carried out on the conditions under nitrogen stream. The peak temperature of the loss elastic modulus E ″ was defined as the glass transition temperature Tg.

(5) Film formation Film formation was performed using a vacuum press TMB-10 manufactured by Toho Machinery Co., Ltd. A polyamide resin was heated and melted at 330 ° C. for 5 minutes in a reduced pressure atmosphere of 500 to 700 Pa, pressed at 5 MPa for 1 minute, and then formed into a film. Then, the reduced pressure atmosphere was returned to normal pressure, and then cooled at room temperature of 5 MPa for 1 minute. Crystallization gave a film.

(6) Saturated water absorption rate A film (dimensions: 20 mm × 10 mm, thickness 0.25 mm; weight about 0.05 g) obtained by molding a polyamide resin under the conditions of (5) is immersed in ion-exchanged water at 23 ° C. The film was taken out every hour and the weight of the film was measured. When the rate of increase in the film weight lasts three times in the range of 0.2%, it is determined that the absorption of water into the polyamide resin film has reached saturation, and the film weight (Xg) before dipping in water The saturated water absorption (%) was calculated from the weight (Yg) of the film when saturation was reached by the following formula.

(7) Ethanol permeability coefficient GTR Tech's differential pressure gas / vapor / liquid permeability measuring device (GTR) for the film (dimensions: diameter 60 mm, thickness: 0.13 mm) molded under the conditions of (5) above. -30XAUB), the film and ethanol vapor were brought into contact at 60 ° C., the amount of ethanol that permeated through the film was measured, and the ethanol permeability coefficient at the point where the amount of permeated ethanol reached a steady state was determined. The smaller the ethanol permeability coefficient, the higher the ethanol barrier property.

[Example 1]
(I) Pre-polycondensation step: The inside of a separable flask having a stirrer, a reflux condenser, a nitrogen inlet tube, and a raw material inlet and having an internal volume of 1 L was replaced with nitrogen gas having a purity of 99.9999%. . Subsequently, 500 ml of dehydrated toluene and 71.8738 g (0.0152 mol) of 1,3-bisaminomethylcyclohexane were charged into this separable flask. This separable flask was placed in an oil bath and heated to 50 ° C., and then 102.1195 g (0.5053 mol) of dibutyl oxalate was charged. Next, the temperature of the oil bath was raised to 130 ° C., and the reaction was carried out for 5 hours under reflux. 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 prepolymer obtained by the above operation was 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 was 13.3 Pa or less. The operation of keeping under reduced pressure and then introducing nitrogen gas to normal pressure was repeated 5 times. Then, it moved to the salt bath kept at 210 degreeC under 50 ml / min nitrogen stream, and temperature rising was started immediately. After the temperature of the salt bath was raised to 330 ° C. over 1 hour, the inside of the container was depressurized to about 66.5 Pa and further reacted for 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 obtained polyamide was a white tough polymer.

[Example 2]
In the prepolymerization step, a separable flask having a volume of 500 ml was used, 200 ml of dehydrated toluene, 19.171 g (0.1344 mol) of 1,3-bisaminomethylcyclohexane, 1.7314 g (0.1.34 g) of 1,6-hexanediamine. 0149 mol) and 30.1957 g (0.1493 mol) of dibutyl oxalate were added, and the reaction was carried out in the same manner as in Example 1 except that the temperature of the salt bath after the temperature increase in the post-polymerization step was 315 ° C. Obtained. The obtained polyamide was a white tough polymer. The film molded from this polyamide was a colorless tough film.

[Example 3]
(I) Pre-polycondensation step: The inside of a separable flask having a stirrer, an air cooling tube, a nitrogen inlet tube, and a raw material inlet and having an internal volume of 5 liters is replaced with nitrogen gas having a purity of 99.9999%. , 1211 g (5.9876 mol) of dibutyl oxalate was charged. While maintaining this container at 20 ° C., 596.2 g (4.1913 mol) of 1,3-bisaminomethylcyclohexane and 208.7 g (1.7963 mol) of 1,6-hexanediamine were added with stirring, and polycondensation was performed. Reaction was performed. Note that all operations from preparation of raw materials to completion of the reaction were performed under a nitrogen stream of 200 ml / min.

