WO2017077901A1 - Résine de polyamide semi-aromatique et son procédé de production - Google Patents

Résine de polyamide semi-aromatique et son procédé de production Download PDF

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Publication number
WO2017077901A1
WO2017077901A1 PCT/JP2016/081514 JP2016081514W WO2017077901A1 WO 2017077901 A1 WO2017077901 A1 WO 2017077901A1 JP 2016081514 W JP2016081514 W JP 2016081514W WO 2017077901 A1 WO2017077901 A1 WO 2017077901A1
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Prior art keywords
polyamide resin
semi
aromatic polyamide
relative viscosity
acid
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PCT/JP2016/081514
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English (en)
Japanese (ja)
Inventor
誠 玉津島
順一 中尾
福田　裕樹
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東洋紡株式会社
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Priority to JP2017510425A priority Critical patent/JPWO2017077901A1/ja
Publication of WO2017077901A1 publication Critical patent/WO2017077901A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/04—Preparatory processes

Definitions

  • the present invention relates to a semi-aromatic polyamide resin suitable for a resin composition for molded parts such as automobile parts and electric / electronic parts, which is excellent in heat resistance and melt fluidity, and further in heat discoloration.
  • thermoplastic resins polyamide resins have been used for clothing, industrial material fibers, engineering plastics, etc., taking advantage of their excellent properties and ease of melt molding.
  • engineering plastics are used not only for automobile parts and industrial machine parts but also for various industrial parts, housing parts, electrical / electronic parts, and the like.
  • High strength, high rigidity, and high heat resistance are generally known as typical characteristics required for engineering plastics.
  • automotive parts as the interior of the car is expanded, the resin parts are becoming smaller. The atmosphere temperature to be exposed tends to increase, and heat resistance higher than that of the conventional one is required.
  • plastics for various metal parts are being promoted for the purpose of reducing fuel consumption in automobiles, but in order to be able to replace metals, it is necessary to increase rigidity by increasing the filling of reinforcing materials and fillers. is there. In order to increase the filling, it is necessary to improve the processability, that is, the fluidity of the polyamide resin itself, and for the development of a high-performance polyamide resin, a higher fluidity of the resin is newly required.
  • Patent Document 2 proposes polyamide 9T obtained mainly from nonanediamine and terephthalic acid.
  • Polyamide 9T has high heat resistance and low water absorption, and it has suppressed defects such as product swelling in the surface mounting process, but the glass transition temperature of the resin is 130 ° C., and it is fully crystallized during molding.
  • the mold temperature In order to complete it, it is necessary to set the mold temperature to a high temperature of 140 ° C. or higher, and there is room for improvement in terms of moldability.
  • it does not describe at all about the color tone of the resin in a manufacturing process or use environment.
  • Patent Document 3 proposes a copolymerized polyamide obtained from an equivalent molar salt of hexamethylenediamine and terephthalic acid and 11-aminoundecanoic acid.
  • This copolymerized polyamide has heat resistance, low water absorption, and excellent stability in the surface mounting process.
  • the glass transition temperature of the resin is 90 ° C., and injection at a relatively low mold temperature. It is a resin that enables molding and satisfies moldability.
  • the color tone of the resin is likely to change in the manufacturing process or use environment, and there is room for improvement in terms of the stability of the color tone of the resin due to external factors.
  • the various semi-aromatic polyamide resins described above have a high melting point and poor melt fluidity compared to aliphatic polyamide resins, and have the disadvantages that they tend to thicken or gel when melted, and have processing stability and high fluidity. There is room for improvement.
  • the polyamide resins that have been proposed in the past can satisfy some of the characteristics such as heat resistance, low water absorption, moldability, discoloration resistance, and high fluidity, but satisfy all of them. Rather, it is currently used while having problems with either.
  • the present invention was devised in view of the current state of the prior art, and the object thereof is an automobile part that is excellent in melt fluidity and color tone stability in addition to a high melting point and low water absorption of 290 ° C. or higher.
  • Another object of the present invention is to provide a semi-aromatic polyamide resin suitable for a resin composition for molded articles such as electric / electronic parts.
  • the present inventor has intensively studied the melting characteristics of semi-aromatic polyamide resin, the resin characteristics including terminal groups, and the production method, and as a result, the present invention has been completed.
  • the present invention has the following configuration. (1) It contains 50 mol% or more of a structural unit obtained from an equimolar molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid, and satisfies the following requirements (a) to (d) Semi-aromatic polyamide resin: (A) the melting point (Tm) is 290-350 ° C .; (B) Ratio of relative viscosity (RV0) of 1.3 to 2.1, and melt flow rate (MFR) in g / 10 minutes and relative viscosity (RV5) (MFR / RV5) Is greater than or equal to 50; Melt flow rate (MFR: g / 10 min): Measured according to ASTM D1238 method, melting point + 20 ° C.
