JP7643152B2 - Composite and method for producing the composite - Google Patents

Description

This disclosure relates to a composite and a method for producing the composite.

From the perspective of preventing global warming and reducing resource risks, biopolymers such as polyamide compounds made from plant-derived compounds have been attracting attention as an alternative to petroleum-based polymers (see, for example, Non-Patent Documents 1-2 and Patent Document 1).

JP 2019-137788 A

C. -H. Lee, H. Takagi, H. Okamoto, M. Kato, A. Usuki. J. Polym. Sci. Part A: Polym. Chem. 47, 6025 (2009). C. -H. Lee, H. Takagi, H. Okamoto, M. Kato. J. Appl. Polym. Sci. 127, 530 (2013).

However, conventional biopolymers do not necessarily have sufficient properties for some applications, and there is a demand for improved properties.
The present disclosure is intended to solve the above problems and can be realized in the following forms.

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1. A polyamide compound containing 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),
Talc and
A complex comprising:

(wherein x is an integer from 6 to 12, and y is an integer from 8 to 18.)

(z is an integer from 2 to 18.)

The composites of the present disclosure have superior properties to conventional polyamide compounds.
According to the manufacturing method of the present disclosure, a composite having superior properties to those of conventional polyamide compounds can be manufactured.

FIG. 1 is a graph showing tensile strength. FIG. 2 is a graph showing the tensile modulus. FIG. 3 is a graph showing the flexural modulus.

Here, another example of the present disclosure is given.
A complex, 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 95:5 to 5:95.
The complex, wherein the content of the talc is 1% by mass or more and 40% by mass or less.
A method for producing a composite, comprising kneading the polyamide compound and the talc in a twin-screw kneading extruder.

The embodiments of the present disclosure are described in detail below. In this specification, when a numerical range is described using "to", it is intended to include the lower limit and the upper limit unless otherwise specified. For example, the description "10 to 20" is intended to include both the lower limit "10" and the upper limit "20". In other words, "10 to 20" has the same meaning as "10 or more and 20 or less".

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The present disclosure will be described in detail below.
1. Composite The composite includes a polyamide compound containing 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), and talc.

(wherein x is an integer from 6 to 12, and y is an integer from 8 to 18.)

(z is an integer from 2 to 18.)

1.1 Polyamide Compound The polyamide compound of the present disclosure may further contain structural units other than those described above, as long as the effects of the present disclosure are not impaired.

In the polyamide compound of the present disclosure, 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%, and more preferably 30 to 50 mol%.
In the polyamide compound of the present disclosure, the content of the diamine unit is not particularly limited. The content of the diamine unit is usually 5 to 50 mol%, preferably 20 to 50 mol%, and more preferably 30 to 50 mol%.
From the viewpoint of the polymerization reaction, the content ratio of the dicarboxylic acid unit and the diamine unit is preferably approximately the same, and the content of the dicarboxylic acid unit is more preferably within ±1 mol % of the content of the diamine unit.

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ｚは２～６の整数が好ましい。） 1.1.1 Dicarboxylic Acid Unit As described above, the polyamide compound of the present disclosure contains a dicarboxylic acid unit represented by the following general formula (1) and a dicarboxylic acid unit represented by the following general formula (2).

(x is an integer from 6 to 12, and y is an integer from 8 to 18.
x is preferably an integer from 8 to 10, and y is preferably an integer from 8 to 14.

(z represents an integer of 2 to 18.
z is preferably an integer of 2 to 6.

The dicarboxylic acid unit represented by general formula (1) is derived from plants and contributes to preventing global warming and reducing resource risks.

When the total amount of dicarboxylic acid units in the polyamide compound of the present disclosure is taken as 100 mol%, the total amount of dicarboxylic acid units represented by the above general formulas (1) and (2) is not particularly limited. The total amount of dicarboxylic acid units represented by general formulas (1) and (2) is preferably 30 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 70 to 100 mol%. When the content of dicarboxylic acid units represented by general formulas (1) and (2) is within this range, a composite having a high flexural modulus is obtained. Furthermore, when the content is within this range, a composite having a high glass transition temperature (Tg) is obtained.

