JP2022162256A - Composite and composite production method - Google Patents

Abstract

To provide a novel composite.SOLUTION: The composite contains a polyamide compound and talc. The polyamide compound comprises a dicarboxylic acid unit represented by the specified general formula (1), a dicarboxylic acid unit represented by the specified general formula (2), and a particular diamine unit represented by the specified general formula (3). In the general formula (1), x is an integer from 6 to 12; and y is an integer from 8 to 18. In the general formula (2), z is an integer from 2 to 18.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to composites and methods of making composites.

Biopolymers such as polyamide compounds using plant-derived compounds as starting materials are attracting attention as a starting material instead of petroleum-based polymers from the viewpoint of global warming prevention and resource risk reduction (for example, Non-Patent Documents 1-2, Patent Document 1 reference).

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, the properties of conventional biopolymers are not necessarily sufficient for some applications, and improvements in properties have been desired.
The present disclosure is intended to solve the above problems, and can be implemented as the following modes.

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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;
A complex containing

(x represents an integer of 6 to 12, and y represents an integer of 8 to 18.)

(z represents an integer from 2 to 18.)

The composites of the present disclosure have properties superior to conventional polyamide compounds.
The manufacturing methods of the present disclosure can produce composites with properties superior to conventional polyamide compounds.

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

Here is another example of the disclosure.
A composite in which the molar ratio of dicarboxylic acid units represented by general formula (1):dicarboxylic acid units represented by general formula (2) is from 95:5 to 5:95.
The composite, wherein the talc content 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 with a twin-screw kneading extruder.

Hereinafter, embodiments of the present disclosure will be described in detail. In this specification, the description using "-" for the numerical range includes the lower limit and the upper limit unless otherwise specified. For example, the description “10 to 20” includes both the lower limit “10” and the upper limit “20”. That is, "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. Complex The complex comprises 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.

(x represents an integer of 6 to 12, and y represents an integer of 8 to 18.)

(z represents 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 within a range that does not impair the effects of the present disclosure.

In the polyamide compound of the present disclosure, the content of dicarboxylic acid units is not particularly limited. The content of dicarboxylic acid units is usually 5 to 50 mol %, preferably 20 to 50 mol %, more preferably 30 to 50 mol %.
In the polyamide compound of the present disclosure, the content of diamine units is not particularly limited. The content of diamine units is usually 5 to 50 mol%, preferably 20 to 50 mol%, 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 substantially the same, and the content of the dicarboxylic acid unit is ±1 mol% of the content of the diamine unit. more preferred.

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

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

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

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

When the total amount of dicarboxylic acid units in the polyamide compound of the present disclosure is 100 mol%, the total content of the dicarboxylic acid units represented by the general formulas (1) and (2) is not particularly limited. It preferably contains a total of 30 to 100 mol% of the dicarboxylic acid units represented by the general formulas (1) and (2), more preferably 50 to 100 mol%, and particularly preferably 70 to 100 mol%. When the content of the dicarboxylic acid units represented by the general formulas (1) and (2) is within this range, a composite with a high flexural modulus can be obtained. Also, within this range, a composite with a high glass transition temperature (Tg) can be obtained.

Polyamide compound WHEREIN: The molar ratio of the dicarboxylic acid unit represented by General formula (1) and the dicarboxylic acid unit represented by General formula (2) is not specifically limited.
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 preferably 95:5 to 5:95, preferably 90:10 to 10:90. more preferably 80:20 to 20:80.

Compounds that can form dicarboxylic acid units other than the dicarboxylic acid units represented by formulas (1) and (2) are not particularly limited.
For example, specific examples of dicarboxylic acid compounds include linear aliphatic dicarboxylic acids having 2 to 25 carbon atoms such as oxalic acid, malonic acid, fumaric acid and maleic acid, or unsaturated fatty acids obtained by fractional distillation of triglycerides. Alicyclic dicarboxylic acids such as dimerized aliphatic dicarboxylic acids having 14 to 48 carbon atoms (dimer acids) and hydrogenated products thereof (hydrogenated dimer acids), 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. Derivatives of these dicarboxylic acid compounds may also be used. Examples of derivatives include carboxylic acid halides and the like. These can be used individually or in combination of 2 or more types.
When the total 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 acids represented by the above general formulas (1) and (2) is not particularly limited. The content of dicarboxylic acid units other than the dicarboxylic acids 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 to have This is because when the content of the dicarboxylic acid units other than the dicarboxylic acid units represented by the general formulas (1) and (2) is within this range, the tensile strength, tensile modulus, flexural 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 100 mol %, the content of diamine units represented by the general formula (3) is not particularly limited. It preferably contains 5 to 100 mol %, more preferably 50 to 100 mol %, and particularly preferably 80 to 100 mol % of the diamine unit represented by the general formula (3). This is because when the content of the diamine acid unit represented by the general formula (3) is within this range, the tensile strength, tensile modulus, flexural elasticity and the like are excellent.

