JP2007332353A - Polyamide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyamide resin having excellent residence heat stability and a high biomass ratio. <P>SOLUTION: The polyamide resin is composed of an adipic acid unit, a pentamethylenediamine unit and a 6-aminocaproic acid unit, wherein the weight ratio between the total amount of the adipic acid unit and the pentamethylenediamine unit and the amount of the 6-aminocaproic acid unit ranges from 97:3 to 75:25. The pentamethylenediamine is preferably produced from lysine by using lysine decarboxylase, a cell capable of producing lysine decarboxylase, or a product produced by any treatment of the cell. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a polyamide resin. Specifically, the present invention uses a raw material containing an adipic acid unit, a pentamethylenediamine unit and a 6-aminocaproic acid unit as constituents and suppressing the generation of carbon dioxide (CO ₂ ) causing global warming. It is related with the polyamide resin excellent in the residence heat stability obtained.

  Conventionally, naphtha, a so-called fossil raw material, has been used as a raw material for polyamide resin, but for the purpose of preventing global warming by suppressing carbon dioxide emissions and forming a recycling-oriented society, the raw material for producing polyamide resin is a raw material derived from biomass. It is envyed to replace it.

  Nylon 56 is known as a polyamide resin manufactured using biomass-derived raw materials. 56 Nylon is produced by heating polycondensation of diaminopentane and adipic acid (for example, see Patent Document 1), or preparing a salt of diaminopentane and adipic acid and heating polycondensation (for example, Patent Document 1). 2) and the like have been proposed.

  The 56 nylon produced in this manner has substantially the same heat resistance and mechanical properties as the 6 nylon and 66 nylon, but has the disadvantage of poor residence heat stability. Resins with poor staying heat stability are not suitable for large molded products with a long molding cycle, such as a resin intake manifold which is an automobile part. Further, even in an extrusion-molded product such as a film or a filament, it is not suitable because a granular defect called fish eye is likely to occur.

  In Patent Document 3, it is proposed to improve the residence heat stability by blending 56 nylon and 66 nylon, but the biomass ratio as the raw material of the polyamide resin is equivalent to the amount of 66 nylon used. (The ratio of the biomass-derived raw material in the use raw material of the polyamide resin) is lowered, which is not desirable.

For these reasons, a polyamide resin having high residence heat stability and a high biomass ratio is desired.
JP 2003-292612 A U.S. Pat. No. 2,130,948 JP 2006-348057 A

  The present invention has been made in view of the above-described conventional situation, and an object thereof is to provide a polyamide resin having excellent residence heat stability and a high biomass ratio.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention contain adipic acid units, pentamethylenediamine units and 6-aminocaproic acid units as constituent components, and are the total of adipic acid units and pentamethylenediamine units. The present inventors have found that the above-mentioned problems can be solved by using a polyamide resin in which the content ratio of the 6-aminocaproic acid unit is within a specific range, and the present invention has been completed.

  That is, the first gist of the present invention includes an adipic acid unit, a pentamethylenediamine unit and a 6-aminocaproic acid unit as constituents, and the weight of the sum of the adipic acid unit and the pentamethylenediamine unit and the 6-aminocaproic acid unit. Polyamide resin having a ratio of 97: 3 to 75:25.

  According to a second aspect of the present invention, in the above polyamide resin, the weight ratio of the sum of adipic acid units and pentamethylenediamine units to 6-aminocaproic acid units is 95: 5 to 80:20. Resin.

  The third gist of the present invention is a polyamide characterized in that, in the above polyamide resin, the total content of adipic acid units, pentamethylenediamine units and 6-aminocaproic acid units is 90% by weight or more of the total components. Resin.

  The fourth gist of the present invention is that in the above polyamide resin, pentamethylenediamine is produced from lysine using lysine decarboxylase, cells that produce lysine decarboxylase, or processed products of the cells. It exists in the polyamide resin characterized by being.

  The fifth gist of the present invention resides in a polyamide film comprising the above polyamide resin.

  The sixth gist of the present invention resides in a polyamide filament comprising the above polyamide resin.