  • Relative viscosity initial relative viscosity measured at 20 ° C. in 96% sulfuric acid
  • RV5 Relative viscosity measured at 20 ° C. in 96% sulfuric acid after melting at + 20 ° C.
  • Terminal amino group concentration (AEG) is 15 eq / ton or less, and terminal amino group concentration (AEG) ) Of eq / ton and the terminal carboxyl group concentration (CEG) of eq / ton (AEG / CEG) is 0.07 or less;
  • the ratio (RV5 / RV0) between the relative viscosity (RV5) and the relative viscosity (RV0) is 0.900 to 1.010.
  • the semi-aromatic polyamide resin is a component other than a structural unit obtained from an equimolar molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid, among aminocarboxylic acids having 11 to 18 carbon atoms or lactams.
  • the semi-aromatic polyamide resin according to any one of (1) to (4), which comprises: (6) A low-order condensate of a semi-aromatic polyamide resin obtained by melt polymerization and having a relative viscosity (RV0) of less than 1.6 and having at least a part of the terminal amino groups blocked (melting point ⁇ 100
  • the solid phase polymerization at a temperature of from °C ° C. to (melting point ⁇ 10) ° C., and the terminal amino group concentration (AEG) is set to 15 eq / ton or less, according to any one of (1) to (5) A method for producing an aromatic polyamide resin.
  • a semi-aromatic polyamide resin can be provided.
  • the semi-aromatic polyamide resin of the present invention means one having an aromatic skeleton derived from dicarboxylic acid or diamine in the repeating unit of the polyamide resin.
  • the semi-aromatic polyamide resin of the present invention contains 50 mol% or more of a structural unit obtained from an equivalent molar salt of a diamine having 2 to 12 carbon atoms and terephthalic acid.
  • the structural unit is preferably 55 mol% or more, more preferably 55 to 75 mol%, and still more preferably 60 to 70 mol%. If the structural unit obtained from an equimolar molar salt of diamine and terephthalic acid is less than 50 mol%, the crystallinity and mechanical properties are undesirably lowered.
  • Examples of the diamine component having 2 to 12 carbon atoms include 1,2-ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 2-methyl-1,5- Pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1,8-octamethylenediamine, 1,9-nonamethylenediamine, 2-methyl-1,8-octamethylenediamine, 1, Examples thereof include 10-decamethylenediamine, 1,11-undecamethylenediamine, and 1,12-dodecamethylenediamine, and these can be used alone or in combination.
  • a semi-aromatic polyamide comprising a structural unit obtained from an equimolar salt of a diamine having 9 or more carbon atoms and terephthalic acid
  • a resin containing 50 mol% or more of a structural unit obtained from an equivalent molar salt of diamine and terephthalic acid and having a melting point of 290 ° C. or more is preferred.
  • the structural unit obtained from an equivalent molar salt of a diamine having 2 to 8 carbon atoms and terephthalic acid is more preferably 55 mol% or more, further preferably 55 to 75 mol%, particularly preferably 60 to 70 mol%.
  • copolymerizable diamine components include 1,13-tridecamethylenediamine, 1,16-hexadecamethylenediamine, 1,18-octadecamethylenediamine, 2,2,4 (or 2,4,4)- Alicyclic diamines such as aliphatic diamines such as trimethylhexamethylenediamine, piperazine, cyclohexanediamine, bis (3-methyl-4-aminohexyl) methane, bis- (4,4'-aminocyclohexyl) methane, isophoronediamine
  • aromatic diamines such as diamine, metaxylylenediamine, paraxylylenediamine, paraphenylenediamine and metaphenylenediamine, and hydrogenated products thereof.
  • copolymerizable acid components include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 5-sulfonic acid sodium isophthalic acid, 5-hydroxyisophthalic acid and other aromatic dicarboxylic acids, fumaric acid, maleic acid, succinic acid, itaconic acid, adipic acid, azelaic acid, sebacic acid, 1,11-undecanedioic acid, 1,12-dodecanedioic acid, 1,14-tetradecanedioic acid, 1,18-octadecanedioic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1, 2-
  • lactams such as ⁇ -caprolactam, 11-aminoundecanoic acid, undecane lactam, 12-aminododecanoic acid, 12-lauryllactam, and aminocarboxylic acids having a structure in which they are ring-opened can be used.
  • the copolymer component it is preferable to copolymerize one or more of diamines having 10 to 18 carbon atoms, dicarboxylic acids, aminocarboxylic acids, and lactams. More preferably, one or more of an aminocarboxylic acid having 11 to 18 carbon atoms or a lactam are copolymerized.
  • the semi-aromatic polyamide resin of the present invention preferably satisfies (A) 7.5 ⁇ [number of carbon atoms in polyamide resin / number of amide bonds in polyamide resin]. Furthermore, the semi-aromatic polyamide resin of the present invention preferably satisfies 7.5 ⁇ [number of carbon atoms in polyamide resin / number of amide bonds in polyamide resin] ⁇ 8.2.
