Polyamide composition

Abstract

To provide a polyamide composition having a reduced carbon footprint (CFP).SOLUTION: To solve the above problem, the present invention provides a polyamide composition comprising (A) a polyamide, wherein the polyamide (A) includes structural units derived from (B) hexamethylenediamine, and the hexamethylenediamine (B) contains hexamethylenediamine produced from biomass using a catalyst.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyamide composition. [Background technology]

[0002] Polyamides have excellent strength, heat resistance, chemical resistance, and specific gravity, meaning that they have a lower specific gravity than metals, and have therefore been used as a metal substitute for automotive mechanical parts and other applications.

[0003] Fossil fuel-derived raw materials, which have traditionally been used in chemical manufacturing processes, are at risk of depletion and are considered to be a contributing factor to global warming. Therefore, in recent years, there has been a desire to switch to renewable raw materials, such as biomass-derived raw materials. As part of the switch to renewable raw materials, technology using metabolically modified microorganisms through genetic engineering is expected to be a new chemical manufacturing process. For example, biopropylene and biobutadiene can be produced from bionaphtha using a cracker, and these can then be used to produce hexamethylenediamine using existing methods (Patent Document 1). It has also been suggested that hexamethylenediamine can be produced from bioethanol, glucose, or fructose (Patent Document 2, Non-Patent Document 1).

[0004] Here, biomass refers to organic resources derived from living organisms. Even if plastics made from this raw material are incinerated, there is no increase in net carbon dioxide emissions, which includes the carbon dioxide absorbed in the process of producing the biomass. Therefore, the carbon footprint (CFP), which is the value calculated by converting greenhouse gases emitted in the entire process from raw material procurement to disposal, is reduced, and the burden on the global environment is small. The above biomass-derived polyamide is described in, for example, Patent Document 3. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] International Publication No. 2023 / 145941 [Patent Document 2] Special Publication No. 2015-506943 [Patent Document 3] Japanese Patent Application Laid-Open No. 2006-348057 [Non-patent literature]

[0006] [Non-Patent Document 1] Molecules. 2018 Sep; 23(9): 2201. Summary of the Invention [Problem to be solved by the invention]

[0007] The biomass-derived polyamide described in Patent Document 3 is limited to polyamides made from pentamethylenediamine, and there is no description of biomass-derived polyamide 66.

[0008] The present invention has been made in view of the above circumstances, and provides polyamide 66 with reduced CFP. [Means for solving the problem]

[0009] That is, the present invention includes the following aspects. (1)(A) comprises a polyamide; the (A) polyamide contains a structural unit derived from (B) hexamethylenediamine, The polyamide composition, wherein the (B) hexamethylenediamine is produced from biomass using a catalyst. (2) The polyamide composition according to (1), wherein the weight-average molecular weight of the polyamide (A) is 20,000 to 200,000. (3) The polyamide composition according to (1) or (2), wherein the Mw / Mn of the polyamide (A) is 1.8 to 5.0. (4) The polyamide composition according to any one of (1) to (3), characterized in that the relative viscosity ηr in sulfuric acid at 25° C. is 1.8 or more. (5) The polyamide composition according to any one of (1) to (4), further comprising a resin (C). (6) The polyamide composition according to any one of (1) to (5), further comprising an additive (D). (7) The polyamide composition according to any one of (1) to (6), further comprising (E) a flame retardant. (8) The polyamide composition according to any one of (1) to (7), further comprising (F) a filler. (9) The polyamide composition according to any one of (1) to (8), wherein the polyamide (A) is subjected to solid-state polymerization. [Effects of the Invention]

[0010] According to the present invention, a polyamide composition having reduced CFP can be obtained. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0012] In this specification, the term "polyamide" refers to a polymer having an amide (-NHCO-) ​​group in the main chain.

[0013] [Polyamide composition] The polyamide composition of the present embodiment contains (A) a polyamide. In this embodiment, the (A) polyamide contains a structural unit derived from (B) hexamethylenediamine, The (B) hexamethylenediamine contains hexamethylenediamine produced from biomass using a catalyst.

[0014] The polyamide composition of the present embodiment has the above-described structure, and thus a polyamide composition with a low CFP can be obtained.

[0015] Hereinafter, the (A) polyamide to (G) filler may be referred to as component (A) to component (G), respectively.