Repeating units that 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 general formula (2) and a diamine unit represented by general formula (3).
Different repeating units may be randomly present in the polyamide compound.
In addition, repeating units of the same kind may be present in the polyamide compound in the form of blocks.

A compound that can constitute a diamine unit other than the diamine unit represented by formula (3) is not particularly limited.
For example, diamines other than the diamine unit represented by general formula (3) include known aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like.

Examples of aliphatic diamines that can constitute diamine units other than the diamine unit represented by formula (3) include 1,1-meta-xylylenediamine, 1,3-propanediamine, and pentamethylenediamine. .
Examples of alicyclic diamines include 4,4'-methylenebis(cyclohexylamine) and 1,3-bis(aminomethyl)cyclohexane.
Aromatic diamines such as 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, 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, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene , octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3,5-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestenyloxy-2,4 -diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, lanostanyl 3,5-diaminobenzoate, 3,6-bis(4-aminobenzoyloxy)cholestane, 3,6-bis (4-amino phenoxy)cholestane, 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-diaminophenyl)piperazine-4-carboxylic acid, 4-(morpholin-4-yl)benzene-1, 3-diamine, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, α-amino-ω-aminophenylalkylene, and the like.
These can be used individually or in combination of 2 or more types.

When the total amount of diamine units in the polyamide compound of the present disclosure 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 diamine units other than the diamine represented by 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 the diamine unit other than the diamine unit represented by the general formula (3) is within this range, the tensile strength, tensile modulus, flexural elasticity, etc. are improved.

1.1.3 Degree of Polymerization of Polyamide Compound The degree of polymerization of the polyamide compound of the present disclosure is not particularly limited. Viscosity numbers measured as follows are preferably in the range of 4.0 to 10.0, more preferably in the range of 5.0 to 8.0.
In addition, the viscosity number measurement is performed as follows.
Test method: JIS K6933 compliant 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) x 1/C
t0: flow-down time of measurement solvent (s)
t: flow-down time of the sample solution (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 and a diamine compound.

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

The polyamide compound of the present disclosure can be produced by polycondensing 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.
A method for producing a polyamide compound is not particularly limited. Examples of methods for producing a polyamide compound include (1) a method using an acid or base catalyst, (2) a method for activating a carboxylic acid, (3) a method using transesterification, and (4) using a condensing agent. and the like are preferably used.

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

Also, a monoamine or monocarboxylic acid may be added as a molecular weight modifier during polycondensation. Moreover, 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 shifted from 1 and adjusted.

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

The concentration of the polyamide compound (polymer concentration) is not particularly limited, although it varies depending on the solubility of the produced polyamide compound in the solvent and the viscosity of the solution. 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 from the content and composition ratio of the polyamide compound composition, solubility, solution viscosity, handleability, and ease of defoaming.

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

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

The polymerization reaction product (polyamide compound) obtained in this way requires neutralization because it involves hydrogen halide as a by-product. 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 and the like are preferably used. be able to. In addition, such a neutralizing agent may be added in the form of powder alone, but it is preferable to use a finely divided neutralizing agent dispersed as a slurry in an organic solvent in terms 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. Also, the solution after the neutralization reaction can be used as it is as the molding solution.

Moreover, the industrial polycondensation method of the polyamide compound of the present disclosure is not particularly limited, and known methods are widely used. Examples thereof include a pressurized salt method, a normal pressure dropping method, a pressurized dropping method, and a reactive extrusion method. Further, the lower the reaction temperature is, the more the polyamide compound can be prevented from yellowing or gelling, and the polyamide compound having stable properties can be obtained.

The pressurized salt method is a method in which a nylon salt is used as a raw material and subjected to melt polycondensation 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 remove condensed water. while polycondensing. While gradually returning the pressure in the can to normal pressure, the temperature was raised to about 10°C above the melting point of the polyamide compound, and then the pressure was gradually reduced to 0.02 MPaG while the temperature was maintained as it was to continue polycondensation. do. When a constant 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, the diamine component is continuously added dropwise to a mixture obtained by heating and melting the dicarboxylic acid component and, if necessary, other components under normal pressure, and polycondensation is performed while removing 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 vessel, and the respective components are stirred and melt-mixed to prepare a mixture. Then, the diamine component is continuously added dropwise to the mixture while pressurizing the inside of the can preferably to about 0.3 to 0.4 MPaG, and polycondensation is carried out while removing condensation water. At this time, the polycondensation reaction is carried out while raising the temperature of the reaction system so that the reaction temperature does not drop below the melting point of the polyamide compound to be produced. When the set molar ratio is reached, the dropwise addition of the diamine component is terminated, and while the pressure inside the can is gradually returned to normal pressure, the temperature is raised to about +10°C, the melting point of the polyamide compound, and then the pressure is gradually reduced to 0.02 MPaG. while maintaining the same temperature to continue the polycondensation. When a constant 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 incorporation into the polyamide backbone by transamidation reaction.