  • the amide group concentration in the polyamide resin is high, and therefore discoloration is likely to occur due to resin degradation due to heat or light. Become.
  • the amide group concentration in the polyamide resin becomes low, and the melting point may be lower than 290 ° C. Heat resistance may be insufficient.
  • the semi-aromatic polyamide resin in the present invention preferably satisfies (B) [the number of carbon atoms on the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin] ⁇ 0.35. Furthermore, the semi-aromatic polyamide resin of the present invention preferably satisfies 0.28 ⁇ [number of carbon atoms on the aromatic ring in the polyamide resin / total number of carbon atoms in the polyamide resin] ⁇ 0.35.
  • the number of carbon atoms on the aromatic ring in the polyamide resin / the total number of carbon atoms in the polyamide resin] exceeds 0.35, the light absorption particularly in the ultraviolet region increases, and the resin is significantly deteriorated by the light. It is easy to become.
  • the aromatic ring concentration in the resin is low.
  • the [number of carbon atoms on the aromatic ring / total number of carbon atoms in the polyamide resin] in the polyamide resin is preferably 0.28 or more.
  • Examples of the semi-aromatic polyamide resin of the present invention include hexamethylenediamine / terephthalic acid / aminoundecanoic acid (or undecalactam), hexamethylenediamine / terephthalic acid / aminododecanoic acid (or 12-lauryllactam), decamethylenediamine / Terephthalic acid / aminoundecanoic acid (or undecalactam) and decamethylenediamine / terephthalic acid / aminododecanoic acid (or 12-lauryl lactam) are particularly preferred, and in particular, from the viewpoint of high melting point, those having 2 to 8 carbon atoms.
  • the structure and the unit 55 to 75 mol% is preferably a copolymer polyamide resin consisting of structural units 45-25 mole% obtained from 11-aminoundecanoic acid or undecanoic lactam. More preferred is a copolymerized polyamide resin comprising 60 to 70 mol% of the structural unit and 40 to 30 mol% of a structural unit obtained from 11-aminoundecanoic acid or undecane lactam.
  • the melting point (Tm) of the semi-aromatic polyamide resin of the present invention is 290 to 350 ° C., preferably 290 to 340 ° C., more preferably 300 to 330 ° C.
  • Tm exceeds the above upper limit, the processing temperature required when molding the semi-aromatic polyamide composition by injection molding or the like becomes extremely high, so that the target physical properties and appearance may not be obtained by decomposition during processing. .
  • Tm is less than the above lower limit, the crystallization rate becomes slow, and in both cases, molding becomes difficult.
  • the semi-aromatic polyamide resin of the present invention has an initial relative viscosity (RV0) measured in 96% concentrated sulfuric acid at 20 ° C. of 1.3 to 2.1, preferably 1.4 to 2.0, more preferably It is 1.4 to 1.95, more preferably 1.5 to 1.9.
  • RV0 initial relative viscosity measured in 96% concentrated sulfuric acid at 20 ° C.
  • the relative viscosity of the semi-aromatic polyamide resin can be controlled by changing the amount of diamine or dicarboxylic acid added during polymerization, the amount of terminal blocking agent added, the polymerization conditions, or the like.
  • RV0 exceeds the above range, it may be difficult to achieve good fluidity, and when it is less than the above range, the mechanical strength of the resin may be inferior.
  • the semi-aromatic polyamide resin of the present invention has a melt flow rate (MFR) value of g / 10 minutes and a relative viscosity value (RV5) measured after melting and staying at a melting point + 20 ° C. for 5 minutes.
  • the ratio is 50 or more, preferably 60 or more.
  • the melt flow rate (MFR) is a numerical value (g / 10 minutes) measured according to ASTM D1238 method at a temperature of melting point + 20 ° C. and a load of 2.16 kg.
  • the ratio of the numerical value of the melt flow rate (MFR) and the numerical value of the relative viscosity (RV5) is less than the above range, thickening or gel is likely to occur during the melt residence of the resin. If the relative viscosity (RV5) becomes too low, the mechanical strength of the resin is inferior, so the upper limit is preferably about 300.
  • the semi-aromatic polyamide resin of the present invention can achieve good fluidity (high melt flow rate (MFR)) with almost no thickening due to melt retention by adopting the production method described later. It is a polyamide resin.
  • the relative viscosity and melt flow rate (MFR) of the semi-aromatic polyamide resin in the above range, the fluidity in the mold during the molding of the semi-aromatic polyamide resin composition is improved, and fine molded products and many It is possible to facilitate the forming process using the individual mold. Further, it is advantageous in melt processability, such as reducing shearing heat generation and suppressing resin foaming when melt-kneading a reinforcing material or filler with semi-aromatic polyamide.
  • the terminal amino group concentration (AEG) of the semi-aromatic polyamide resin of the present invention is 15 eq / ton or less, preferably 10 eq / ton or less, more preferably 5 eq / ton or less.