[0016] Each component of the polyamide composition of the present embodiment will be described in detail below. <(A) Polyamide> Examples of (A) polyamides include (a-1) polyamides obtained by condensing diamines and dicarboxylic acids. Also included are copolymers of (a-1) with (a-2) polyamides obtained by ring-opening polymerization of lactams, and / or (a-3) polyamides obtained by self-condensation of ω-aminocarboxylic acids. Polyamides may be used alone. Although two or more types may be used in combination, the (A) polyamide of this embodiment is a polyamide that contains structural units derived from (B) hexamethylenediamine, and the (B) hexamethylenediamine is produced from biomass using a catalyst.

[0017] The diamine (monomer) used in the production of (a-1) polyamide must contain hexamethylenediamine produced from biomass using a catalyst. Other diamines include, but are not limited to, linear aliphatic diamines, branched aliphatic diamines, alicyclic diamines, and aromatic diamines. Examples of the linear aliphatic diamine include, but are not limited to, hexamethylenediamine and pentamethylenediamine. Examples of branched aliphatic diamines include, but are not limited to, 2-methylpentanediamine and 2-ethylhexamethylenediamine. Examples of alicyclic diamines include, but are not limited to, cyclohexanediamine, cyclopentanediamine, and cyclooctanediamine. Examples of aromatic diamines include, but are not limited to, p-phenylenediamine and m-phenylenediamine. (a-1) As the dicarboxylic acid (monomer) used in the production of polyamide, petroleum-derived dicarboxylic acids and biomass-derived dicarboxylic acids can be used alone or in combination. Specific examples of dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids. Examples of the aliphatic dicarboxylic acid include, but are not limited to, adipic acid, pimelic acid, and sebacic acid. The alicyclic dicarboxylic acid is not limited to the following, but examples thereof include cyclohexanedicarboxylic acid. Examples of aromatic dicarboxylic acids include, but are not limited to, phthalic acid and isophthalic acid. The diamines and dicarboxylic acids as the monomers may be condensed either alone or in combination of two or more.

[0018] (a-2) Examples of lactams used in the production of polyamides include, but are not limited to, pyrrolidone, caprolactam, undecalactam, and dodecalactam. (a-3) The ω-aminocarboxylic acid used in the production of polyamide is not limited to the following, but examples thereof include ω-amino fatty acids, which are ring-opened compounds of the above lactams with water. Furthermore, two or more kinds of the lactam or ω-aminocarboxylic acid may be used in combination and condensed.

[0019] Specific examples of the (A) polyamide contained in the polyamide composition include polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene dodecamide), polyamide 6T (polyhexamethylene terephthalamide), and polyamide 6I (polyhexamethylene isophthalamide), which contain structural units derived from (B) hexamethylene diamine, and the (B) hexamethylene diamine is produced by using a catalyst from biomass. Examples of the polyamides include polyamides containing hexamethylenediamine produced using the above-mentioned compound, and copolymerized polyamides containing these as a constituent component. Furthermore, examples of the polyamides that can be produced using the above-mentioned compound include polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecane amide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), and polyamide 9T (polynonamethylene terephthalamide). Examples of the copolymer include copolymer polyamides containing the copolymer as a component. Among these, the polyamide resin is preferably polyamide 66, polyamide 610, polyamide 612, polyamide 6I, polyamide 66 / 6, or polyamide 66 / 6I.

[0020] The amount of polyamide (A) in the polyamide composition can be, for example, 10.0 mass% or more and 99.8 mass% or less, for example, 20.0 mass% or more and 90.0 mass% or less, or for example, 30.0 mass% or more and 80.0 mass% or less, relative to the total mass of polyamide.

[0021] In producing (A) polyamide, the amount of dicarboxylic acid added and the amount of diamine containing (B) hexamethylenediamine added are preferably approximately the same molar amount. Taking into consideration the amount of diamine that escapes to the outside of the reaction system during the polymerization reaction, the molar amount of all diamines relative to the molar amount of all dicarboxylic acids is preferably 0.9 to 1.2, more preferably 0.95 to 1.1, and even more preferably 0.98 to 1.05.

[0022] The method for producing (A) polyamide preferably further comprises a step of increasing the degree of polymerization of (A) polyamide, and may optionally comprise a step of capping the ends of the resulting polymer with an end-capping agent.