  Since the polyamide resin of the present invention is excellent in staying heat stability, it is particularly effective for suppressing deterioration of large injection molded products and fish eyes of extrusion molded products. Moreover, since the biomass ratio is high, in various industrial fields, a remarkable effect for reducing the environmental load can be expected more than ever, and the industrial value of the present invention is extremely high.

  Hereinafter, the present invention will be described in detail. However, the description of the constituent elements described below is a representative example of embodiments of the present invention, and the present invention is not limited to these contents.

[Polyamide resin]
The polyamide resin of the present invention contains adipic acid units, pentamethylenediamine units and 6-aminocaproic acid units as constituents, and the weight ratio of the total of adipic acid units and pentamethylenediamine units to 6-aminocaproic acid units is 97: 3 to 75:25, preferably 95: 5 to 80:20, more preferably 90:10 to 82:18, that is, an adipic acid unit, a pentamethylenediamine unit, and 6-aminocaprone constituting the polyamide resin The ratio of the total amount of adipic acid units and pentamethylenediamine units to the total amount of acid units is 97 wt% or less, 75 wt% or more, preferably 95 wt% or less, 80 wt% or more, more preferably 90 wt%. It is a polyamide resin having a weight percentage of 82% by weight or less. If this ratio exceeds 97% by weight, the residence heat stability, the pinhole resistance and stretchability of the film, the flexibility and stretchability of the filament will decrease, and if it is less than 75% by weight, the heat resistance will decrease with the melting point decrease, There is a risk of film strength and filament strength being lowered.

  In addition, the polyamide resin of the present invention preferably has a total content of adipic acid units, pentamethylenediamine units and 6-aminocaproic acid units of 90% by weight or more, particularly 95% by weight or more of the total components. If this ratio is less than 90% by weight, it is difficult to achieve both the thermal stability and the high biomass ratio.

  Therefore, the polyamide resin of the present invention has an adipic acid unit, pentamethylenediamine, which is an essential structural unit, within a range of less than 10% by weight, preferably less than 5% by weight of the constituent components, and within a range not impairing the effects of the present invention. A copolymer component other than the unit and the 6-aminocaproic acid unit may be contained. In this case, the copolymerization component includes amino acids such as 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams other than ε-caprolactam such as ω-laurolactam, oxalic acid, malonic acid and succinic acid. , Aliphatic dicarboxylic acids such as glutaric acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, octadecanedioic acid, cyclohexanedicarboxylic acid, etc. Aromatic dicarboxylic acids such as alicyclic dicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1, 7-diaminoheptane, 1,8-diaminooctane Tan, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane 1,16-diaminohexadecane, 1,17-diaminoheptadecane, 1,18-diaminooctadecane, 1,19-diaminononadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopentane, etc. Aliphatic diamines, cyclohexanediamine, alicyclic diamines such as bis- (4-aminohexyl) methane, and aromatic diamines such as xylylenediamine.

  These copolymerization components may be used individually by 1 type, and may use 2 or more types together.

  The polyamide resin of the present invention may be a homopolyamide blend or a copolymer as long as it has the above structural units. That is, it may be a blend of polyamide 56 homopolymer and polyamide 6 homopolymer, or a copolyamide having pentamethylenediamine, adipic acid, and 6-aminocaproic acid as a structural unit, but is a copolyamide. Is particularly preferable in achieving the effects of the present invention.

  Among the polyamide resins of the present invention, known methods can be used as a method for producing homopolyamides and polyamide copolymers, and specifically disclosed in “Polyamide Resin Handbook” (published by Nikkan Kogyo Co., Ltd .: Osamu Fukumoto). Has been. As a method for producing the polyamide 56/6 copolymer, a method obtained by polycondensation of adipic acid, pentamethylenediamine and ε-caprolactam is preferable. Specifically, a method (heat polycondensation) in which a salt of pentamethylenediamine and adipic acid and ε-caprolactam are mixed in the presence of water and heated to advance a dehydration reaction is preferable. In this case, the copolymer composition ratio in the obtained polyamide resin can be changed by changing the mixing ratio of the salt of pentamethylenediamine and adipic acid and ε-caprolactam.