In the polyamide compound, the molar ratio of the dicarboxylic acid unit represented by the general formula (1) to the dicarboxylic acid unit represented by the general formula (2) is not particularly limited.
The molar ratio of the dicarboxylic acid units represented by the general formula (1): the dicarboxylic acid units represented by the general formula (2) is preferably from 95:5 to 5:95, more preferably from 90:10 to 10:90, and even more preferably from 80:20 to 20:80.

Compounds capable of constituting dicarboxylic acid units other than the dicarboxylic acid units represented by the general formulae (1) and (2) are not particularly limited.
For example, specific examples of dicarboxylic acid compounds include straight-chain aliphatic dicarboxylic acids having 2 to 25 carbon atoms, such as oxalic acid, malonic acid, fumaric acid, and maleic acid, or aliphatic dicarboxylic acids such as dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acids) obtained by dimerizing unsaturated fatty acids obtained by fractional distillation of triglycerides and hydrogenated products thereof (hydrogenated dimer acids), alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, and aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 1,3-benzenediacetic acid, and 1,4-benzenediacetic acid. Derivatives of these dicarboxylic acid compounds may also be used. Examples of derivatives include carboxylic acid halides. These may be used alone or in combination of two or more.
When the total amount of dicarboxylic acid units in the polyamide compound of the present disclosure is 100 mol%, the content of dicarboxylic acid units other than the dicarboxylic acid represented by the above general formula (1) (2) is not particularly limited. The content of dicarboxylic acid units other than the dicarboxylic acid represented by the general formula (1) (2) is preferably less than 50 mol%, more preferably less than 20 mol%, and particularly preferably less than 10 mol%. When the content of dicarboxylic acid units other than the dicarboxylic acid units represented by the general formula (1) (2) is within this range, tensile strength, tensile modulus, bending modulus, etc. are improved.

1.1.2 Diamine Unit The diamine unit in the polyamide compound of the present disclosure includes at least a diamine unit represented by general formula (3).

When the total amount of diamine units in the polyamide compound of the present disclosure is taken as 100 mol%, the content of the diamine units represented by the above general formula (3) is not particularly limited. It is preferable to contain 5 to 100 mol%, more preferably 50 to 100 mol%, and particularly preferably 80 to 100 mol% of the diamine units represented by general formula (3). This is because when the content of the diamine acid units represented by general formula (3) is within this range, the tensile strength, tensile modulus, bending elasticity, etc. are excellent.

Repeating units which may be contained in the polyamide compound include the following combinations of dicarboxylic acid units and diamine units.
[A] A combination of a dicarboxylic acid unit represented by general formula (1) and a diamine unit represented by 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 randomly in the polyamide compound.
Furthermore, the same kind of repeating units may be present in the polyamide compound in the form of blocks.

Compounds capable of constituting diamine units other than the diamine unit represented by formula (3) are not particularly limited.
For example, diamines other than the diamine unit represented by formula (3) include known aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like.

Examples of aliphatic diamines that can form diamine units other than the diamine unit represented by 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 aromatic diamines 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)benzene, and 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-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecane 2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestanyl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzoyloxy)cyclohexyl-3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzoyloxy)cyclohexyl-3,5-diaminobenzoate Examples of the diaminobenzoate include 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-diaminophenyl)piperazine-4-carboxylic acid, 4-(morpholin-4-yl)benzene-1,3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, and α-amino-ω-aminophenylalkylene.
These may be used alone or in combination of two or more.

When the total amount of diamine units in the polyamide compound of the present disclosure is taken as 100 mol%, the content of diamine units other than the diamine represented by the above general formula (3) is not particularly limited. The content of diamine units 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%. This is because when the content of diamine units other than the diamine units represented by the general formula (3) is within this range, the tensile strength, tensile modulus, bending elasticity, etc. are improved.

1.1.3 Degree of polymerization of polyamide compound There is no particular limitation on the degree of polymerization of the polyamide compound of the present disclosure. The viscosity number measured as follows is preferably in the range of 4.0 to 10.0, particularly preferably in the range of 5.0 to 8.0.
The viscosity number is measured as follows.
Test method: Based on JIS K6933 Test conditions: Measurement solvent: 96% sulfuric acid Viscometer: Ubbelohde viscometer Solution concentration: 0.005 g/mL
Measurement temperature: 25°C

Calculation formula: Viscosity number (mL/g) = (t/t ₀ -1) x 1/C
t0: Flow time of the measurement solvent (s)
t: sample solution flow time (s)
C: Solution concentration (g/mL)

1.1.4 Method for Producing Polyamide Compound The method for producing the polyamide compound of the present disclosure is not particularly limited. The polyamide compound of the present disclosure can be produced, for example, by reacting a dicarboxylic acid compound with a diamine compound.