[0023] Specific methods for producing (A) polyamide include various methods such as those exemplified in the following 1) to 4). 1) A method in which an aqueous solution of a salt of dicarboxylic acid and (B) a diamine containing hexamethylenediamine, or a mixture of dicarboxylic acid and (B) a diamine containing hexamethylenediamine, or an aqueous suspension of these, is heated and polymerized while maintaining the molten state (hereinafter, this may be referred to as "thermal melt polymerization method"). 2) A method of increasing the degree of polymerization of (A) polyamide obtained by the hot melt polymerization method while maintaining it in a solid state at a temperature below the melting point (hereinafter sometimes referred to as "hot melt polymerization / solid state polymerization method"). 3) A method of polymerizing a salt of a diamine containing dicarboxylic acid (B) hexamethylenediamine, or a mixture of a dicarboxylic acid (B) and a diamine containing hexamethylenediamine while maintaining the salt in a solid state (hereinafter, this may be referred to as a "solid-state polymerization method"). 4) A method of polymerization using a dicarboxylic acid halide component and (B) a diamine component containing hexamethylenediamine (hereinafter, sometimes referred to as a "solution method"). Among these, a specific production method for (A) polyamide is preferably a production method including a thermal melt polymerization method. Furthermore, when producing (A) polyamide by a thermal melt polymerization method, it is preferable to maintain the molten state until the polymerization is completed. Examples of methods for maintaining the molten state include a method of producing (A) polyamide under polymerization conditions suitable for the composition of the polyamide. Examples of polymerization conditions include the following: First, the polymerization pressure in the thermal melt polymerization method is controlled to 14 kg / cm or more and 25 kg / cm or less (gauge pressure), and heating is continued. Next, the pressure in the vessel is reduced to atmospheric pressure (gauge pressure: 0 kg / cm) over 30 minutes or more, thereby obtaining (A) polyamide with the desired composition.

[0024] In the method for producing (A) polyamide, the polymerization form is not particularly limited, and may be a batch system or a continuous system. The polymerization apparatus used for producing (A) polyamide is not particularly limited, and known apparatuses can be used, such as autoclave-type reactors, tumbler-type reactors, and extruder-type reactors such as kneaders.

[0025] Hereinafter, as a method for producing (A) polyamide, (Aa) is produced by a batch-type hot melt polymerization method. A method for producing polyamide 66 will be specifically shown, but the method for producing (Aa) polyamide 66 is not limited thereto. First, an aqueous solution containing about 40% by mass or more and 60% by mass or less of (Aa) the raw material components of polyamide 66 (adipic acid, (B) hexamethylenediamine) is concentrated to about 65% by mass or more and 90% by mass or less in a concentration tank operated at a temperature of 110°C or more and 180°C or less and a pressure of about 0.035 MPa or more and 0.6 MPa or less (gauge pressure) to obtain a concentrated solution. Next, the obtained concentrated solution is transferred to an autoclave, and heating is continued until the pressure in the autoclave reaches about 1.2 MPa or more and 2.2 MPa or less (gauge pressure). Thereafter, in the autoclave, the pressure is maintained at approximately 1.2 MPa to 2.2 MPa (gauge pressure) while removing at least one of the water and gas components, and when the temperature reaches approximately 220°C to 260°C, the pressure is reduced to atmospheric pressure (gauge pressure: 0 MPa). After the pressure inside the autoclave is reduced to atmospheric pressure, the pressure can be reduced as needed to effectively remove the by-produced water. The autoclave is then pressurized with an inert gas such as nitrogen, and the polyamide melt is extruded from the autoclave as a strand. The extruded strand is cooled and cut to obtain pellets of (A) polyamide 66.

[0026] The polymer terminals of (A) polyamide are not particularly limited, but can be classified and defined as follows: 1) amino terminus, 2) carboxy terminus, 3) terminus with a capping agent, and 4) other terminus. 1) The amino terminal is a polymer terminal having an amino group (-NH2 group) and is derived from the raw material (B) hexamethylenediamine unit. 2) The carboxyl end is a polymer end having a carboxyl group (-COOH group) and is derived from the raw material adipic acid. 3) The term "terminals formed by a capping agent" refers to terminals formed when a capping agent is added during polymerization. Examples of the capping agent include the above-mentioned terminal capping agents. 4) Other terminals are polymer terminals that are not classified into the above 1) to 3). Specific examples of other terminals include terminals generated by deammoniating an amino terminal, terminals generated by decarboxylating a carboxy terminal, etc.