In the present invention, the heating polycondensation is preferably carried out by increasing the maximum temperature of the polymerization reaction mixture during the production of the polyamide resin to 200 ° C. or higher. The upper limit of the maximum temperature is usually 300 ° C. or less in consideration of the thermal stability of the polyamide resin during the polymerization reaction, and the maximum temperature is, for example, 240 to 290 ° C.
The polymerization method may be a batch method or a continuous method.

  The polyamide resin produced by the above method can be further subjected to solid phase polymerization after heat polycondensation. Thereby, the molecular weight of the polyamide resin can be increased. The solid phase polymerization can be performed by heating in a vacuum or an inert gas at a temperature of, for example, 100 ° C. or higher and lower than the melting point of the resin.

  In the polyamide resin of the present invention, as the raw material component pentamethylenediamine, lysine decarboxylase, cells that produce lysine decarboxylase, or those produced from lysine using processed products of the cells are used. It is preferable that the biomass ratio (ratio of the biomass-derived raw material in the raw material used for the polyamide resin) can be increased.

  The polyamide resin of the present invention preferably has a biomass ratio of 30.8% by weight or more by using pentamethylenediamine thus produced from lysine. The higher the biomass ratio, the greater the effect of suppressing the generation of carbon dioxide that causes global warming, which is preferable.

  In addition, the production of pentamethylenediamine from lysine is specifically the enzymatic desorption of lysine while adding an acid to the lysine solution so that the pH of the solution is maintained at a pH suitable for the enzymatic decarboxylation reaction. It can be carried out by carrying out a carbonic acid reaction. Examples of the acid used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, and organic acids such as acetic acid. After the reaction, free pentamethylenediamine can be collected from the obtained reaction product solution by a usual separation and purification method. In addition, when a dicarboxylic acid such as adipic acid is used as the acid, pentamethylenediamine dicarboxylate which is a raw material for producing polyamide can be directly collected. A method for producing pentamethylenediamine / adipate by enzymatic decarboxylation of lysine using adipic acid as an acid is described in JP-A-2005-6650.

The degree of polymerization of the polyamide resin of the present invention is not particularly limited, and is usually 1.5 to 8.0 as a relative viscosity of a 98 wt% sulfuric acid solution of polyamide resin at 25 ° C. (polyamide resin concentration: 0.01 g / ml). , Preferably 1.8 to 5.0. When this relative viscosity is less than 1.5, the practical strength may be insufficient, and when it exceeds 8.0, the fluidity may be lowered and the moldability may be impaired.
The melting point of the polyamide resin of the present invention is usually 210 to 255 ° C, preferably 220 to 250 ° C.
The method for measuring the relative viscosity of the polyamide resin is as shown in the Examples section below.

  In the polyamide resin of the present invention, other components can be blended at any stage from the production (polycondensation) of the polyamide resin to the molding as long as the effects of the present invention are not impaired. Other ingredients that can be incorporated include antioxidants and / or heat stabilizers, weathering agents, crystal nucleating agents, inorganic fillers, release agents and / or lubricants, pigments, dyes, plasticizers, antistatic agents, difficult A flame retardant, other polymers are mentioned.

  Here, examples of the antioxidant and / or the thermal stabilizer include hindered phenols, hydroquinones, phosphites, and substituted products thereof, copper halides, iodine compounds, and the like.

  Examples of the weathering agent include resorcinol, salicylate, benzotriazole, benzophenone, and hindered amine compounds.

  Examples of the crystal nucleating agent include inorganic fine particles such as talc, kaolin, silica, and boron nitride, metal oxides, high melting point nylon, and the like.

Inorganic fillers include graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, nickel, aluminum, copper, iron, Stainless steel, glass fiber, glass flake, glass bead, carbon fiber, talc, silica, kaolin, clay, wollastonite, mica, boron nitride, potassium titanate, aluminum borate, bentonite, montmorillonite, synthetic mica, etc. Glass fiber having a high reinforcing effect and relatively inexpensive is preferable.
As glass fiber, glass fiber usually used for thermoplastic resin can be used, and chopped strand produced from E glass (non-alkali glass) is preferable, and the fiber diameter is usually 1 to 20 μm, preferably 5 to 5 μm. 15 μm. The glass fiber is preferably surface-treated with a silane coupling agent or the like in order to improve adhesion with the polyamide resin.

