JP2019137788A - Polyamide compound, and method for producing polyamide compound - Google Patents

Abstract

To provide a novel polyamide compound.SOLUTION: A polyamide compound contains a specific dicarboxylic acid unit (1), a specific dicarboxylic acid unit (2), and a specific diamine unit (3). The polyamide compound has excellent mechanical physical properties and excellent thermal stability, while exhibiting very high transparency.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyamide compound and a method for producing a polyamide compound.

From the viewpoint of global warming prevention and resource risk reduction, polymers using plant-derived compounds as starting materials instead of petroleum polymers have attracted attention (for example, see Non-Patent Documents 1 to 3).
However, polylactic acid as a typical example is a plant-derived compound, but has problems in heat resistance and hydrolysis resistance. Therefore, the application range is limited only with polylactic acid.
Under such circumstances, development of plant-derived high-performance polymers other than polylactic acid is desired.

  Conventionally known polyamide compounds include PA6 polymerized with ε-caprolactam, PA66, PA610, PA1010 polymerized with dicarboxylic acid and diamine, and the like. Moreover, PA11 which is a plant-derived polyamide compound is obtained by polymerization of 11-aminoundecanoic acid.

  However, the application range of conventional polyamide compounds obtained by polymerization of ε-caprolactam, dicarboxylic acid and diamine, and 11-aminoundecane is limited. Therefore, development of a novel polyamide compound has been desired.

S. Chatti, M. Bortolussi, A. Loupy, J. C. Blais, D. Bogdal, M. Majdoub. Eur. Polym. J. 38, 1851 (2002). S. Chatti, H. R. Kricheldorf. G. Schwarz. J. Polym. Sci. Part A: Polym. Chem. 44, 3616 (2006). C. -H. Lee, H. Takagi, H. Okamoto, M. Kato. J. Appl. Polym. Sci. 127, 530 (2013).

  The present invention has been made in view of the above circumstances, and an object thereof is to provide a novel polyamide compound.

In view of the above-described conventional techniques, the present inventors have developed a novel polyamide compound as a result of intensive studies.
And this novel polyamide compound discovered the fact that it has the characteristic different from the conventional polyamide compound. The present invention has been made based on this finding.

That is, the invention described in claim 1
A dicarboxylic acid unit represented by the following general formula (1):
A dicarboxylic acid unit represented by the following general formula (2);
It is a polyamide compound characterized by containing the diamine unit represented by following General formula (3).

(X = 9, y = 11)

(Z represents 6 or 8)

  In the invention according to claim 2, the molar ratio of the dicarboxylic acid unit represented by the general formula (1): the dicarboxylic acid unit represented by the general formula (2) is 90:10 to 10:90. The polyamide compound according to 1.

Invention of Claim 3 is a manufacturing method of the polyamide compound of Claim 1 or 2, Comprising:
An acid chloride capable of constituting a dicarboxylic acid unit represented by the general formula (1);
An acid chloride capable of constituting a dicarboxylic acid unit represented by the general formula (2);
It is made to react with the diamine which can comprise the diamine unit represented by General formula (3).

The polyamide compound of the present invention has characteristics different from those of conventional polyamide compounds. In particular, the polyamide compound of the present invention has high transparency.
According to the method for producing a polyamide compound of the present invention, a polyamide compound having high transparency can be produced.

2 is a photograph showing the transparency of the polyamide compound of Example 4 and Comparative Example 1. FIG.

  The items shown here are exemplary and illustrative of the embodiments of the present invention, and are the most effective and easy-to-understand explanations of the principles and conceptual features of the present invention. It is stated for the purpose of providing what seems to be. In this respect, it is not intended to illustrate the structural details of the present invention beyond what is necessary for a fundamental understanding of the present invention. It will be clear to those skilled in the art how it is actually implemented.

The present invention will be described in detail below.
[1] Polyamide compound The polyamide compound of the present invention is represented by the dicarboxylic acid unit represented by the following general formula (1), the dicarboxylic acid unit represented by the following general formula (2), and the following general formula (3). Containing diamine units.