  • Examples of the method for measuring the terminal amino group concentration include a method of obtaining from the integral value of the spectrum corresponding to each terminal group obtained by 1 H-NMR from the viewpoint of measurement accuracy and simplicity.
  • the heat of processing increases the viscosity of the semi-aromatic polyamide resin composition.
  • the resin may be poorly filled in the mold during molding.
  • excessive shearing heat generation may cause foaming of the resin.
  • the semi-aromatic polyamide resin of the present invention has a ratio (AEG / CEG) of the terminal amino group concentration (AEG) in eq / ton and the terminal carboxyl group concentration (CEG) in eq / ton. It is 0.07 or less, preferably 0.06 or less, more preferably 0.05 or less, still more preferably 0.04 or less, and particularly preferably 0.02 or less.
  • AEG and CEG from the viewpoint of measurement accuracy and simplicity, there is a method of obtaining from an integral value of a spectrum corresponding to each terminal group obtained by 1 H-NMR.
  • the semi-aromatic polyamide resin of the present invention has a ratio (RV5 / RV0) of relative viscosity (RV5) and initial relative viscosity (RV0) measured after melting and staying at melting point + 20 ° C. for 5 minutes from 0.900 to 1. 010, preferably 0.900 to 1.000, more preferably 0.950 to 1.000.
  • the semi-aromatic polyamide resin of the present invention has an initial relative viscosity (RV0), a relative viscosity after melt residence (RV5), a melt flow rate (MFR), a terminal amino group concentration (AEG), and a terminal carboxyl group.
  • RV0 initial relative viscosity
  • RV5 relative viscosity after melt residence
  • MFR melt flow rate
  • AEG terminal amino group concentration
  • CEG concentration
  • the semi-aromatic polyamide resin of the present invention has a difference ( ⁇ b *) between the initial b * value (b * 0) and the b * value (b * 1) after ultraviolet irradiation without blending a light fastness imparting agent. ) Can be made 20.0 or less, more preferably 19.0 or less, and even more preferably 18.0 or less.
  • the b * value here is a value defined in the CIEL * a * b * color system. The b * value was measured using a Toshiba Machine injection molding machine EC-100N with the cylinder temperature set to the melting point + 20 ° C.
  • ⁇ b * of the semi-aromatic polyamide resin of the present invention is in the above range, it is used for lighting parts typified by LED reflectors and exterior parts such as automobiles that are required to suppress discoloration due to ultraviolet rays in the use environment. Is possible.
  • a semi-aromatic polyamide resin obtained by melt polymerization and having a relative viscosity (RV) in which at least a part of terminal amino groups is end-capped is less than 1.6 is used.
  • RV relative viscosity
  • the melting point is the melting point of the low-order condensate of the semi-aromatic polyamide resin.
  • solid phase polymerization refers to a step of proceeding the polymerization reaction at an arbitrary temperature within a range where the semi-aromatic polyamide resin does not melt.
  • the equipment for performing the solid phase polymerization is not particularly limited, and examples thereof include a blender and a vacuum dryer.
  • the relative viscosity (RV) of the low-order condensate is more preferably less than 1.55, and even more preferably less than 1.50.
  • the temperature of the solid phase polymerization is more preferably (melting point ⁇ 100) ° C. to (melting point ⁇ 20) ° C., and more preferably (melting point ⁇ 100) ° C. to (melting point ⁇ 40) ° C.
  • the terminal blocking rate of the low-order condensate before being subjected to solid phase polymerization is 5% or more, preferably 10% or more, more preferably 15% or more.
  • the upper limit of the terminal blocking rate of the low-order condensate is 40% or less, preferably 35% or less, and more preferably 30% or less.
  • the end capping rate is defined as the total amount of end groups (eq / ton) of each end group (AEG, CEG and end blocker-bound end) obtained by 1 H-NMR as the total end amount. It can be calculated from the quantity.
  • the end-capping rate of the low-order condensate before being subjected to solid-phase polymerization is below the above range, the final semi-aromatic polyamide resin will have a higher relative viscosity, and may increase viscosity or gel due to residence. There is.
  • the end-capping rate of the low-order condensate exceeds the above range, the semi-aromatic polyamide resin finally obtained may have a low relative viscosity, and the reaction rate may be reduced.
  • the relative viscosity (RV) of the low-order condensate exceeds the above range, the relative viscosity (RV) of the semi-aromatic polyamide resin obtained by solid-phase polymerization of the low-order condensate becomes high. The fluidity at the time becomes low, which is not preferable in terms of melt processability.
  • the polymerization temperature of the low-order condensate is preferably at least the lower limit of the above range.
  • the higher the heat that is applied to the low-order condensate during polymerization the more generation of sites that are the starting points for the cleavage and degradation of polyamide molecular chains, and the color tone of the semi-aromatic polyamide resin that is finally obtained Reduce stability. Accordingly, the polymerization temperature of the low-order condensate is preferably not more than the upper limit of the above range.