(Ii) Post-polycondensation step: The prepolymer obtained by the above operation was charged into a 5 L pressure vessel equipped with a stirrer, thermometer, torque meter, pressure gauge, nitrogen gas inlet and polymer outlet. The operation of keeping the inside of the pressure vessel under a pressure of 3.0 MPa or more and then releasing the nitrogen gas to normal pressure was repeated 5 times, and then the system was heated up under a nitrogen stream and normal pressure. The internal temperature was raised to 120 ° C. over 1.5 hours. At this time, butanol was confirmed to be distilled. While distilling butanol, the temperature was raised to 290 ° C. over 5 hours and allowed to react for 2 hours. Thereafter, the temperature in the system was lowered to 285 ° C., stirring was stopped, and the mixture was allowed to stand for 25 minutes. Then, the system was pressurized to 3.5 MPa with nitrogen, 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 was a white tough polymer.

[Example 4]
A separable flask having a volume of 500 ml was used in the prepolymerization step, 200 ml of dehydrated toluene, 12.6565 g (0.0890 mol) of 1,3-bisaminomethylcyclohexane, and 6.8907 g (0. 0593 mol) and 29.985 g (0.1483 mol) of dibutyl oxalate, and the reaction was carried out in the same manner as in Example 1 except that the temperature of the salt bath after the temperature increase in the post-polymerization step was 280 ° C. Got. The obtained polyamide was a white tough polymer. The film formed from this polyamide was a colorless transparent tough film.

[Example 5]
A separable flask having a volume of 500 ml was used in the prepolymerization step, 200 ml of dehydrated toluene, 19.0488 g (0.1339 mol) of 1,3-bisaminomethylcyclohexane, and 2.5674 g (0. 0149 mol) and 30.0861 g (0.1488 mol) of dibutyl oxalate, and the reaction was conducted in the same manner as in Example 1 except that the temperature of the salt bath after the temperature increase in the post-polymerization step was 310 ° C. Got. The obtained polyamide was a white tough polymer. The film molded from this polyamide was a white tough film.

[Example 6]
In the pre-polymerization step, a separable flask having a volume of 500 ml was used, 200 ml of dehydrated toluene, 14.814 g (0.1042 mol) of 1,3-bisaminomethylcyclohexane, and 7.6850 g (0.62 g) of 1,10-decanediamine. 0446 mol) and 30.1029 g (0.1488 mol) of dibutyl oxalate, and the reaction was carried out in the same manner as in Example 1 except that the temperature of the salt bath after the temperature increase in the post-polymerization step was 280 ° C. Got. The obtained polyamide was a white tough polymer. The film formed from this polyamide was a white opaque opaque film.

[Example 7]
In the prepolymerization step, a separable flask having a volume of 500 ml was used, 200 ml of dehydrated toluene, 12.6736 g (0.0891 mol) of 1,3-bisaminomethylcyclohexane, and 10.3522 g (0. 352 g) of 1,10-decanediamine. 0594 mol) and 30.0245 g (0.1485 mol) of dibutyl oxalate, and the reaction was carried out in the same manner as in Example 1 except that the temperature of the salt bath after the temperature increase in the post-polymerization step was 270 ° C. Got. The obtained polyamide was a white tough polymer. The film formed from this polyamide was a white opaque opaque film.

[Comparative Example 1]
In the prepolymerization step, a separable flask having a volume of 300 ml was used, 100 ml of dehydrated toluene, 13.3596 g (0.0844 mol) of 1,9-nonanediamine, and 2-methyl-1,8-octanediamine. The reaction was conducted in the same manner as in Example 1 except that 3584 g (0.0149 mol) and 20.0852 g (0.0993 mol) of dibutyl oxalate were charged and the temperature of the salt bath after the temperature increase in the post-polymerization step was 260 ° C. To obtain a polyamide. The obtained polyamide was a colorless and transparent polymer.