(X = 9, y = 11)

(Z represents 6 or 8)

  The polyamide compound of the present invention may further contain structural units other than those described above as long as the effects of the present invention are not impaired.

In the polyamide compound of the present invention, the content of the dicarboxylic acid unit is not particularly limited. The content of the dicarboxylic acid unit is usually 5 to 50 mol%, preferably 20 to 50 mol%, more preferably 30 to 50 mol%.
In the polyamide compound of the present invention, the content of the diamine unit is not particularly limited. Content of a diamine unit is 5-50 mol% normally, Preferably it is 20-50 mol%, More preferably, it is 30-50 mol%.
The proportion of the content of the dicarboxylic acid unit and the diamine unit is preferably substantially the same from the viewpoint of the polymerization reaction, and the content of the dicarboxylic acid unit is ± 1 mol% of the content of the diamine unit. More preferred.

[1-1] Dicarboxylic acid unit In the polyamide compound of the present invention, as described above, the dicarboxylic acid unit represented by the following general formula (1) and the dicarboxylic acid unit represented by the following general formula (2): contains.

(X = 9, y = 11)

(Z represents 6 or 8)

  The dicarboxylic acid unit represented by the general formula (1) is derived from a plant and contributes to prevention of global warming and resource risk reduction.

  When the total of the dicarboxylic acid units in the polyamide compound of the present invention is 100 mol%, the total content of the dicarboxylic acid units represented by the above general formulas (1) and (2) is not particularly limited. The dicarboxylic acid units represented by the general formulas (1) and (2) are preferably contained in a total amount of 30 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 70 to 100 mol%. This is because when the content of the dicarboxylic acid units represented by the general formulas (1) and (2) is within this range, transparency, impact resistance and the like are excellent.

In the polyamide compound, the molar ratio between the dicarboxylic acid unit represented by the general formula (1) and the dicarboxylic acid unit represented by the general formula (2) is not particularly limited.
The molar ratio of the dicarboxylic acid unit represented by the general formula (1): the dicarboxylic acid unit represented by the general formula (2) is preferably 90:10 to 10:90, and 80:20 to 20:80. More preferably, it is more preferably 70:30 to 30:70.

The compound which can comprise dicarboxylic acid units other than the dicarboxylic acid units represented by the general formulas (1) and (2) is not particularly limited.
For example, specific examples of dicarboxylic acid compounds include C2-C25 linear aliphatic dicarboxylic acids such as oxalic acid, malonic acid, fumaric acid, maleic acid, or unsaturated fatty acids obtained by fractionation of triglycerides. Aliphatic dicarboxylic acids such as dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acid) and hydrogenated products thereof (hydrogenated dimer acid), and alicyclic groups such as 1,4-cyclohexanedicarboxylic acid Examples include dicarboxylic acids and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,3-benzenediacetic acid, and 1,4-benzenediacetic acid. In addition, derivatives of these dicarboxylic acid compounds may be used. Examples of the derivatives include carboxylic acid halides. These can be used alone or in combination of two or more.
When the total of the dicarboxylic acid units in the polyamide compound of the present invention is 100 mol%, the content of dicarboxylic acid units other than the dicarboxylic acid represented by the general formulas (1) and (2) is not particularly limited. The content of dicarboxylic acid units other than the dicarboxylic acid represented by the general formulas (1) and (2) is preferably less than 50 mol%, more preferably less than 20 mol%, and less than 10 mol%. It is particularly preferred. This is because, when the content of dicarboxylic acid units other than the dicarboxylic acid units represented by the general formulas (1) and (2) is within this range, transparency and impact resistance are improved.

[1-2] Diamine Unit The diamine unit in the polyamide compound of the present invention includes at least a diamine unit represented by the general formula (3).

  When the total of the diamine units in the polyamide compound of the present invention is 100 mol%, the content of the diamine units represented by the above general formula (3) is not particularly limited. The diamine unit represented by the general formula (3) is preferably contained in an amount of 5 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 80 to 100 mol%. It is because transparency, impact resistance, etc. will be excellent when content of the diamine acid unit represented by General formula (3) is made into this range.