  Examples of release agents and / or lubricants include aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, and polyethylene waxes.

Examples of the pigment include cadmium sulfide, phthalocyanine, carbon black and the like.
Examples of the dye include nigrosine and aniline black. Examples of the plasticizer include octyl p-oxybenzoate and N-butylbenzenesulfonamide.

  Examples of antistatic agents include alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, and betaine amphoteric antistatic agents. Can be mentioned.

  Flame retardants include hydroxides such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins or their brominated flame retardants. And a combination of antimony trioxide and the like.

  Other polymers include other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, SAN resin, polystyrene, and the like.

  Each of these may be used alone or in combination of two or more.

  The polyamide resin of the present invention can be molded into a desired shape by any molding method such as injection molding, film molding, melt spinning, blow molding, vacuum molding, etc., for example, an injection molded product, film, sheet, filament, It can be a tapered filament, a fiber, or the like. The polyamide resin of the present invention can also be used for adhesives, paints and the like.

  Specific examples of applications of the polyamide resin of the present invention include automobile manifolds, vehicle-related parts, intake manifolds, hinged clips (molded products with hinges), cable ties, resonators, air cleaners, engine covers, rocker covers, and cylinder head covers. , Timing belt cover, gasoline tank, gasoline sub tank, radiator tank, intercooler tank, oil reservoir tank, oil pan, electric power steering gear, oil strainer, canister, engine mount, junction block, relay block, connector, corrugated tube, protector, etc. For under hood parts, door handles, fenders, hood bulges, roof rail legs, door mirror stays, bumpers, spoilers, ho Automobile exterior parts such as Rukaba, cup holders, console boxes, accelerator pedals, clutch pedals, shift lever pedestals, automobile interior parts such as a shift lever knob and the like.

  Further, the polyamide resin of the present invention includes fishing line-related materials such as fishing lines, fishing nets, switches, ultra-small slide switches, DIP switches, switch housings, lamp sockets, cable ties, connectors, connector housings, connector shells, ICs. Sockets, coil bobbins, bobbin covers, relays, relay boxes, condenser cases, motor internal parts, small motor cases, gears / cams, dancing pulleys, spacers, insulators, casters, terminal blocks, power tool housings, starter insulation parts , Fuse box, terminal housing, bearing retainer, speaker diaphragm, heat-resistant container, microwave oven part, rice cooker part, printer / ribbon guide, etc. It can be used computer-related parts, facsimile-copier-related parts, in various applications such as mechanical related parts.

[the film]
When producing a film by forming the polyamide resin of the present invention into a film, if necessary, an inorganic filler for improving slipperiness, an antiblocking agent, a crystal nucleating agent, an antioxidant and / or a heat stabilizer, Add additives such as weathering agents, mold release agents and / or lubricants, pigments, dyes, plasticizers, antistatic agents, flame retardants, etc. and mix them according to conventional methods, for example, T-die method, water-cooled inflation method, air-cooled inflation method The film may be formed by, for example.

  Here, as the inorganic filler, talc, graphite, barium sulfate, magnesium sulfate, calcium carbonate, calcium silicate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead , Nickel, aluminum, copper, iron, stainless steel, glass fiber, glass flake, glass bead, carbon fiber, silica, kaolin, calcined kaolin, clay, zeolite, wollastonite, mica, boron nitride, potassium titanate, aluminum borate, Bentonite, montmorillonite, synthetic mica and the like can be used, and among these, talc, kaolin, calcined kaolin, silica and zeolite are preferred. These may be used alone or in combination of two or more.

Moreover, since there exists a possibility that transparency may be impaired when there is too much addition amount of an inorganic filler and there exists a possibility that slipperiness may not improve when there is little, 0.005-0 with respect to 100 weight part of polyamide resins. .1 part by weight is preferred.
The inorganic filler is particularly preferably a particulate inorganic filler. More preferably, the aspect which uses together an inorganic filler and a mold release agent and / or a lubricant is mentioned. In this case, the release agent and / or lubricant is preferably used in an addition amount of 0.01 to 0.5 parts by weight with respect to 100 parts by weight of the polyamide resin.

  The thickness of the film thus obtained is appropriately determined according to its use, but is usually about 1 to 70 μm.