1.2 Talc Talc is not particularly limited. For example, talc is plate-like particles of magnesium silicate having a layered structure, and its composition is a mineral such as Mg ₃ Si ₄ O ₁₀ (OH) ₂ .
The content of talc in the composite is not particularly limited. 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, and 2% by mass, based on 100% by mass of the entire composite. 30 mass % or less is more preferable, and 5 mass % or more and 20 mass % or less is still more preferable.

1.2.1 Particle size (D50)
The particle size (D50) (median size) of talc is not particularly limited. The particle diameter (D50) of 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, from the viewpoint of improving the tensile strength, tensile modulus, bending elastic modulus, etc. of the composite, and is 2 μm. It is more preferable that the thickness is not less than 8 μm and not more than 8 μm. The particle size (D50) can be measured by laser diffraction method.

1.2.2 Apparent Density The apparent density of talc is not particularly limited. The apparent density of talc is preferably 0.05 g/mL or more and 0.7 g/mL or less, and 0.08 g/mL or more and 0.08 g/mL or more, from the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite. 6 g/mL or less is more preferable, and 0.1 g/mL or more and 0.5 g/mL or less is even more preferable. The apparent density can be measured according to JIS K5101.

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

1.2.4 Water content The water content of talc is not particularly limited. The water content of talc is preferably 0.1% or more and 0.5% or less, and 0/1% or more and 0.3% or less, from the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite. more preferred. Moisture content can be measured according to JIS K5101.

1.2.5 Oil Absorption The oil absorption of talc is not particularly limited. 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, from the viewpoint of improving the tensile strength, tensile modulus, flexural modulus, etc. of the composite. The oil absorption can be measured according to JIS K5101.

1.2.6 Chromaticity The whiteness of talc is not particularly limited. The whiteness of 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. Whiteness can be measured by the Hunter method.

1.3 Composite Properties In the composites of the present disclosure, talc is well dispersed in the polyamide compound. Therefore, the composite has high tensile strength, tensile modulus, and bending elasticity.
The dispersibility of talc in general synthetic polymers is not so high. However, in the composites of the present disclosure, talc is highly dispersible. The reason is presumed 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 (nC _x H _2x+1 ) has an affinity with Mg, Si, etc. of talc. Since it is high, it is presumed that the dispersibility of talc is high.
Further, when x = 9 and y = 11 in the general formula (1), the dicarboxylic acid unit represented by the general formula (1) is derived from a plant, and talc is a natural ore. Be environmentally friendly.
These features are not found in composites using conventional synthetic polymers.

1.4 Additives Lubricants, crystallization nucleating agents, anti-whitening agents, delustering agents, heat stabilizers, weather stabilizers, ultraviolet absorbers, plasticizers, flame retardants, and other additives may be added to the composite of the present disclosure depending on the application and performance. Additives such as retardants, antistatic agents, anti-coloring agents, antioxidants and impact modifiers may be added. These additives can be added as necessary within a range that does not impair the effects of the composite of the present disclosure.

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

2. Composite Manufacturing Method The composite manufacturing method is not particularly limited. The composite can be suitably produced by kneading the polyamide compound and talc with a twin-screw kneading extruder.

EXAMPLES Hereinafter, the present disclosure will be described more specifically with reference to examples. In addition, in the following description, a polyamide compound may also be called a "biopolymer." In addition, the composite may also be referred to as a “bio-polymer compound”.

1. Synthesis of Polyamide Compound (Synthesis of PA ₈₀ AC ₂₀ BPE ₁₀₀ )
A _polyamide compound _{( PA80AC20BPE100} ) was synthesized according to the following scheme. Z=4 in the scheme below.

Specifically, 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BPE) (41.1 g, 100.0 mmol) and THF were placed in a separable flask (1000 mL) under a nitrogen atmosphere. (300 mL) was added, and after stirring at 0°C for 10 minutes using a mechanical stirrer, triethylamine (30.8 mL, 220.0 mmol) was added, followed by stirring at 0°C for 10 minutes. After that, acid chloride (1′) (57.2 g, 80.0 mmol) and adipol chloride (3.7 g, 20.0 mmol) were dissolved in THF (100 mL), 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 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, 1533.1, 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. Manufacture of Composite A composite (composite material) was obtained by kneading 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 with a twin-screw kneading extruder. . The composite was pelletized.
Observation of the composite with an electron microscope (SEM) confirmed a morphology in which talc was uniformly dispersed in the polyamide compound.