The repeating unit that may be contained in the polyamide compound includes a combination of the following dicarboxylic acid unit and diamine unit.
[A] A combination of a dicarboxylic acid unit represented by the general formula (1) and a diamine unit represented by the general formula (3).
[B] A combination of a dicarboxylic acid unit represented by the general formula (2) and a diamine unit represented by the general formula (3).
Different types of repeating units may be present in the polyamide compound randomly.
Further, the same type of repeating units may be present in the polyamide compound in the form of blocks.

The compound which can comprise diamine units other than the diamine unit represented by General formula (3) is not specifically limited.
Examples of diamines other than the diamine unit represented by the general formula (3) include known aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like.

Examples of the aliphatic diamine that can constitute a diamine unit other than the diamine unit represented by the general formula (3) include 1,1-metaxylylenediamine, 1,3-propanediamine, and pentamethylenediamine. .
Examples of the alicyclic diamine include 4,4′-methylenebis (cyclohexylamine) and 1,3-bis (aminomethyl) cyclohexane.
Examples of the aromatic diamine include o-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4 ′. -Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diaminofluorene, 4,4'-diamino-2,2'-dimethylbiphenyl, 9,9-bis (4-aminophenyl) fluorene 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benze 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 3,5-diaminobenzoic acid, dodecanoxy-2,4-diaminobenzene Tetradecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diamino Benzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2 , 5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, Cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-amino) Phenoxy) Cholesta 4- (4′-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4′-trifluoromethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4- ( (Aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2,4-dia Nophenyl) piperazine-4-carboxylic acid, 4- (morpholin-4-yl) benzene-1,3-diamine, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, α-amino-ω- Examples thereof include aminophenylalkylene.
These can be used alone or in combination of two or more.

  When the total of the diamine units in the polyamide compound of the present invention is 100 mol%, the content of diamine units other than the diamine represented by the general formula (3) is not particularly limited. The content of the diamine unit other than the diamine represented by the general formula (3) is preferably less than 50 mol%, more preferably less than 30 mol%, and particularly preferably less than 10 mol%. . It is because transparency, impact resistance, etc. will improve if content of diamine units other than the diamine unit represented by General formula (3) is made into this range.

[1-3] Degree of polymerization of polyamide compound The degree of polymerization of the polyamide compound of the present invention is not particularly limited. The viscosity number measured as follows is preferably in the range of 4.0 to 10.0, particularly in the range of 5.0 to 8.0.
The viscosity number is measured as follows.
Test method: Conforms to JIS K6933 Test conditions: Measurement solvent; 96% sulfuric acid Viscometer: Ubbelohde viscometer Solution concentration: 0.005 g / mL
Measurement temperature: 25 ° C

Formula: Viscosity number (mL / g) = (t / t ₀ −1) × 1 / C
t ₀ : Flowing time of measurement solvent (s)
t: Flow time of sample solution (s)
C: Solution concentration (g / mL)

[1-4] Properties of polyamide compound The polyamide compound of the present invention contains a dicarboxylic acid unit represented by the general formula (1). Since this dicarboxylic acid unit has a long chain, it tends to be difficult to align. On the other hand, the dicarboxylic acid unit represented by the general formula (2) also tends to be difficult to align. In the polyamide compound of the present invention, it is considered that transparency is enhanced by combining these dicarboxylic acid units.
Another feature of the polyamide compound of the present invention is high impact resistance.
These characteristics are not found in conventional polyamides obtained by polymerization of ε-caprolactam, dicarboxylic acid and diamine, and 11-aminoundecane.

[2] Method for producing polyamide compound The method for producing the polyamide compound of the present invention is not particularly limited. The polyamide compound of the present invention can be produced, for example, by reacting a dicarboxylic acid compound with a diamine compound.

  As the dicarboxylic acid compound, in addition to dicarboxylic acid, a carboxylic acid derivative in which the hydroxyl group of the carboxyl group of dicarboxylic acid is substituted with another hetero atom (atom other than carbon, hydrogen, or metal) can also be used. Examples of the carboxylic acid derivative include acyl halides (acid halides) in which the hydroxyl group is replaced by halogen.