[Comparative Example 2]
Using a separable flask having a volume of 300 ml in the pre-polymerization step, 100 ml of dehydrated toluene, 8.0400 g (0.0508 mol) of 2-methyl-1,8-octanediamine 1.4188 g of 1,9-nonanediamine (0.009 mol), 1,6-hexanediamine 4.6294 g (0.0398 mol), and dibutyl oxalate 20.0.1352 g (0.0996 mol) were charged, and the temperature of the salt bath after the temperature increase in the post-polymerization step A polyamide was obtained by carrying out the reaction in the same manner as in Example 1 except that the temperature was 270 ° C. The obtained polyamide was a white polymer.

[Comparative Example 3]
Using a separable flask having a volume of 300 ml in the prepolymerization step, 100 ml of dehydrated toluene, 6.0656 g (0.0522 mol) of 1,6-hexanediamine, 2-methyl-1,5-pentanediamine 6 0.0652 g (0.0522 mol) and dibutyl oxalate 21.1149 g (0.1044 mol) were added, and the temperature of the salt bath after the temperature increase in the post-polymerization step was 280 ° C., as in Example 1. Reaction was performed to obtain polyamide. The obtained polyamide was a white polymer.

  The diamine composition, the relative viscosity ηr, the melting point Tm, the crystallization temperature Tc, the 1% weight loss temperature Td, the temperature difference (Tm−Tc), and the glass transition temperature of the polyamides obtained in Examples 1-7 and Comparative Examples 1-3. Table 1 shows Tg, saturated water absorption, and ethanol permeability coefficient.

  As is clear from the results shown in Table 1, the polyamide resins of Examples 1 to 7 are compared with the conventional polyoxamide resins (Comparative Examples 1 to 3), (a) heat resistance estimated from the melting point Tm, (b) Estimated from melt formability estimated from temperature difference (Tm-Tc), (c) dimensional stability at high temperature estimated from glass transition temperature (Tg), (d) low water absorption, and (e) ethanol permeability coefficient It can be seen that all of the ethanol barrier properties can be sufficiently secured.

  The polyamide resin of the present invention is a polyoxamide resin excellent in heat resistance, dimensional stability at high temperatures, low water absorption, ethanol barrier properties, etc., and excellent in melt molding processability. Therefore, the polyamide resin of the present invention can be suitably used as a molding material for industrial materials, industrial materials, household goods, and the like. Specifically, various injection molded products, sheets, films, pipes, tubes, monofilaments, fibers, etc., automobile members (particularly members used around the engine), optical equipment members, electrical / electronic equipment, information / communication related equipment, It can be used for a wide range of applications such as precision equipment, civil engineering / building supplies, medical supplies, and household items.

Claims (8)

A polyamide resin comprising a unit derived from a dicarboxylic acid and a unit derived from a diamine,
The dicarboxylic acid comprises oxalic acid compound A;
The polyamide resin in which the diamine contains diamine B having the structure of the following formula (1).

  Furthermore, the polyamide resin of Claim 1 containing diamine C other than the said diamine B.   The polyamide resin according to claim 1 or 2, wherein the diamine B is 1,3-bisaminomethylcyclohexane.   The polyamide resin according to any one of claims 1 to 3, comprising 50 mol% or more of the unit derived from the diamine B with respect to all units derived from the diamine.   Glass transition temperature is 104 degreeC or more, The polyamide resin of any one of Claims 1-4.   The polyamide resin according to any one of claims 1 to 5, wherein a temperature difference between a melting point and a crystallization temperature is 34 ° C or more.   The polyamide resin according to claim 2, wherein a molar ratio of the diamine B to the diamine C is 100: 0 to 60:40.   The polyamide resin according to claim 7, wherein a molar ratio of the diamine B to the diamine C is 90:10 to 60:40.