3. 3. Evaluation of Mechanical Properties 3.1 Preparation of Test Piece A test piece was prepared from 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 160-240°C and a mold temperature of 14-18°C. As a test piece, a JIS K7161 (t=2 mm) multi-purpose test piece 5A type (dumbbell shape), width 10 mm×length 80 mm×thickness 4 mm test piece (strip shape) was molded. Dumbbell-shaped specimens were used for tensile tests. The strip-shaped test piece was processed into a K7110 type 1 test piece and used for the Charpy impact test and bending test.

3.2 Tensile Test Tensile properties were evaluated by performing a tensile test in accordance with JIS K 7161-2 to evaluate yield stress (tensile strength), tensile breaking strain, and tensile modulus. In the measurement, the width and thickness of the test piece were measured and used. 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 A bending test was performed to evaluate bending elastic modulus and bending strength. The bending test complied 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 and obtaining a Charpy impact value. The bending test complied with JIS K7111-1. In the test, the width and thickness of the test piece were measured. A Charpy impact tester, Toyo Seiki Seisakusho DG-UB, was used for the measurement.

3.5 Test Results Table 1 and Figures 1 to 3 show the test results.

From the test results in Table 1 and FIGS. 1-3, it can be seen that the composite has much 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 thermogravimetric/differential calorimetric analysis (TG/DTA). In addition, Tg measurement was evaluated based on JIS K7121. Td and thermal decomposition temperature measurement were evaluated according to JIS K7120.
Thermal analysis equipment EXSTAR DSC7020 manufactured by Hitachi High-Tech Science Co., Ltd. and TG8120 manufactured by Rigaku Co., Ltd. were used for the measurement, and the measurement conditions were as follows.
DSC measurement was carried out in a measurement temperature range of -50 to 280°C, a heating rate of 10°C/min, and in a nitrogen stream (50 mL/min).
For TG/DT measurement, measurement temperature: room temperature to 500°C, temperature increase rate: 10°C/min, and measurement was performed in a nitrogen stream (150 mL/min).

4.2 Measurement results Table 2 shows the measurement results.

From the measurement results in Table 2, it was confirmed that the composite has higher thermal stability than the biopolymer alone.

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

The foregoing examples are for illustrative purposes only and are not to be construed as limiting the present disclosure. While the present disclosure has been described with reference to exemplary embodiments, it is understood that the words used in describing and illustrating the present disclosure are words of description and illustration, rather than words of limitation. Changes may be made within the scope of the appended claims, as detailed herein, without departing from the scope or essence of the disclosure in its form. Although reference has been made herein to particular structures, materials and examples in the recitation of the disclosure, it is not intended that the disclosure be limited to the disclosure herein, but rather the disclosure as set forth in the appended claims. It covers all functionally equivalent structures, methods and uses within its scope.

The present disclosure is not limited to the embodiments detailed above, and various modifications or changes are possible within the scope of the claims of the present disclosure.

The composite of the present disclosure can be used in a wide range of other applications, as well as applications to which conventional polyamide compounds have been applied. For example, it can be used as any member of automobiles, railroad vehicles, ships, airplanes, and the like. For example, it is used as an interior material, an exterior material, and the like. Among these, automobile supplies include automobile interior materials, automobile instrument panels, automobile exterior materials, and the like. Specifically, door substrates, package trays, pillar garnishes, switch bases, quarter panels, side panels, armrests, automotive door trims, seat structural materials, seat backboards, ceiling materials, console boxes, automotive dashboards, etc. Instrument panels, deck trims, bumpers, spoilers, cowlings, etc. Further examples include interior materials and exterior materials for buildings, furniture, and the like. That is, they include door covering materials, door structural materials, and covering materials for various types of furniture (desks, chairs, shelves, chests of drawers, etc.). Other examples include packaging bodies, containers (trays and the like), protective members, partition members, and the like.

Claims (4)

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;
A complex containing

(x represents an integer of 6 to 12, and y represents an integer of 8 to 18.)

(z represents an integer from 2 to 18.)

2. The complex according to claim 1, wherein the molar ratio of dicarboxylic acid units represented by general formula (1) to dicarboxylic acid units represented by general formula (2) is from 95:5 to 5:95. The composite according to claim 1 or 2, 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 3,
A method for producing a composite, comprising kneading the polyamide compound and the talc with a twin-screw kneading extruder.

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