[filament]
When a filament is produced by spinning the polyamide resin of the present invention, it may be spun by a spinning extruder or the like according to a conventional method.

  The molding temperature at the time of filament (monofilament) spinning is usually a temperature equal to or higher than the melting point of the polyamide resin, and preferably 10 ° C. higher than the melting point of the polyamide resin.

  There is no restriction | limiting in particular in the fineness of the filament obtained in this way, The wide range of 50-30000Tex is employable.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded.
In addition, the analysis method of the structural unit of a polyamide resin is as follows.

[Analysis of adipic acid units and 6-aminocaproic acid units in polyamide resin]
The sample was hydrolyzed with 6N hydrochloric acid. 1N sodium hydroxide was added dropwise to the hydrolyzed solution for neutralization to obtain a hydrolysis stock solution. An HPLC mobile phase (0.01 M-octanesulfonic acid / acetonitrile = 85/15) was added to the hydrolysis stock solution to prepare an analytical sample solution. This analytical sample solution was analyzed by liquid chromatography. The conditions are as follows. After the analysis, the content of the structural unit was determined using a calibration curve prepared in advance.
Equipment: Agilent HP-1100
Column: CAPCELL PAK C18 MG S-3 4.6mml.D. × 75mm
Column temperature: 40 ° C
Mobile phase: 0.01M-octanesulfonic acid / acetonitrile = 85/15
Flow rate: 1ml / min
Detector: PDA (UV205nm)
Injection volume: 5μl

[Analysis of pentamethylenediamine units and hexamethylenediamine units in polyamide resin]
The sample was hydrolyzed with 6N hydrochloric acid. The hydrolyzed solution was dried with a rotary evaporator, dried under reduced pressure at 40 ° C. for 1 hour, and then acylated with trifluoroacetic anhydride. Excess trifluoroacetic anhydride was distilled off with a rotary evaporator and then dissolved in acetonitrile to obtain an analytical sample solution. This analytical sample solution was analyzed by gas chromatography. The conditions were as follows. After the analysis, the content of the structural unit was determined using a calibration curve prepared in advance.
Column: SPB-1 SULFUR, 30m × 0.32mml.D., 4.00μm film thickness
Carrier: He 2.0ml / min (Constant Flow Mode)
Column temperature: 80 ° C (0min) to 10 ° C / min to 280 ° C (30min)
Inlet: Temperature 230 ℃, Spllt
Ratio 20: 1
Injection volume: 1μl

  The evaluation methods for various physical properties and characteristics of the polyamide resin are as follows.

(1) Relative viscosity (ηr)
A 98 wt% sulfuric acid solution of polyamide resin (concentration: 0.01 g / ml) was prepared and measured at 25 ° C. using an Ostwald viscometer.

(2) Melting point (mp)
DSC (differential scanning calorimetry) was performed using “Robot DSC” manufactured by Seiko Denshi Kogyo. First, about 5 mg of polyamide resin was put in a sample pan, heated to 290 ° C. in a nitrogen atmosphere, held for 3 minutes and completely melted, and then cooled to 30 ° C. at a temperature decreasing rate of 20 ° C./min. The temperature of the exothermic peak observed at this time is defined as the cooling crystallization temperature (Tc). Subsequently, after maintaining at 30 ° C. for 3 minutes, the temperature was increased from 30 ° C. to 290 ° C. at a temperature increase rate of 20 ° C./min. The endothermic peak observed at this time was measured, and the temperature of the observed endothermic peak was defined as the melting point (Tm). When multiple endothermic peaks were detected, the highest temperature was taken as the melting point.

(3) Stability of residence heat 7 g of polyamide resin is put into a test tube with a capacity of 18 ml, and this test tube is immersed in an oil bath having a melting point + 30 ° C. under a nitrogen atmosphere, and the sample is recovered after 9 hours. The viscosity was measured. The viscosity retention was calculated from the relative viscosity before and after the residence test. A high viscosity retention indicates that the residence heat stability is excellent.

  Moreover, the evaluation method of the film and monofilament which consist of polyamide resins is as follows.