[0027] (A) Properties of polyamide The weight average molecular weight Mw can be used as an index of the molecular weight of polyamide. The weight average molecular weight Mw of polyamide can be, for example, 10,000 or more and 200,000 or less, for example, 15,000 or more and 100,000 or less, for example, 20,000 or more and 90,000 or less, or for example, 25,000 or more and 85,000 or less. The weight average molecular weight Mw can be measured by gel permeation chromatography (GPC) as described in the examples below.

[0028] (A) The molecular weight distribution of polyamide is indicated by the weight average molecular weight Mw / number average molecular weight Mn. The Mw / Mn of the (A) polyamide can be 1.8 or more and 5.0 or less, for example, 1.8 or more and 4.0 or less, for example, 1.9 or more and 3.0 or less.

[0029] Examples of methods for controlling the Mw / Mn of (A) polyamide within the above range include a method of adding a known polycondensation catalyst such as phosphoric acid or sodium hypophosphite as an additive during the hot melt polymerization of (A) polyamide 66, and a method of controlling polymerization conditions such as heating conditions and reduced pressure conditions. (A) The Mw / Mn of the polyamide was obtained using GPC as described in the Examples below. The weight average molecular weight Mw and number average molecular weight Mn can be used to calculate the molecular weight.

[0030] <(B) Hexamethylenediamine> The polyamide (A) contained in the polyamide composition of the present embodiment is obtained, for example, by polycondensation of a dicarboxylic acid and hexamethylenediamine (B) as described above. (B) Hexamethylenediamine is produced from petroleum resources or biomass using a catalyst. Examples of biomass include bionaphtha, bioethanol, glucan, glucose, fructose, and sucrose. Examples of catalysts include metal catalysts and organic catalysts.

[0031] (B) Hexamethylenediamine in this embodiment includes (B) hexamethylenediamine derived from biomass. The proportion of (B) hexamethylenediamine derived from biomass in (B) hexamethylenediamine constituting (A) polyamide is not particularly limited, but is preferably 50% by weight or more, more preferably 60% by weight or more, even more preferably 70% by weight or more, and even more preferably 80% by weight or more. By setting the ratio of biomass-derived (B) hexamethylenediamine in (B) hexamethylenediamine constituting (A) polyamide to the above lower limit or more, the CFP of the polyamide composition can be further reduced. The proportion of component (B) derived from biomass can be calculated, for example, according to the method described in ASTM6866, by combusting a sample and calculating the concentration of radioactive carbon contained in the sample.

[0032] <(C) Resin> The polyamide composition of the present embodiment may further contain, but is not particularly limited to, a resin (C). The resin is not particularly limited, but examples thereof include polyamide resin, polyester resin, polyacetal resin, polycarbonate resin, polyacrylic resin, polyphenylene ether resin (including modified polyphenylene ether obtained by blending or graft polymerizing polyphenylene ether with other resins), polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyketone resin, polyphenylene ether ketone resin, polyimide resin, polyamideimide resin, polyetherimide resin, polyurethane resin, polyolefin resin (for example, α-olefin (co)polymer), and various ionomers. When a polyamide resin is used as the resin, a polyamide different from the above-mentioned (A) polyamide is used.

[0033] <(D) Additives> The polyamide composition of the present embodiment may further contain, but is not limited to, additive (D), such as a heat stabilizer, lubricant, catalyst, colorant (dye, pigment), flow modifier, molecular weight modifier, antioxidant, compatibilizer, oligomer, or polymer.

[0034] The heat stabilizer may be any that inhibits thermal degradation of the material, prevents discoloration due to heat, and improves heat aging resistance and weather resistance, and includes, but is not limited to, copper-based stabilizers such as copper compounds such as copper acetate and copper iodide, phenol-based stabilizers such as hindered phenol compounds, phosphite-based stabilizers, hindered amine-based stabilizers, triazine-based stabilizers, sulfur-based stabilizers, etc. Other examples include the antioxidants mentioned above, such as alkylphenols, alkylene bisphenols, and alkylphenol thioethers, and ultraviolet absorbers such as salicylic acid esters, benzotriazole, and hydroxybenzophenone.