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

The polyamide compound of the present disclosure can be produced by polycondensing a diamine component capable of forming a diamine unit and a dicarboxylic acid component capable of forming a dicarboxylic acid unit. The degree of polymerization can be controlled by adjusting the polycondensation conditions, etc.
The method for producing the polyamide compound is not particularly limited. For example, the method for producing the polyamide compound may be preferably, for example, (1) a method using an acid or base catalyst, (2) a method using a carboxylic acid, (3) a method using transesterification, or (4) a method using a condensing agent.

As a suitable production method, for example, a production method is adopted in which a dicarboxylic acid is activated to produce an acid chloride, and the acid chloride is reacted with a diamine to produce a polyamide compound. That is, a production method is preferably adopted in which an acid chloride capable of forming a dicarboxylic acid unit represented by the above general formula (1), an acid chloride capable of forming a dicarboxylic acid unit represented by the above general formula (2), and a diamine capable of forming a diamine unit represented by the above general formula (3) are reacted.
In addition, if a dicarboxylic acid is activated to form an acid chloride and then reacted with a diamine, a polyamide compound can be produced efficiently.

In addition, a monoamine or a monocarboxylic acid may be added as a molecular weight regulator during polycondensation. In addition, the ratio (molar ratio) of the diamine component and the carboxylic acid component constituting the polyamide compound may be adjusted to be different from 1 in order to suppress the polycondensation reaction and achieve the desired degree of polymerization.

When polymerization is carried out by a dehydrohalogenation reaction between a carboxylic acid dihalide such as the above-mentioned acid chloride and a diamine, it is preferable to carry out the reaction at a relatively low temperature in order to control the reaction rate, since the reaction proceeds rapidly.
For example, it is preferable to carry out the treatment at a temperature in the range of -10°C to 100°C.
The reaction solvent is not particularly limited, and a wide variety of known solvents can be used. For example, examples of organic polar solvents as reaction solvents include dimethylacetamide, N-methylpyrrolidone, dimethylsulfone, dimethylformamide, N-methylcaprolactam, tetramethylurea, and N,N'-dimethyl-2-imidazolidinone. These may be used alone or as a mixed solvent of two or more. If necessary, hydrogen chloride or a metal halide salt, such as lithium chloride, calcium chloride, or potassium chloride, may be used in combination to improve solubility.

The concentration of the polyamide compound (polymer concentration) is not particularly limited, although it depends on the solubility of the produced polyamide compound in a 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, etc.
The concentration of the polyamide compound is determined by comprehensively considering the content and composition ratio of the polyamide compound composition, solubility, solution viscosity, handleability, and ease of degassing.

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

In addition, in the case of the polyamide compounds of the present disclosure, in order to improve the properties, a method of addition intended to block the polymer may be adopted, such as reacting a portion of the diamine or acid chloride and then adding the remaining raw materials.

The polymerization reaction product (polyamide compound) thus obtained contains hydrogen halide as a by-product, and therefore requires neutralization. The neutralizing agent is not particularly limited as long as it is a commonly 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. Although such a neutralizing agent may be added alone in the form of a powder, it is preferable to use a finely powdered neutralizing agent dispersed in an organic solvent as a slurry from the viewpoints of reactivity and operability.

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 it is as a molding solution.

The method for industrial polycondensation of the polyamide compound of the present disclosure is not particularly limited, and known methods are widely used. For example, the pressurized salt method, the atmospheric pressure dropping method, the pressurized dropping method, the reactive extrusion method, etc. are included. In addition, the lower the reaction temperature is, the more the yellowing and gelling of the polyamide compound can be suppressed, and the more stable the polyamide compound can be obtained.

In the pressurized salt method, nylon salt is used as a raw material and melt polycondensation is carried out under pressure. Specifically, after preparing an aqueous nylon salt solution containing a diamine component, a dicarboxylic acid component, and optionally other components, the aqueous solution is concentrated and then heated under pressure to polycondense while removing the condensation water. While gradually returning the pressure inside the tank to normal pressure, the temperature is raised to about the melting point of the polyamide compound +10°C and maintained at that temperature, and then the pressure is gradually reduced to 0.02 MPaG while maintaining the temperature to continue polycondensation. When a certain stirring torque is reached, the tank is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound.