The polyamide compound of the present invention can be produced by polycondensation of a diamine component that can constitute a diamine unit and a dicarboxylic acid component that can constitute a dicarboxylic acid unit. The degree of polymerization can be controlled by adjusting the polycondensation conditions and the like.
The method for producing the polyamide compound is not particularly limited. As a method for producing a polyamide compound, for example, (1) a method using an acid or base catalyst, (2) a carboxylic acid activation method, (3) a method utilizing transesterification, and (4) a condensing agent are used. And the like is preferably used.

As a suitable production method, for example, a production method in which dicarboxylic acid is activated to form acid chloride, and acid chloride and diamine are reacted to form a polyamide compound is employed. That is, an acid chloride that can constitute the dicarboxylic acid unit represented by the above general formula (1), an acid chloride that can constitute the dicarboxylic acid unit represented by the above general formula (2), and the above general formula A production method of reacting with a diamine capable of constituting the diamine unit represented by (3) is suitably employed.
If the dicarboxylic acid is activated to form acid chloride and then reacted with diamine, a polyamide compound can be efficiently produced.

  Moreover, you may add a monoamine and monocarboxylic acid as a molecular weight modifier at the time of polycondensation. Further, in order to suppress the polycondensation reaction and obtain a desired degree of polymerization, the ratio (molar ratio) between the diamine component and the carboxylic acid component constituting the polyamide compound may be adjusted by shifting from 1.

When polymerization is carried out by a dehydrohalogenation reaction by the reaction of a carboxylic acid dihalide such as the above-mentioned acid chloride and a diamine, the reaction proceeds rapidly, so that the reaction is preferably carried out at a relatively low temperature for reaction rate control.
For example, it is preferably performed in the range of −10 ° C. to 100 ° C.
The reaction solvent is not particularly limited, and known solvents can be widely applied. Examples of the organic polar solvent as the reaction solvent include dimethylacetamide, N-methylpyrrolidone, dimethylsulfone, dimethylformamide, N-methylcaprolactam, tetramethylurea, N, N′-dimethyl-2-imidazolidinone and the like. . These may be used singly or as a mixed solvent of two or more. Further, if necessary, the solubility may be improved by using hydrogen chloride and a metal halide salt such as lithium chloride, calcium chloride, potassium chloride and the like in combination.

The polyamide compound concentration (polymer concentration) is not particularly limited, although it varies depending on the solubility of the produced polyamide compound in the solvent and the solution viscosity. The concentration of the polyamide compound is preferably 0.1 to 40% by mass, for example, from the viewpoint of productivity.
The concentration of the polyamide compound is determined by comprehensively judging the content and composition ratio of the polyamide compound, the solubility, the solution viscosity, the handleability, and the ease of defoaming.

  The method for adding the raw material is not particularly limited. For example, after adding diamine to the reaction solvent and dissolving it at a low temperature, a dicarboxylic acid halide such as acid chloride as one raw material is added. In this case, in order to prevent deterioration of the diamine, it is preferable to carry out under an inert atmosphere (for example, under a nitrogen atmosphere or an argon gas atmosphere). The molar ratio of diamine and acid halide should basically be equimolar, but diamine or acid component as one raw material may be added excessively to control the degree of polymerization, or monofunctional An appropriate amount of an organic substance such as aniline, naphthylamine, acetic acid chloride, or benzoyl chloride may be added.

  In addition, in the case of the polyamide compound of the present invention, in order to improve the characteristics, an addition method intended to block the polymer is adopted, such as reacting a part of diamine or acid chloride and then adding the remaining raw materials. You can do it.

Since the polymerization reaction product (polyamide compound) thus obtained is accompanied by hydrogen halide which is a by-product, neutralization is required. The neutralizing agent is not particularly limited as long as it is a generally known basic compound.
As the neutralizing agent, triethylamine, tripropylamine, benzyldimethylamine, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, magnesium oxide, calcium oxide, tetraethylammonium salt, etc. are preferably used. be able to. In addition, such a neutralizing agent may be added alone in powder form, but it is preferable from the viewpoint of reactivity and operability to use a finely divided powder dispersed in an organic solvent as a slurry. .