[Pin-hole resistance of film]
Pinhole resistance was evaluated by the number of pinholes after repeated bending fatigue tests.
The repeated bending fatigue test (Gelboflex test) is performed at 23 ° C., 65% RH or 0 in accordance with MIL-B-131C using a Gelboflex tester manufactured by Rigaku Corporation under a predetermined environmental condition. Under the condition of ° C., the film was repeatedly bent and fatigued 1000 times, and then the number of pinholes generated in the film was counted.
In addition, the number of pinholes was counted with a poroscope DCH8E manufactured by HELMUT FISCHER GMBH (Germany). This is a device that puts a sample film on a grounded metal plate, scans the film surface with a brush charged at 1.2 kV, allows current to flow if there is a pinhole, and counts the number of pinholes. .

[Fineness of monofilament, Young's modulus, linear strength, knot strength]
According to JIS L1013, the fineness, Young's modulus, linear strength, and knot strength of the monofilament were measured.

  In the following examples and comparative examples, equimolar salts of pentamethylenediamine and adipic acid were prepared according to the methods described in Examples 1 to 3 of JP-A-2005-6650. For ε-caprolactam, a product of Mitsubishi Chemical Corporation was used. In addition, a Rhodia product was used as an equimolar salt of hexamethylenediamine and adipic acid.

Example 1:
After adding 25 kg of water to 25 kg of a mixture of equimolar salts of pentamethylenediamine and adipic acid and ε-caprolactam (see Table 1 for weight ratio), 1.25 g of phosphorous acid is added, and the mixture is completed under a nitrogen atmosphere. The raw material aqueous solution was obtained. The raw material aqueous solution was transferred to an autoclave which had been previously purged with nitrogen by a plunger pump. The jacket temperature was adjusted to 280 ° C., the autoclave pressure was adjusted to 1.47 MPa, and the contents were heated to 270 ° C. Next, after gradually releasing the pressure in the autoclave, the pressure was further reduced and the reaction was terminated when a predetermined stirring power was reached. After completion of the reaction, the pressure was restored with nitrogen, and the contents were introduced into a cooling water tank in the form of a strand and then pelletized with a rotary cutter. The obtained pellets were dried under conditions of 120 ° C. and 1 torr (0.13 kPa) until the water content became 0.1% by weight or less to obtain a polyamide resin.
The obtained polyamide resin was evaluated, and the results are shown in Table 1.

Example 2:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 1 in Example 1.
The obtained polyamide resin was evaluated, and the results are shown in Table 1.

Comparative Example 1:
A polyamide resin was obtained in the same manner as in Example 1, except that the monomer composition of the raw material aqueous solution was changed as shown in Table 1 in Example 1.
The obtained polyamide resin was evaluated, and the results are shown in Table 1.

  In Table 1, the biomass ratio of the polyamide resin obtained in each example is also shown.

  From Table 1, it can be seen that the polyamide resin of the present invention has a high biomass ratio and is excellent in residence heat stability.

Example 3:
After adding 25 kg of water to 25 kg of a mixture of equimolar salts of pentamethylenediamine and adipic acid and ε-caprolactam (see Table 2 for weight ratio), 1.25 g of phosphorous acid is added, and the mixture is completely removed under a nitrogen atmosphere. The raw material aqueous solution was obtained. The raw material aqueous solution was transferred to an autoclave which had been previously purged with nitrogen by a plunger pump. The jacket temperature was adjusted to 280 ° C., the autoclave pressure was adjusted to 1.47 MPa, and the contents were heated to 270 ° C. Next, after gradually releasing the pressure in the autoclave, the pressure was further reduced and the reaction was terminated when a predetermined stirring power was reached. After completion of the reaction, the pressure was restored with nitrogen, and the contents were introduced into a cooling water tank in the form of a strand and then pelletized with a rotary cutter. Unreacted monomers and oligomers were extracted and removed from the resulting pellets using 1.5 times the amount of boiling water of the pellets. The pellets from which the unreacted substances had been removed were dried at 120 ° C. and 1 torr (0.13 kPa) until the water content became 0.1% or less to obtain a polyamide resin.