In the normal pressure dropping method, the diamine component is continuously dropped into a mixture of a dicarboxylic acid component and, if necessary, other components, which are heated and melted under normal pressure, and polycondensation is carried out while removing the condensation water. The polycondensation reaction is carried out 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 tank, and each component is stirred and melted and mixed to prepare a mixture. Next, the diamine component is continuously dropped into the mixture while pressurizing the inside of the tank to about 0.3 to 0.4 MPaG, and polycondensation is performed while removing condensation 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 dropping of the diamine component is stopped, and while gradually returning the inside of the tank to normal pressure, the temperature is raised to about the melting point + 10°C of the polyamide compound and maintained, and then the temperature is gradually reduced to 0.02 MPaG while maintaining the temperature, and polycondensation is continued. When a certain stirring torque is reached, the inside of the tank is pressurized to about 0.3 MPaG with nitrogen to recover the polyamide compound.
The reactive extrusion method is a method for incorporating the polyamide into the backbone by an amidation exchange reaction.

1.2 Talc There is no particular limitation on the talc. For example, talc is a plate-like particle of magnesium silicate having a layered structure, and its composition is, for example, Mg ₃ Si ₄ O ₁₀ (OH) ₂ or other mineral.
The content of talc in the composite is not particularly limited, but from the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite, the content of talc is preferably 1% by mass or more and 40% by mass or less, more preferably 2% by mass or more and 30% by mass or less, and even more preferably 5% by mass or more and 20% by mass or less, based on 100% by mass of the entire composite.

1.2.1 Particle size (D50)
The particle size (D50) (median size) of the talc is not particularly limited. From the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite, the particle size (D50) of the talc is preferably 0.1 μm or more and 50 μm or less, more preferably 0.5 μm or more and 25 μm or less, and even more preferably 2 μm or more and 8 μm or less. The particle size (D50) can be measured by a laser diffraction method.

1.2.2 Apparent density The apparent density of talc is not particularly limited. From the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite, the apparent density of talc is preferably 0.05 g/mL or more and 0.7 g/mL or less, more preferably 0.08 g/mL or more and 0.6 g/mL or less, and even more preferably 0.1 g/mL or more and 0.5 g/mL or less. The apparent density can be measured in accordance with JIS K5101.

1.2.3 Specific surface area The specific surface area of talc is not particularly limited. From the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite, the specific surface area of talc is preferably 1.5 m ² /g or more and 100 m ² /g or less, more preferably 3 m ² /g or more and 20 m ² /g or less, and even more preferably 5 m ² /g or more and 10 m ² /g or less. The specific surface area can be measured by the BET method.

1.2.4 Moisture The moisture content of talc is not particularly limited. From the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite, the moisture content of talc is preferably 0.1% or more and 0.5% or less, and more preferably 0.1% or more and 0.3% or less. The moisture content can be measured in accordance with JIS K5101.

1.2.5 Oil Absorption The oil absorption of talc is not particularly limited. From the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite, the oil absorption of talc is preferably 20 ml/100 g or more and 60 ml/100 g or less, more preferably 20 ml/100 g or more and 60 ml/100 g or less. The oil absorption can be measured in accordance with JIS K5101.

1.2.6 Color The whiteness of the talc is not particularly limited. The whiteness of the talc is preferably 90% or more and 100% or less, more preferably 95% or more and 100% or less, in order to suppress the influence of impurities on the tensile strength, tensile modulus, flexural modulus, etc. of the composite. The whiteness can be measured by the Hunter method.

1.3 Composite Properties In the composite of the present disclosure, talc is well dispersed in the polyamide compound, and therefore the composite has high tensile strength, tensile modulus, and flexural elasticity.
In general synthetic polymers, the dispersibility of talc is not so high. However, in the composite of the present disclosure, the dispersibility of talc is high. The reason is presumed to be as follows. In the polyamide compound used in the composite of the present disclosure, the amide bond has a high affinity with the hydroxyl group of talc, and the long alkyl chain (n-C _x H _2x+1 ) has a high affinity with Mg, Si, etc. of talc, so it is presumed that the dispersibility of talc is high.
Furthermore, when x=9 and y=11 in the above general formula (1), the dicarboxylic acid unit represented by the above general formula (1) is derived from plants, and talc is a natural mineral, making the complex environmentally friendly.
These characteristics are not available in composites made from conventional synthetic polymers.