[0035] When a heat stabilizer is added to the polyamide composition of this embodiment, the content of the heat stabilizer is preferably 0.005 to 10 parts by mass per 100 parts by mass of the (A) polyamide. By setting the content of the heat stabilizer to 0.005 parts by mass or more, the effect of improving the thermal stability can be sufficiently obtained. Furthermore, by setting the content to 10 parts by mass or less, good manufacturability can be obtained in the extrusion process.

[0036] The polyamide composition of this embodiment may contain a lubricant. The content of the lubricant in the polyamide composition of this embodiment is 0.01 to 2.0 parts by mass, preferably 0.05 to 1.0 part by mass, and more preferably 0.08 to 0.8 parts by mass, relative to 100 parts by mass of the (A) polyamide.

[0037] The polyamide composition of the present embodiment may contain a colorant. By containing a colorant, it is possible to color a molded article.

[0038] Examples of colorants include, but are not limited to, dyes such as nigrosine, pigments such as titanium oxide and carbon black, metal particles such as aluminum, colored aluminum, nickel, tin, copper, gold, silver, platinum, iron oxide, stainless steel, and titanium, and metallic pigments such as mica pearl pigments, colored graphite, colored glass fiber, and colored glass flakes. These colorants can be used alone or in combination of two or more.

[0039] In the polyamide composition of this embodiment, the content of the colorant is preferably 0.01 parts by mass or more and 0.5 parts by mass or less, more preferably 0.05 parts by mass or more and 0.25 parts by mass or less, and even more preferably 0.1 parts by mass or more and 0.2 parts by mass or less, relative to 100 parts by mass of the (A) polyamide.

[0040] <(E) Flame retardant> The polyamide composition of the present embodiment may further contain a flame retardant (E). Examples of the flame retardant include, but are not limited to, halogen-containing flame retardants, phosphorus-based flame retardants, and melamine cyanurate. Furthermore, a combination of two or more flame retardants may be used, or a flame retardant aid may be used.

[0041] In the polyamide composition of this embodiment, the content of the flame retardant is preferably 1 part by mass or more and 50 parts by mass or less, more preferably 3 parts by mass or more and 45 parts by mass or less, and even more preferably 5 parts by mass or more and 35 parts by mass or less, per 100 parts by mass of the (A) polyamide.

[0042] <(F) Filler> The polyamide composition of the present embodiment may further contain a filler (F). By containing the filler (F), the polyamide composition of the present embodiment can further improve mechanical properties such as strength and rigidity when molded into an article.

[0043] The (F) filler is not particularly limited, and examples thereof include glass fiber, carbon fiber, calcium silicate fiber, potassium titanate fiber, aluminum borate fiber, glass flake, calcium carbonate, talc, kaolin, mica, hydrotalcite, zinc carbonate, calcium hydrogen phosphate, wollastonite, zeolite, boehmite, magnesium oxide, calcium silicate, sodium aluminosilicate, magnesium silicate, ketjen black, acetylene black, furnace black, carbon nanotubes, graphite, brass, copper, silver, aluminum, nickel, iron, calcium fluoride, montmorillonite, swellable fluoromica, apatite, milled fiber, etc. may be used alone or in combination of two or more.

[0044] Among these, the (F) filler is preferably glass fiber, carbon fiber, glass flake, talc, kaolin, mica, calcium hydrogen phosphate, wollastonite, carbon nanotubes, graphite, calcium fluoride, montmorillonite, swellable fluoromica, or apatite, from the viewpoint of rigidity, strength, and the like. Furthermore, the (F) filler is more preferably one or more selected from the group consisting of glass fiber, calcium carbonate, talc, mica, wollastonite, and milled fiber, further preferably glass fiber or carbon fiber, and particularly preferably glass fiber.

[0045] In the polyamide composition of this embodiment, the content of the (F) filler relative to 100 parts by mass of the (A) polyamide is preferably 0 parts by mass or more and 150 parts by mass or less, more preferably 10 parts by mass or more and 140 parts by mass or less, even more preferably 20 parts by mass or more and 135 parts by mass or less, particularly preferably 25 parts by mass or more and 130 parts by mass or less, and most preferably 30 parts by mass or more and 100 parts by mass or less. When the content of the (F) filler is equal to or greater than the above lower limit, the mechanical properties such as strength and rigidity of the molded article tend to be improved. On the other hand, when the content of the (F) filler is equal to or less than the above upper limit, the molded article tends to have better surface appearance.