  • the semi-aromatic polyamide resin of the present invention may be melt-kneaded again using an extruder after solid-phase polymerization.
  • Examples of the catalyst used for producing the semi-aromatic polyamide resin include phosphoric acid, phosphorous acid, hypophosphorous acid or a metal salt, ammonium salt and ester thereof.
  • Specific examples of the metal species of the metal salt include potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin, tungsten, germanium, titanium, and antimony.
  • As the ester, ethyl ester, isopropyl ester, butyl ester, hexyl ester, isodecyl ester, octadecyl ester, decyl ester, stearyl ester, phenyl ester and the like can be added.
  • alkali compounds such as sodium hydroxide, potassium hydroxide, and magnesium hydroxide, from a viewpoint of melt retention stability improvement.
  • the timing for adding the end-capping agent may be during raw material charging or low-order condensation.
  • the end-capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but acid anhydrides such as monocarboxylic acid or monoamine, phthalic anhydride, mono Isocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used.
  • terminal blocking agent examples include aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
  • aliphatic monocarboxylic acids such as acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecanoic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid.
  • Acid cycloaliphatic carboxylic acid and other alicyclic monocarboxylic acids, benzoic acid, toluic acid, ⁇ -naphthalenecarboxylic acid, ⁇ -naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids, maleic anhydride , Acid anhydrides such as phthalic anhydride, hexahydrophthalic anhydride, fats such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine Group monoamines, Examples thereof include alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine and naphth
  • the end-capping agent is preferably a monocarboxylic acid or an acid anhydride.
  • the amount of the end-capping agent may be an amount in which the end-capping rate of the low-order condensate falls within the above range.
  • the amount of the end-capping agent is preferably 1 to 6 mol% with respect to the amine component (the total of diamine and aminocarboxylic acid (or lactam)) constituting the semiaromatic polyamide resin, and preferably 2 to 5 More preferred is mol%.
  • additives for conventional polyamide can be used for the semi-aromatic polyamide resin of the present invention.
  • Additives include fibrous reinforcements / fillers, stabilizers, impact modifiers, flame retardants, mold release agents, slidability improvers, colorants, plasticizers, crystal nucleating agents, semi-aromatic polyamides of the present invention Examples thereof include a polyamide resin different from the resin, and a thermoplastic resin other than the polyamide resin.
  • fibrous reinforcing material examples include glass fiber, carbon fiber, metal fiber, ceramic fiber, organic fiber, and whisker. These fibrous reinforcing materials may be used not only alone but also in combination of several kinds.
  • fillers reinforcing fillers, conductive fillers, magnetic fillers, flame retardant fillers, thermal conductive fillers and the like are listed according to purpose. Specifically, glass beads, glass flakes, glass balloons, silica, talc , Kaolin, wollastonite, mica, alumina, hydrotalcite, montmorillonite, hydroxyapatite, graphite, carbon nanotube, fullerene, zinc oxide, indium oxide, tin oxide, iron oxide, titanium oxide, magnesium oxide, aluminum hydroxide, water Magnesium oxide, red phosphorus, calcium carbonate, potassium titanate, lead zirconate titanate, barium titanate, aluminum nitride, boron nitride, zinc borate, aluminum borate, barium sulfate, magnesium sulfate, zinc sulfide, iron, aluminum, copper, Etc. The. These fillers may be used not only alone but also in combination of several kinds. Although it does not specifically limit as a shape,
  • Stabilizers include organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and copper compounds. Copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cupric chloride, cupric bromide, cupric iodide, cupric phosphate, cupric pyrophosphate, Copper salts of organic carboxylic acids such as copper sulfide, copper nitrate, and copper acetate can be used. Further, as a component other than the copper compound, an alkali metal halide compound is preferably contained.
  • organic antioxidants such as hindered phenol antioxidants, sulfur antioxidants, phosphorus antioxidants, heat stabilizers, light stabilizers such as hindered amines, benzophenones, and imidazoles. Examples include ultraviolet absorbers, metal deactivators, and
  • alkali metal halide compound examples include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, bromide.
  • alkali metal halide compound examples include lithium chloride, lithium bromide, lithium iodide, sodium fluoride, sodium chloride, bromide.
  • examples thereof include sodium, sodium iodide, potassium fluoride, potassium chloride, potassium bromide, potassium iodide and the like. These additives may be used alone or in combination of several kinds.
  • the semi-aromatic polyamide resin of the present invention may be polymer blended with a polyamide resin having a composition different from that of the semi-aromatic polyamide resin of the present invention.
  • thermoplastic resin other than the polyamide resin having a composition different from that of the semi-aromatic polyamide resin of the present invention may be added to the semi-aromatic polyamide resin of the present invention.
  • thermoplastic resins can be blended in a molten state by melt kneading.