  The polyamide compound solution obtained by the above method can be separated in a poor solvent such as water or methanol. The solution after the neutralization reaction can also be used as a molding solution as it is.

  Moreover, it does not specifically limit as an industrial polycondensation method of the polyamide compound of this invention, A well-known method is used widely. Examples thereof include a pressurized salt method, a normal pressure dropping method, a pressure dropping method, and a reactive extrusion method. Further, when the reaction temperature is as low as possible, yellowing and gelation of the polyamide compound can be suppressed, and a polyamide compound having stable properties can be obtained.

  The pressurized salt method is a method of performing melt polycondensation under pressure using a nylon salt as a raw material. Specifically, after preparing a nylon salt aqueous solution containing a diamine component, a dicarboxylic acid component, and other components as necessary, the aqueous solution is concentrated and then heated under pressure to remove condensed water. While polycondensing. While the inside of the can is gradually returned to normal pressure, the temperature is raised to about the melting point of the polyamide compound + 10 ° C. and held, and then the pressure is gradually reduced to 0.02 MPaG and kept at the same temperature to continue polycondensation. To do. When a certain stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound.

  In the normal pressure dropping method, a diamine component is continuously dropped into a mixture obtained by heating and melting a dicarboxylic acid component and, if necessary, other components under normal pressure, and polycondensation is performed while removing condensed water. The polycondensation reaction is performed while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the polyamide compound to be produced.

In the pressure dropping method, first, a dicarboxylic acid component and, if necessary, other components are charged into a polycondensation can, and the components are stirred and melt mixed to prepare a mixture. Next, the diamine component is continuously dropped into the mixture while the inside of the can is preferably pressurized to about 0.3 to 0.4 MPaG, and polycondensation is performed while removing condensed water. At this time, the polycondensation reaction is performed while raising the temperature of the reaction system so that the reaction temperature does not fall below the melting point of the polyamide compound to be produced. When the set molar ratio is reached, the addition of the diamine component is terminated, the temperature inside the can is gradually raised to normal pressure, the temperature is raised to about the melting point of the polyamide compound + 10 ° C., and then the pressure is gradually reduced to 0.02 MPaG. However, it is maintained at the same temperature and the polycondensation is continued. When a certain stirring torque is reached, the inside of the can is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound.
The reactive extrusion method is a method of incorporating into a polyamide skeleton by an amide exchange reaction.

[3] Polyamide composition using a polyamide compound The polyamide compound of the present invention can be applied to a lubricant, a crystallization nucleating agent, a whitening inhibitor, a matting agent, a heat stabilizer, a weather stabilizer, an ultraviolet absorber, depending on the application and performance. An additive such as an agent, a plasticizer, a flame retardant, an antistatic agent, an anti-coloring agent, an antioxidant, and an impact resistance improving material may be added to form a polyamide composition. These additives can be added as necessary within a range not impairing the effects of the present invention. In addition, the polyamide compound of the present invention may be mixed with various resins according to required applications and performances to form a polyamide composition.

[4] Use of polyamide compound The polyamide compound of the present invention can be used for a wide variety of other uses as well as the use of conventional polyamide compounds.

  Hereinafter, the present invention will be described more specifically with reference to examples. In addition, the polyamide compound appearing in the following description is sometimes referred to as “biopolyamide”.

1. Synthesis of Polyamide Compound <Comparative Example 1> (Synthesis of synthesis of PA ₈₀ AC ₂₀ BPE ₁₀₀ )
Polyamide Synthesis of Compound _{(PA 80} AC 20 _{BPE 100)} is (synthesized along Examples 1-4 also similar scheme) was performed along the scheme below. In the case of Comparative Example 1, Z = 4, and in Examples 1-4, Z = 6 or 8.