[0046] <Other additives> The polyamide composition may contain other additives commonly used in polyamides, provided that the purpose of this embodiment is not impaired. Examples of other additives include fibrillating agents, lubricants, fluorescent bleaching agents, plasticizers, UV absorbers, antistatic agents, flow improvers, reinforcing agents, spreading agents, nucleating agents, rubbers, toughening agents, and other polymers. The content of other additives in the polyamide composition of this embodiment can be appropriately determined by one skilled in the art depending on the purpose.

[0047] [Method of producing polyamide composition] In the method for producing the polyamide composition, the method for adding each of the constituent components is not particularly limited, as long as it is a method of mixing component (A) with, as needed, components (C) to (F) and the other additives described above.

[0048] Examples of methods for mixing the constituent materials include a method in which the materials are mixed using a Henschel mixer or the like, and then fed to a melt kneader and kneaded therein; and a method in which component (A) and components (C) to (F) are melted in a single-screw or twin-screw extruder from a top feeder, and filler (F) and other additives are added as needed from a side feeder.

[0049] The components constituting the polyamide composition may be supplied to the melt kneader by supplying all of the components at once to the same supply port, or by supplying component (A) and, if necessary, components (C) to (F) from different supply ports.

[0050] The melt-kneading temperature is preferably about 250°C or higher and 375°C or lower in terms of resin temperature. The melt-kneading time is preferably about 0.5 minutes or more and 5 minutes or less.

[0051] The melt-kneading device is not particularly limited, and known devices such as melt-kneaders such as a single-screw or twin-screw extruder, a Banbury mixer, or a mixing roll can be used.

[0052] In addition, in the method for producing the polyamide composition, the component (A) can be subjected to solid-state polymerization. do. The solid-state polymerization can be carried out using a commonly used apparatus. That is, it can be carried out batchwise in a cone-type tumbler or continuously in a fluidized-bed drying oven. The polyamide resin pellets of this embodiment are heated to a temperature below the melting point of the polyamide resin, and an inert gas such as nitrogen is passed through or the mixture is kept under reduced pressure to carry out solid-state polymerization and achieve a high degree of polymerization.

[0053] When the component (A) is mixed with the components (C) to (F) and other additives as needed, and then subjected to solid-state polymerization to produce a polyamide composition, it is preferable to compound the components by melt kneading before carrying out solid-state polymerization.

[0054] [Uses of polyamide composition] Molded articles obtained from the polyamide composition according to an embodiment of the present invention are suitable for use as material parts for various applications, such as automobiles, machinery and industrial applications, electrical and electronic applications, industrial materials, construction materials, daily necessities and household goods, etc. Among these, they are particularly suitable for use as automobile parts because of their excellent heat aging resistance and electrical properties. [Example]

[0055] The present invention will be described in detail below with reference to specific examples and comparative examples, but the present invention is not limited to the following examples. Each of the components of the resin compositions used in the examples and comparative examples will be described below.

[0056] <Polyamide> Polyamide 66 (A-1) to (A-7) shown below were obtained under the synthesis conditions described below. (A-1) Polyamide 66: Biomass-derived ratio of HMD 100% (A-2) Polyamide 66: Biomass-derived ratio of HMD 80% (A-3) Polyamide 66: Biomass-derived ratio of HMD 50% (A-4) Polyamide 610: Biomass-derived ratio of HMD 100% (A-5) Polyamide 612: Biomass-derived ratio of HMD 100% (A-6) Polyamide 66: Biomass-derived ratio of HMD 20% (A-7) Polyamide 66: Solid-state polymerized product with 100% biomass-derived HMD

[0057] [(A-1) Synthesis of Polyamide PA66: Example 1] The polyamide polymerization reaction was carried out by the hot melt polymerization method as follows. First, 1500 g of an equimolar salt of (B) hexamethylenediamine synthesized from adipic acid and bionaphtha was dissolved in 1500 g of distilled water to prepare a homogeneous aqueous solution containing 50% by weight of the raw material monomers. This aqueous solution was charged into a 5.4 L autoclave and purged with nitrogen. Next, the solution was concentrated by gradually removing water vapor while stirring at a temperature of 110°C to 150°C to a solution concentration of 70% by weight. The internal temperature was then raised to 220°C. The autoclave was then pressurized to 1.8 MPa. The reaction was continued for 1 hour while gradually removing water vapor to maintain the pressure at 1.8 MPa until the internal temperature reached 245°C. The pressure was then reduced over 1 hour. The autoclave was then maintained at a reduced pressure of 650 torr (86.66 kPa) for 10 minutes using a vacuum device. The final internal temperature of the polymerization was 265°C. Next, the mixture was pressurized with nitrogen and formed into strands from the lower spinneret (nozzle), cooled with water, cut, and discharged in pellet form. The pellets were dried at 100°C in a nitrogen atmosphere for 12 hours to obtain Polyamide A-1 (PA66). The resulting polyamide A-1 (PA66) had a weight average molecular weight of 40,000 and a molecular weight distribution (Mw / Mn) of 2.0.