  • the thermoplastic resin may be made into a fiber or particle and dispersed in the copolymerized polyamide of the present invention.
  • ethylene-propylene rubber EPM
  • ethylene-propylene-diene rubber EPDM
  • ethylene-acrylic acid copolymer ethylene-acrylic acid ester copolymer
  • ethylene-methacrylic acid copolymer ethylene- Polyolefin resins such as methacrylic acid ester copolymer, ethylene vinyl acetate copolymer, styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-isoprene -Styrene copolymer (SIS), vinyl polymer resin such as acrylate copolymer, polybutylene terephthalate or polybutylene naphthalate as hard segment, polytetramethylene glycol or polycaprolactone or poly Polyester block copolymer in which the turbo sulfonate diol as
  • flame retardants examples include halogen flame retardants, non-halogen flame retardants, and flame retardant aids. These may be used alone or in combination.
  • halogen flame retardants include brominated polystyrene, brominated polyphenylene ether, brominated bisphenol type epoxy polymer, brominated styrene maleic anhydride polymer, brominated epoxy resin, brominated phenoxy resin, decabromodiphenyl ether, decabromo.
  • Biphenyl, brominated polycarbonate, perchlorocyclopentadecane, brominated cross-linked aromatic polymer and the like can be mentioned.
  • Non-halogen flame retardants include melamine cyanurate, red phosphorus, phosphinic acid metal salts, and nitrogen-containing phosphoric acid compounds.
  • Flame retardant aids include antimony compounds such as antimony trioxide, antimony pentoxide, sodium antimonate, zinc stannate, zinc borate, zinc sulfide, molybdenum compounds, iron oxide, aluminum hydroxide, magnesium hydroxide, silicone resin , Fluororesin, montmorillonite, silica, metal carbonate and the like.
  • antimony compounds such as antimony trioxide, antimony pentoxide, sodium antimonate, zinc stannate, zinc borate, zinc sulfide, molybdenum compounds, iron oxide, aluminum hydroxide, magnesium hydroxide, silicone resin , Fluororesin, montmorillonite, silica, metal carbonate and the like.
  • release agent examples include long chain fatty acids or esters thereof, metal salts, amide compounds, polyethylene wax, silicone, polyethylene oxide, and the like.
  • sliding property improving material examples include high molecular weight polyethylene, acid-modified high molecular weight polyethylene, fluorine resin powder, molybdenum disulfide, silicone resin, silicone oil, zinc, graphite, mineral oil, and the like.
  • the molded product obtained from the semi-aromatic polyamide resin of the present invention is excellent in heat resistance and color tone stability in an actual use environment, so that connectors, switches, relays, and prints that require heat resistance are required. It can be suitably used as an electrical / electronic component such as a wiring board, a component having a function of reflecting light, such as an LED or a reflector of a lighting fixture.
  • the semi-aromatic polyamide resin of the present invention is excellent in heat resistance and melt processability, so it is possible to increase the filling of reinforcing materials, fillers, etc., and engine peripheral parts that require high rigidity It can be used for automobile parts such as cooling parts and fuel parts, and industrial parts such as gears and screws and other sliding parts.
  • the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
  • the measured value described in the Example is measured by the following method.
  • Relative viscosity 0.25 g of semi-aromatic polyamide resin dried under reduced pressure at 105 ° C. for 15 hours was dissolved in 25 ml of 96% sulfuric acid and measured at 20 ° C. using an Ostwald viscometer.
  • the sample was taken out from the liquid nitrogen and allowed to stand at room temperature for 30 minutes, and then the temperature was raised again from room temperature at 20 ° C./minute using a differential scanning calorimeter DSCQ100 (manufactured by TA Instruments) at 350 ° C. for 3 minutes. Retained. At that time, the endothermic peak temperature due to melting at the time of temperature rise was defined as the melting point (Tm).
  • a melt indexer manufactured by Toyo Seiki
  • RV5 post-residence relative viscosity
  • the b * value here is a value defined in the CIEL * a * b * color system.
  • Melt flow rate Measured by ASTM D1238 method at a melting point + 20 ° C. and a load of 2.16 kg.
  • Example 1 1,6-hexamethylenediamine 8.57 kg (73.8 mol), terephthalic acid 12.24 kg (73.7 mol), 11-aminoundecanoic acid 7.99 kg (39.7 mol), diphosphorous acid as catalyst 9 g of sodium, 150 g of acetic acid (2.5 mol) as end-capping agent and 16.20 kg of ion-exchanged water were charged into a 50 liter autoclave, pressurized with N 2 from normal pressure to 0.05 MPa, let to release, and returned to normal pressure. Returned. This operation was performed 3 times, N 2 substitution was performed, and then uniform dissolution was performed at 135 ° C. and 0.3 MPa with stirring.