Specifically, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (41.1 g, 100.0 mmol) and THF were added to a separable flask (Separable flash (1000 mL)) under a nitrogen atmosphere. (300 mL) was added, stirred using a mechanical stirrer at 0 ° C. for 10 minutes, triethylamine (30.8 mL, 220.0 mmol) was added, and the mixture was stirred at 0 ° C. for 10 minutes. Thereafter, acid chloride (1 ′) (57.2 g, 80.0 mmol) and adipol chloride (3.7 g, 20.0 mmol) were dissolved in THF (100 mL), and the mixture was added dropwise and reacted at 0 ° C. for 4 hours. After completion of the reaction, the product was purified by reprecipitation using water and washed with water and methanol. The product was vacuum dried (80 ° C., 16 hours). White fiber, yield: 92.0 g. FT-IR (ATR, cm ⁻¹ ): 3290.0 (NH, amide), 2918.7, 2854.1, 1653.7 (C═O, carbonyl), 1601.6, 1533.1, 1497.5 , 1461.8, 1409.7, 1222.6, 1174.4, 1014.4, 831.2, 727.0, 512.0.

<Example 1> (Synthesis of PA ₇₀ SC ₃₀ BPE ₁₀₀ )
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (41.1 g, 100.0 mmol) and THF (300 mL), triethylamine (30.8 mL, 220.0 mmol), acid chloride (1 ') (50.1 g, 70.0 mmol) and Suberoyl chloride (6.3 g, 30.0 mmol), similar to the synthesis of PA ₈₀ AC ₂₀ BPE ₁₀₀ , except that THF (150 mL) was used. went. White fiber, yield: 90.0 g. FT-IR (ATR, cm ⁻¹ ): 3285.1 (NH, amide), 2922.6, 2850.3, 1653.7 (C═O, carbonyl), 1605.4, 1533.1, 1501.3 , 1461.8, 1405.9, 1226.5, 1170.6, 1014.4, 827.3, 715.5, 508.2.

<Example 2> (Synthesis of PA ₅₀ SC ₅₀ BPE ₁₀₀ )
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (41.1 g, 100.0 mmol) and THF (300 mL), triethylamine (30.8 mL, 220.0 mmol), acid chloride (1 ') (35.8 g, 50.0 mmol), Suberoyl chloride (10.6 g, 50.0 mmol), and THF (150 mL) were used in the same manner as in the synthesis of PA ₈₀ AC ₂₀ BPE ₁₀₀ . White fiber, yield: 80.0 g. FT-IR (ATR, cm ⁻¹ ): 3281.3 (NH, amide), 2922.6, 2850.3, 1657.5 (C═O, carbonyl), 1605.4, 1533.1, 1497.5 , 1461.8, 1409.7, 1226.5, 1170.6, 1014.4, 827.3, 715.5, 508.2.

<Example 3> (Synthesis of PA ₇₀ SeC ₃₀ BPE ₁₀₀ )
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (41.1 g, 100.0 mmol) and THF (300 mL), triethylamine (30.8 mL, 220.0 mmol), acid chloride (1 ') (50.1 g, 70.0 mmol), sebacoyl chloride (7.2 g, 30.0 mmol) and THF (150 mL) were used in the same manner as in the synthesis of PA ₈₀ AC ₂₀ BPE ₁₀₀ . White fiber, yield: 90.0 g. FT-IR (ATR, cm ⁻¹ ): 3285.1 (NH, amide), 2918.7, 2850.3, 1657.5 (C═O, carbonyl), 1605.4, 1538.0, 1497.5 , 1457.9, 1405.9, 1226.5, 1170.6, 1010.5, 831.2, 719.3, 515.9.

<Example 4> (Synthesis of PA ₅₀ SeC ₅₀ BPE ₁₀₀ )
2,2-bis [4- (4-aminophenoxy) phenyl] propane (BPE) (41.1 g, 100.0 mmol) and THF (300 mL), triethylamine (30.8 mL, 220.0 mmol), acid chloride (1 ') (35.8 g, 50.0 mmol), except for sebacoyl chloride (12.0 g, 50.0 mmol) and THF (150 mL), the same procedure as in the synthesis of PA ₈₀ AC ₂₀ BPE ₁₀₀ was performed. White fiber, yield: 80.0 g. FT-IR (ATR, cm ⁻¹ ): 3285.1 (NH, amide), 2918.7, 2850.3, 1657.5 (C═O, carbonyl), 1605.4, 1538.0, 1497.5 , 1457.9, 1405.9, 1226.5, 1170.6, 1010.5, 831.2, 719.3, 515.9.