With respect to 100 parts by weight of the obtained polyamide resin, 0.03 part by weight of talc having an average particle diameter of 3.0 μm and 0.1 part by weight of ethylenebisstearic acid amide (manufactured by Kao Corporation, Kao Wax EB-FF) are dried. Using a polyamide resin composition obtained by blending as a raw material, using a T-die type film forming machine having an extruder cylinder diameter of 40 mm, a film having a thickness of 25 μm at an extruder cylinder set temperature of 260 ° C. and a cooling roll temperature of 90 ° C. A film was formed.
Pinhole resistance was evaluated using the obtained film. The results are shown in Table 2.

Further, using the obtained polyamide resin, spinning was performed by a spinning extruder equipped with a gear pump and a nozzle having 18 holes with a diameter of 0.6 mm at the tip of a single screw extruder. The cylinder temperature of the extruder and the set temperature of the gear pump are set to 260 ° C, and the spinning is cooled and solidified through a 20 ° C cooling water tank, and then the first drawing (98 ° C, steam atmosphere, draw ratio of 3.5 times) is performed. Then, the second stretching (175 ° C., hot air atmosphere, stretching ratio adjusted to the total stretching ratio) was performed, and finally heat setting (175 ° C., hot air atmosphere, relaxation ratio 5%) was performed.
Various physical properties were measured using the obtained monofilament. The results are shown in Table 2.

Comparative Example 2:
25 kg of caprolactam manufactured by Mitsubishi Chemical Co., Ltd., 0.75 kg of water, and 1.74 g of disodium hydrogen phosphite pentahydrate were placed in a container, and the mixture was purged with nitrogen and dissolved at 100 ° C. This aqueous raw material solution was transferred to an autoclave, the jacket temperature was set to 280 ° C., and heating was started. After the temperature of the contents was raised to 270 ° C., the pressure in the autoclave was gradually released, and then the pressure was further reduced and the polycondensation reaction was completed when a predetermined stirring power was reached. After completion of the reaction, the pressure was restored with nitrogen, and the contents were introduced into a cooling water tank in the form of a strand and then pelletized with a rotary cutter. Unreacted monomers and oligomers were extracted and removed from the resulting pellets using 1.5 times the amount of boiling water of the pellets. The pellets from which the unreacted substances had been removed were dried at 120 ° C. and 1 torr (0.13 kPa) until the water content became 0.1% or less to obtain a polyamide resin.
Using the resulting polyamide resin, film formation and evaluation, monofilament spinning and evaluation were performed in the same manner as in Example 3. The results are shown in Table 2.

Comparative Example 3:
In Example 3, a polyamide resin was obtained in the same manner as in Example 3 except that the charged monomer composition of the raw material aqueous solution was changed as shown in Table 2.
Using the resulting polyamide resin, film formation and evaluation, monofilament spinning and evaluation were performed in the same manner as in Example 3. The results are shown in Table 2.

  In Table 2, the biomass ratio of the polyamide resin obtained in each example is also shown.

  As is clear from Table 2, also in the physical properties of the film, Example 3 is superior to Comparative Examples 2 and 3 with fewer pinholes. In addition, regarding the physical properties of the monofilament, Example 3 is superior to Comparative Examples 2 and 3 in that the Young's modulus is lower than that of Comparative Examples 2 and 3 in any case where the draw ratio is 5.27 times and 4.10 times.

Claims (6)

  A polyamide resin comprising adipic acid units, pentamethylenediamine units and 6-aminocaproic acid units as constituents, wherein the weight ratio of the sum of adipic acid units and pentamethylenediamine units to 6-aminocaproic acid units is 97: 3 Polyamide resin characterized by being 75:25.   2. The polyamide resin according to claim 1, wherein a weight ratio of a total of adipic acid units and pentamethylenediamine units to 6-aminocaproic acid units is 95: 5 to 80:20.   The polyamide resin according to claim 1 or 2, wherein the total content of adipic acid units, pentamethylenediamine units and 6-aminocaproic acid units is 90% by weight or more of the total components.   The pentamethylenediamine is produced from lysine using lysine decarboxylase, a cell that produces lysine decarboxylase, or a processed product of the cell, according to any one of claims 1 to 3. The polyamide resin described in 1.   A polyamide film comprising the polyamide resin according to claim 1.   A polyamide filament comprising the polyamide resin according to any one of claims 1 to 4.