  • the solution was continuously supplied by a liquid feed pump, heated to 240 ° C. with a heating pipe, and heated for 1 hour. Thereafter, the reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate (terminal blocking ratio 16). %). Thereafter, the low-order condensate was taken out in the atmosphere at room temperature and normal pressure, and then dried in an environment of 70 ° C. and a vacuum degree of 50 Torr using a vacuum dryer. After drying, the low-order condensate was reacted for 6 hours in an environment of 220 ° C.
  • the obtained semiaromatic polyamide resin had a relative viscosity (RV0) of 2.03, a melting point of 315 ° C., a terminal amino group concentration of 2 eq / ton and a terminal carboxyl group concentration of 111 eq / ton analyzed by 1 H-NMR. Details of the properties of the semi-aromatic polyamide resin obtained in Example 1 are shown in Table 1.
  • Example 2 The amount of acetic acid was changed to 206 g (3.4 mol), and the low-order condensate in which the end-capping ratio of the low-order condensate was 20% was dried in the same manner as in Example 1 and then blender (capacity 0.1 m 3 ). Was used for 1 hour in an environment of 260 ° C. and a vacuum of 50 Torr to obtain a semi-aromatic polyamide resin.
  • the obtained semiaromatic polyamide resin had a relative viscosity (RV0) of 1.91, a melting point of 314 ° C., a terminal amino group concentration of 1 eq / ton and a terminal carboxyl group concentration of 109 eq / ton analyzed by 1 H-NMR. Details of the properties of the semi-aromatic polyamide resin obtained in Example 2 are shown in Table 1.
  • Example 3 The low-order condensate in which the amount of acetic acid was changed to 256 g (4.3 mol) and the end-capping ratio of the low-order condensate was 23% was dried in the same manner as in Example 1 and then blender (capacity 0.1 m 3 ). Was used for 1 hour in an environment of 250 ° C. and a vacuum of 50 Torr to obtain a semi-aromatic polyamide resin.
  • the obtained semiaromatic polyamide resin had a relative viscosity (RV0) of 1.77, a melting point of 318 ° C., a terminal amino group concentration of 0 eq / ton and a terminal carboxyl group concentration of 129 eq / ton analyzed by 1 H-NMR. Details of the properties of the semi-aromatic polyamide resin obtained in Example 3 are shown in Table 1.
  • Example 4 The low-order condensate in which the amount of acetic acid was changed to 305 g (5.1 mol) and the end-capping ratio of the low-order condensate was 28% was dried in the same manner as in Example 1 and then blender (capacity 0.1 m 3 ). Was used for 1 hour in an environment of 235 ° C. and a vacuum of 50 Torr to obtain a semi-aromatic polyamide resin.
  • the obtained semi-aromatic polyamide resin had a relative viscosity (RV0) of 1.70, a melting point of 312 ° C., a terminal amino group concentration of 0 eq / ton and a terminal carboxyl group concentration of 141 eq / ton analyzed by 1 H-NMR. Details of the properties of the semi-aromatic polyamide resin obtained in Example 4 are shown in Table 1.
  • reaction mixture was supplied to a pressure reaction can, heated to 290 ° C., and a part of water was distilled off so as to maintain the internal pressure of the can at 3 MPa to obtain a low-order condensate (end blockage of 0). %).
  • the obtained semiaromatic polyamide resin had a relative viscosity (RV0) of 2.02, a melting point of 314 ° C., a terminal amino group concentration of 16 eq / ton and a terminal carboxyl group concentration of 128 eq / ton analyzed by 1 H-NMR. Details of the properties of the obtained semi-aromatic polyamide resin of Comparative Example 1 are shown in Table 1.
  • a semi-aromatic polyamide resin was obtained in the same manner as in Comparative Example 1 except that the amount of acetic acid was changed to 161 g (2.7 mol).
  • the obtained semiaromatic polyamide resin had a relative viscosity (RV0) of 1.81, a melting point of 312 ° C., a terminal amino group concentration of 11 eq / ton and a terminal carboxyl group concentration of 147 eq / ton analyzed by 1 H-NMR. Details of the properties of the obtained semi-aromatic polyamide resin of Comparative Example 2 are shown in Table 1.
  • a semi-aromatic polyamide resin was obtained in the same manner as in Comparative Example 1 except that the amount of acetic acid was changed to 176 g (2.9 mol).
  • the obtained semiaromatic polyamide resin had a relative viscosity (RV0) of 1.76, a melting point of 315 ° C., a terminal amino group concentration of 12 eq / ton and a terminal carboxyl group concentration of 155 eq / ton analyzed by 1 H-NMR. Details of the properties of the obtained semi-aromatic polyamide resin of Comparative Example 3 are shown in Table 1.
  • Examples 1 to 4 not only have a high melting point, but also have a low terminal amino group concentration (AEG), and a low relative viscosity ratio RV5 / RV0 before and after thermal history. Thus, it can be seen that no increase in relative viscosity is observed due to the heat history during processing. As a result, it is possible to remarkably suppress the strand foaming and fluidity deterioration that occur when the reinforcing material or the filler is highly filled, which is seen in the conventional semi-aromatic polyamide resin, It is very advantageous to obtain a material excellent in moldability.