1.4 Additives Depending on the application and performance, additives such as lubricants, crystallization nucleating agents, whitening inhibitors, matting agents, heat stabilizers, weathering stabilizers, UV absorbers, plasticizers, flame retardants, antistatic agents, color inhibitors, antioxidants, and impact modifiers may be added to the composite of the present disclosure. These additives can be added as necessary to the extent that they do not impair the effects of the composite of the present disclosure.

1.5 Uses of the Composite The composites of the present disclosure can be used in a wide range of applications.

2. Method for Producing the Composite The method for producing the composite is not particularly limited. The composite can be suitably produced by kneading a polyamide compound and talc in a twin-screw kneading extruder.

The present disclosure will be explained in more detail below with reference to examples. In the following explanation, the polyamide compound may also be referred to as a "biopolymer." The composite may also be referred to as a "biopolymer composite material."

1. Synthesis of polyamide compound (synthesis of PA ₈₀ AC ₂₀ BPE ₁₀₀ )
The synthesis of the polyamide compound (PA ₈₀ AC ₂₀ BPE ₁₀₀ ) was carried out according to the following scheme: In the following scheme, Z=4.

In detail, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BPE) (41.1 g, 100.0 mmol) and THF (300 mL) were placed in a separable flask (1000 mL) under a nitrogen atmosphere, and the mixture was stirred at 0° C. for 10 minutes using a mechanical stirrer. Triethylamine (30.8 mL, 220.0 mmol) was then 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 added dropwise, and the mixture was reacted at 0° C. for 4 hours. After 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 fibrous, yield: 92.0 g. FT-IR (ATR, cm ^-1 ): 3290.0 (NH, amide), 2918.7, 2854.1, 1653.7 (C=O, carbonyl), 1601.6, 153 3.1, 1497.5, 1461.8, 1409.7, 1222.6, 1174.4, 1014.4, 831.2, 727.0, 512.0.
The polyamide compound was pelletized.
The chemical formula of this polyamide compound is shown below.

2. Production of Composite 90 parts by mass of the polyamide compound (PA ₈₀ AC ₂₀ BPE ₁₀₀ ) synthesized as described above and 10 parts by mass of talc were kneaded in a twin-screw kneading extruder to obtain a composite (composite material). The composite was pelletized.
When the composite was observed under an electron microscope (SEM), a morphology in which talc was uniformly dispersed in the polyamide compound was confirmed.

3. Mechanical Property Evaluation 3.1 Preparation of Test Pieces Test pieces were prepared from the pellets using an injection molding machine (small electric injection molding machine SE18DUZ, manufactured by Sumitomo Heavy Industries, Ltd.). The molding conditions were a resin temperature of 160 to 240°C and a mold temperature of 14 to 18°C. As test pieces, multipurpose test pieces 5A type (dumbbell-shaped) of JIS K7161 (t = 2 mm) and test pieces (strip-shaped) measuring 10 mm wide x 80 mm long x 4 mm thick were molded. The dumbbell-shaped test pieces were used for tensile tests. The strip-shaped test pieces were processed into type 1 test pieces of K7110 and used for Charpy impact tests and bending tests.

3.2 Tensile test Tensile properties were evaluated by performing a tensile test in accordance with JIS K 7161-2, and the yield stress (tensile strength), tensile breaking strain, and tensile modulus were evaluated. The width and thickness of the test piece were measured and used for the measurement. A universal material testing machine Model 5966 (manufactured by Instron) was used for the measurement. The measurement conditions were a tensile speed of 100 mm/min, a tensile load of 50 kN, and a measurement temperature of 23°C.

3.3 Bending test Bending properties were evaluated by performing a bending test to evaluate the bending modulus and bending strength. The bending test was performed in accordance with JIS K7171. In the test, the width and thickness of the test piece were measured. A universal material testing machine Model 5966 (manufactured by Instron) was used for the measurement. The measurement conditions were a test speed of 2 mm/min, a maximum load of 10 kN, and a measurement temperature of 23°C.