[0058] [Synthesis of (A-2), (A-3), (A-6), and (C-3) Polyamide PA66: Examples 2, 3, and 29, and Comparative Example 1] Polyamide 66 was synthesized using the same procedure as in the synthesis of polyamide 66 (A-1) described above, except that the biomass-derived ratio of (B) hexamethylenediamine was used as described above, and the remainder was petrochemically derived hexamethylenediamine.

[0059] [(A-4) Synthesis of Polyamide PA610: Example 4] Polyamide 610 was synthesized using the same procedure as in the synthesis of (A-1) polyamide 66 described above, except that sebacic acid was used instead of adipic acid. The resulting polyamide 610 had a weight-average molecular weight of 24,000 and a molecular weight distribution (Mw / Mn) of 2.0.

[0060] [(A-5) Synthesis of Polyamide PA612: Example 5] Polyamide 612 was synthesized using the same procedure as in the synthesis of (A-1) polyamide 66 described above, except that dodecanedioic acid was used instead of adipic acid. The resulting polyamide 612 had a weight-average molecular weight of 24,000 and a molecular weight distribution (Mw / Mn) of 2.0.

[0061] [(A-7) Polyamide PA66 solid-state polymer: Example 8] Polyamide 66 obtained by the same procedure as in the synthesis of (A-1) polyamide 66 described above was placed in an evaporator-type solid-state polymerization apparatus and subjected to solid-state polymerization for 6 hours at 230°C under a nitrogen gas flow. The obtained polyamide 66 had a weight-average molecular weight of 48,000 and a molecular weight distribution (Mw / Mn) of 2.2.

[0062] <Components other than polyamide> Components (C) to (F) contained in each of the examples and comparative examples are shown below. [(C) Resin] C-1: Polyphenylene ether modified with maleic anhydride (m-PPE) C-2: Ethylene-ethyl hydrogen maleate random copolymer (content of ethyl hydrogen maleate units relative to the mass of all structural units of the copolymer: 8% by mass) C-3: Biomass-derived ratio of polyamide 66 HMD 0% C-4: Polyamide 6I Biomass-derived ratio of HMD: 0% C-5: Polyamide 6I / 6T HMD biomass-derived ratio 0% C-6: Polyamide 4T / 6T HMD biomass-derived ratio 0% C-7: Polyamide 66 / 6I HMD biomass-derived ratio 0%

[0063] [(D) Additives] D-1: Maleic anhydride grafted ethylene-butene copolymer (Mitsui Chemicals, Tafmer MD715) D-2: Ethylene-butene copolymer (Mitsui Chemicals, Inc., Tafmer™ DF605) D-3: Polyethylene-polystyrene graft copolymer (NOF Corporation, MODIPER-A1100) D-4: Polyolefin-polyamide polymer (Arkema, APOLHYA LP91) D-5: Polyethyleneimine (BASF, Lupasol FG) D-6: Antioxidant (BASF, Irganox 1098) D-7: Nigrosine dye (Orient Chemical Co., Ltd., TH807) D-8: Carbon black (primary particle size 27 nm) D-9: Adipic acid (Wako Pure Chemical Industries, Ltd., adipic acid) D-10: Calcium stearate (manufactured by Nippon Oil & Fats Co., Ltd., calcium stearate) D-11: Sodium aluminate (Wako Pure Chemical Industries, Ltd., sodium aluminate) D-12: Mixture of copper iodide and potassium iodide (both copper iodide and potassium iodide are manufactured by Wako Pure Chemical Industries, Ltd.) 1 part by mass of copper iodide is mixed with 10 parts by mass of potassium iodide. D-13: Nigrosine (Orient Chemical Co., Ltd., Nubian Black TN-870) D-14: Copper iodide (Wako Pure Chemical Industries, Ltd., copper iodide) D-15: Potassium iodide (Wako Pure Chemical Industries, Ltd., potassium iodide) D-16: Zinc sulfide (SACHTLEBEN, Sactris HD) D-17: Polyoxymethylene monolaurate (Kao Corporation, Emanone) D-18: Laser-transmitting colorant (Orient Chemical Industry Co., Ltd., eBIND LTW-8071H)