2. Mechanical property evaluation 2-1. Preparation of test piece For the preparation of a test piece by injection molding, a scale-up synthesis of each polyamide compound and a collected sample (about 500 g) were used. Using Mini Test Press-10, manufactured by Toyoseiki, it was formed into a flat plate, cut into pellets. A test piece was prepared from the pellet using an injection molding machine (small electric injection molding machine SE18DUZ, manufactured by Sumitomo Heavy Industries, Ltd.). As molding conditions, the resin temperature was 140 to 200 ° C, and the mold temperature was 14 to 18 ° C. As a test piece, a multipurpose test piece 5A type (dumbbell shape) of JIS K 7162 (t 2 mm), a width 10 mm × length 80 mm × thickness 4 mm test piece (strip shape) was molded. The dumbbell-shaped test piece was used for the tensile test. The strip-shaped test piece was processed into a K7110 type 1 test piece and used for the Charpy impact test and the bending test.

2-2. Tensile test
For tensile properties, a tensile test was performed to evaluate yield stress (tensile strength), tensile modulus, and elongation at break. As a test piece, a multipurpose test piece 5A type (dumbbell shape) of JIS K 7162 was used. In measurement, the width and thickness of the test piece were measured and used. For the measurement, an AGI-50kN type tester manufactured by Shimadzu Corporation was used. The measurement conditions were a tensile speed of 1 mm / min, a tensile load of 50 kN, and a measurement temperature of 23 ° C.

2-3. Bending test Bending characteristics were evaluated by bending test and bending elastic modulus and bending strength. The test piece is 2-1. The K7110 type 1 test piece prepared in step 1 was evaluated according to K7171. In the test, the width and thickness of the test piece were measured. For the measurement, an AGS-X 10 kNX 5 testing machine manufactured by Shimadzu Corporation was used. The measurement conditions were a test speed of 2 mm / min, a maximum load of 10 kN, and a measurement temperature of 23 ° C.

2-4. Charpy impact test The impact characteristics were evaluated by conducting a Charpy test with a notch and obtaining a Charpy impact value. The test piece is 2-1. The K7110 type 1 test piece prepared in step 1 was notched in accordance with K7111. In the test, the width and thickness of the test piece were measured. For the measurement, a Charpy impact tester, Toyo Seiki Seisakusho DG-UB, was used.

2-5. Test results Tables 1 to 3 show the test results.

  From the test results of Tables 1 to 3, it can be seen that the polyamide compound of the example is a resin having high impact resistance, hard and tenacious, like the polyamide compound of the comparative example.

3. Evaluation of physical properties 3-1. Measuring method The glass transition temperature (Tg) of the polyamide compound was determined by differential scanning calorimetry (DSC). The 5% weight loss temperature (Td) and the thermal decomposition temperature of the polyamide compound were determined by simultaneous thermogravimetric / differential calorimetric analysis (TG / DTA). The Tg measurement was evaluated according to JIS K7121. Td and thermal decomposition temperature measurements were evaluated according to JIS K7120.
For the measurement, Hitachi High-Tech Science Co., Ltd. thermal analyzer EXSTAR DSC7020 and Rigaku Co., Ltd. TG8120 were used, and the measurement conditions were as follows.
About DSC measurement, it measured in measurement temperature range: -50-280 degreeC, temperature increase rate: 10 degree-C / min, and nitrogen stream (50 mL / min).
For TG / DT measurement, measurement was performed at a measurement temperature: room temperature to 500 ° C., a heating rate: 10 ° C./min, and in a nitrogen stream (150 mL / min).

3-2. Measurement results Tables 4 to 6 show the measurement results.

  From the measurement results of Tables 4 to 6, it was confirmed that the polyamide compound of the example was a resin having high thermal stability, like the polyamide compound of the comparative example.