3.4 Charpy impact test The impact properties were evaluated by performing a notched Charpy test to determine the Charpy impact value. The bending test was performed in accordance with JIS K7111-1. The width and thickness of the test piece were measured. A Charpy impact tester, DG-UB, manufactured by Toyo Seiki Seisakusho Co., Ltd., was used for the measurement.

3.5 Test Results The test results are shown in Table 1 and Figures 1 to 3.

The test results in Table 1 and Figures 1 to 3 show that the composite has significantly higher tensile strength, tensile modulus, and flexural modulus than the biopolymer alone.

4. Physical property evaluation 4.1 Measurement method The glass transition temperature (Tg) was determined by differential scanning calorimetry (DSC). The 5% weight loss temperature (Td) was determined by simultaneous thermogravimetry and differential thermal analysis (TG/DTA). The Tg measurement was evaluated in accordance with JIS K7121. The Td and thermal decomposition temperature measurements were evaluated in accordance with JIS K7120.
For the measurement, a thermal analyzer EXSTAR DSC7020 manufactured by Hitachi High-Tech Science Corporation and a TG8120 manufactured by Rigaku Corporation were used, and the measurement conditions were as follows.
The DSC measurement was performed at a temperature range of −50 to 280° C., at a temperature rise rate of 10° C./min in a nitrogen gas flow (50 mL/min).
The TG/DT measurements were performed at a measurement temperature of room temperature to 500° C., at a temperature rise rate of 10° C./min, in a nitrogen gas flow (150 mL/min).

4.2 Measurement results The measurement results are shown in Table 2.

The measurement results in Table 2 confirm that the complex has higher thermal stability than the biopolymer alone.

5. Effects of the Examples The composites of the examples have excellent mechanical properties and also have excellent thermal stability.

The foregoing examples are merely illustrative and are not to be construed as limiting the present disclosure. While the present disclosure has been described with reference to exemplary embodiments, the words used in describing and illustrating the present disclosure are to be understood as descriptive and exemplary rather than limiting. As detailed herein, changes may be made within the scope of the appended claims without departing from the scope or nature of the present disclosure in its form. Although the detailed description of the present disclosure has been made with reference to specific structures, materials, and examples, it is not intended that the present disclosure be limited to those disclosed herein, but rather that the present disclosure extends to all functionally equivalent structures, methods, and uses within the scope of the appended claims.

This disclosure is not limited to the embodiments detailed above, and various modifications and variations are possible within the scope of the claims of this disclosure.

The composite of the present disclosure can be used in a wide range of applications, including those for which conventional polyamide compounds have been used. For example, it can be used as any component of an automobile, a railroad vehicle, a ship, an airplane, etc. For example, it can be used as an interior material and an exterior material. Among these, examples of automotive products include interior materials for automobiles, instrument panels for automobiles, and exterior materials for automobiles. Specific examples include door substrates, package trays, pillar garnishes, switch bases, quarter panels, side panels, armrests, automobile door trims, seat structural materials, seat backboards, ceiling materials, console boxes, automobile dashboards, various instrument panels, deck trims, bumpers, spoilers, cowlings, etc. Furthermore, examples of interior materials and exterior materials for buildings, furniture, etc. That is, examples of door covering materials, door structural materials, and covering materials for various furniture (desks, chairs, shelves, chests, etc.) can be mentioned. Other examples include packaging bodies, containers (trays, etc.), protective members, and partition members.

Claims (5)

A polyamide compound containing 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),
Talc and
Including,
It does not include a modified polyester elastomer obtained by reacting a monomer selected from unsaturated carboxylic acids and unsaturated carboxylic acid derivatives with a polyester elastomer,
Does not contain styrene resins containing rubber polymers,
Does not contain polyphenylene ether
The composite does not contain a rubbery polymer .

(wherein x is an integer from 6 to 12, and y is an integer from 8 to 18.)

(z is an integer from 2 to 18.)

The composite according to claim 1 , wherein the polymer does not include any other polymer than the polyamide compound . 3. The composite 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 95:5 to 5:95. The composite according to claim 1 , wherein the talc content is 1% by mass or more and 40% by mass or less. A method for producing the composite according to any one of claims 1 to 4 , comprising the steps of:
The polyamide compound and the talc are kneaded in a twin-screw kneading extruder.

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