[0064] [(E) Flame retardant] E-1: Brominated polystyrene (ALBEMARLE CORPORATION, SAYTEX HP-3010G) E-2: Melamine cyanurate (Nissan Chemical, MC-4500) E-3: Aluminum phosphinate (Clariant, Exolit OP1230) E-4 Antimony trioxide (Daiichi F.R. Co., Ltd., Antimony trioxide)

[0065] [(F) Filler] F-1: Glass fiber (Nippon Electric Glass Co., Ltd., ECS 03T-275H) F-2: Glass fiber (Nippon Electric Glass Co., Ltd., ECS 03-T297) F-3: Glass fiber (average minor axis 7 μm, average major axis 28 μm) F-4: Wollastonite (NYCO, 400WC) F-5: Carbon fiber (Toho Tenax, HTC413) F-6: Talc (average particle size 19.4 μm) F-7: Glass fiber roving (manufactured by Chongqing International Composite Materials Co., Ltd., ER4301H)

[0066] [Production of Polyamide Compositions: Examples 6, 7, 9 to 28, and 30] Each polyamide composition was produced by the following method using the above-mentioned (A) polyamide, (C) additional resin, (D) additive, (E) flame retardant, and (F) filler in the types and proportions shown in Tables 1 and 2.

[0067] A twin-screw extruder (ZSK-26MC, manufactured by Coperion) was used as the polyamide composition production device. The twin-screw extruder had an upstream feed port in the first barrel from the upstream side of the extruder, a downstream first feed port in the sixth barrel, and a downstream second feed port in the ninth barrel. In addition, in the twin-screw extruder, the temperature from the upstream feed port to the die was set to the melting point Tm of each polyamide + 20°C, the screw rotation speed was set to 250 rpm, and the output rate was set to 25 kg / h. In a specific production method using the above production equipment, (A) polyamide, (C) further resin, (D) additive, (E) flame retardant, and (F) filler were dry-blended in the types and proportions shown in Tables 1 and 2, then fed into the upstream feed port of a twin-screw extruder, and (F) filler was fed into the downstream first feed port of the twin-screw extruder. The molten mixture extruded from the die head was cooled in the form of strands and pelletized to obtain pellets of each polyamide composition. The resulting polyamide composition pellets were dried in a nitrogen stream to reduce the moisture content in the polyamide composition to 500 ppm or less.

[0068] <Evaluation: CFP calculation> The carbon footprint (CFP) of each of the obtained samples of the examples and comparative examples was calculated and evaluated. Regarding CFP, see the GHG Protocol “Product Standard " and it was determined that the smaller the CFP value, the smaller the environmental impact and therefore the better.

[0069] [Table 1] [Industrial Applicability]

[0070] According to the present invention, a polyamide composition having reduced CFP can be provided.

Claims

1. (A) A polyamide composition comprising a polyamide, the (A) polyamide contains (B) a structural unit derived from hexamethylenediamine, A polyamide composition, wherein the (B) hexamethylenediamine contains hexamethylenediamine produced from biomass using a catalyst.

2. 2. The polyamide composition according to claim 1, wherein the weight average molecular weight of the polyamide (A) is 20,000 to 200,000.

3. 2. The polyamide composition according to claim 1, wherein the Mw / Mn of the polyamide (A) is 1.8 to 5.

0.

4. 2. The polyamide composition according to claim 1, wherein the relative viscosity ηr in sulfuric acid at 25° C. is 1.8 or more.

5. The polyamide composition according to claim 1, further comprising a resin (C).

6. The polyamide composition according to claim 1, further comprising (D) an additive.

7. The polyamide composition according to claim 1, further comprising (E) a flame retardant.

8. The polyamide composition according to claim 1, further comprising (F) a filler.

9. The polyamide composition according to claim 1, wherein the polyamide (A) is subjected to solid-state polymerization.

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