4). X-ray diffraction analysis (XRD)
4-1. Measuring method The crystallinity of the polyamide compound was evaluated by XRD analysis. For the measurement, an X-ray scattering device Rigaku NANO-Viewer manufactured by Rigaku Corporation was used, and the measurement conditions were as follows.
Detector: Pilatus 100K
X-ray wavelength: 0.154 nm (CuKα ray)
Beam size: φ0.4mm
Exposure time: 0.5h

4-2. Measurement results Table 7 shows the measurement results.

  From the measurement results in Table 7, each sample of Comparative Example 1 and Example 4 showed a peak in the vicinity of 2θ = 18.0 degrees. No crystalline peak was observed. The peak around 2θ = 18.0 degrees was derived from amorphous, and it was confirmed that the samples of Comparative Example 1 and Example 4 were amorphous.

5). Evaluation of transparency 5-1. Evaluation Method A test piece (strip shape) 10 mm wide x 80 mm long x 4 mm thick was prepared as a test piece. The test piece was placed on a copy sheet on which the character string “TBRL” was printed, and the transparency of the test piece was evaluated based on the degree to which the character string was seen through the test piece. In addition, transparency was evaluated under the light of a fluorescent lamp.

5-2. Evaluation Results FIG. 1 is a photograph showing the transparency of the test pieces of Example 4 and Comparative Example 1. In the test piece of Example 4, compared with the test piece of Comparative Example 1, the character string was confirmed more clearly. Thus, the test piece of Example 4 was very transparent compared to the test piece of Comparative Example 1. In addition, also about the test piece of Examples 1-3, transparency was very high similarly to the test piece of Example 4.

6). Effects of Examples The polyamide compounds of Examples have very high transparency while having excellent mechanical properties and excellent thermal stability.

  The foregoing examples are for illustrative purposes only and are not to be construed as limiting the invention. Although the invention has been described with reference to exemplary embodiments, it is to be understood that the language used in the description and illustration of the invention is illustrative and exemplary rather than limiting. As detailed herein, changes may be made in the form of the appended claims without departing from the scope or essence of the invention. Although specific structures, materials and examples have been referred to in the detailed description of the invention herein, it is not intended to limit the invention to the disclosure herein, but rather, the invention is claimed. It covers all functionally equivalent structures, methods and uses within the scope.

  The present invention is not limited to the embodiments described in detail above, and various modifications or changes can be made within the scope of the claims of the present invention.

  The polyamide compound of the present invention can be used for a wide variety of other applications as well as the applications to which conventional polyamide compounds have been applied. For example, it can be used as any member such as an automobile, a railway vehicle, a ship, and an airplane. For example, it is used as an interior material and an exterior material. Among these, examples of the automobile article include an automobile interior material, an automobile instrument panel, and an automobile exterior material. Specifically, door base material, package tray, pillar garnish, switch base, quarter panel, side panel, armrest, automotive door trim, seat structure material, seat backboard, ceiling material, console box, automotive dashboard, various types Instrument panels, deck trims, bumpers, spoilers, cowlings, etc. Furthermore, for example, interior materials and exterior materials such as buildings and furniture can be mentioned. That is, door covering materials, door structural materials, and covering materials for various furniture (desks, chairs, shelves, bags, etc.) can be mentioned. In addition, a packaging body, a container (such as a tray), a protective member, a partition member, and the like can be given.

Claims (3)

A dicarboxylic acid unit represented by the following general formula (1):
A dicarboxylic acid unit represented by the following general formula (2);
And a diamine unit represented by the following general formula (3).


(X = 9, y = 11)

(Z represents 6 or 8)

  The polyamide compound according to claim 1, wherein the molar ratio of the dicarboxylic acid unit represented by the general formula (1): the dicarboxylic acid unit represented by the general formula (2) is 90:10 to 10:90. A method for producing a polyamide compound according to claim 1 or 2,
An acid chloride capable of constituting a dicarboxylic acid unit represented by the general formula (1);
An acid chloride capable of constituting a dicarboxylic acid unit represented by the general formula (2);
The manufacturing method of the polyamide compound characterized by making it react with the diamine which can comprise the diamine unit represented by General formula (3).