  • AEG terminal amino group concentration
  • Comparative Examples 2 and 3 have a high melting point and low RV0 and RV5 / RV0, so heat resistance, kneadability and formability are satisfactory, but AEG and AEG / CEG are high, and ⁇ b * is high. Insufficient color stability.
  • the semi-aromatic polyamide resin of the present invention is useful as a resin composition for molded articles such as automobile parts and electric / electronic parts, which are excellent in heat resistance and melt fluidity and also in color tone stability.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyamides (AREA)

Abstract

La présente invention décrit une résine de polyamide semi-aromatique qui présente une excellente résistance à la chaleur et fluidité à l'état fondu, et en outre présente une excellente résistance à la décoloration thermique, et convient pour une composition de résine pour articles moulés tels que des pièces automobiles, des pièces électriques/électroniques, et similaires. La résine de polyamide semi-aromatique contient 50 % en mole ou plus d'un motif constitutif obtenu à partir d'un sel équimolaire d'une diamine possédant 2 à 12 atomes de carbone et d'acide téréphtalique, et satisfait les exigences (a)-(d) : (a) le point de fusion (Tm) est 290 à 350°C ; (b) la viscosité initiale relative (RV0) est 1,3 à 2,1, et le rapport (MFR/RV5) de la valeur numérique de la vitesse d'écoulement à l'état fondu (MFR) à la valeur numérique de la viscosité relative (RV5) obtenue après que la masse fondue soit maintenue à une température de 20°C au-dessus du point de fusion durant 5 minutes est de 50 ou plus ; (c) la concentration en groupes amino terminaux (AEG) est de 15 éq./tonne ou moins, et le rapport (AEG/CEG) de AEG à la concentration en groupes carboxyle terminaux (CEG) est de 0,07 ou moins ; et (d) le rapport (RV5/RV0) de la viscosité relative (RV5) à la viscosité relative (RV0) est de 0,900 à 1,010.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019189145A1 (fr) 2018-03-29 2019-10-03 東洋紡株式会社 Résine de polyamide semi-aromatique et son procédé de production
CN111133038A (zh) * 2017-09-25 2020-05-08 东洋纺株式会社 具有以半芳香族聚酰胺树脂组合物构成的成形品为构成成分的成形体
WO2020122170A1 (fr) 2018-12-14 2020-06-18 東洋紡株式会社 Résine de polyamide semi-aromatique et procédé pour sa production
WO2021059901A1 (fr) * 2019-09-27 2021-04-01 東洋紡株式会社 Composition de resine polyamide semi-aromatique renforcee inorganique
WO2021065205A1 (fr) * 2019-09-30 2021-04-08 東洋紡株式会社 Composition de resine polyamide semi-aromatique renforcee inorganique
WO2021235348A1 (fr) * 2020-05-18 2021-11-25 宇部興産株式会社 Résine de polyamide, composition contenant ladite résine de polyamide et corps moulé contenant ladite résine de polyamide et composition
CN114585688A (zh) * 2019-11-29 2022-06-03 东洋纺株式会社 半芳香族聚酰胺树脂组合物、及金属镀敷成形体

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228689A (ja) * 1994-02-16 1995-08-29 Kuraray Co Ltd ポリアミド樹脂
JPH1192657A (ja) * 1997-09-19 1999-04-06 Daicel Huels Ltd 金属粉体複合成形品用ポリアミド樹脂
WO2011052464A1 (fr) * 2009-10-27 2011-05-05 東洋紡績株式会社 Polyamide copolymérisé
WO2012098840A1 (fr) * 2011-01-17 2012-07-26 株式会社クラレ Composition de résine et article moulé la contenant
WO2015029780A1 (fr) * 2013-08-30 2015-03-05 東洋紡株式会社 Composition de résine polyamide à point de fusion élevé présentant d'excellentes propriétés de vibration après absorption d'eau et d'aspect

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07228689A (ja) * 1994-02-16 1995-08-29 Kuraray Co Ltd ポリアミド樹脂
JPH1192657A (ja) * 1997-09-19 1999-04-06 Daicel Huels Ltd 金属粉体複合成形品用ポリアミド樹脂
WO2011052464A1 (fr) * 2009-10-27 2011-05-05 東洋紡績株式会社 Polyamide copolymérisé
WO2012098840A1 (fr) * 2011-01-17 2012-07-26 株式会社クラレ Composition de résine et article moulé la contenant
WO2015029780A1 (fr) * 2013-08-30 2015-03-05 東洋紡株式会社 Composition de résine polyamide à point de fusion élevé présentant d'excellentes propriétés de vibration après absorption d'eau et d'aspect

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111133038A (zh) * 2017-09-25 2020-05-08 东洋纺株式会社 具有以半芳香族聚酰胺树脂组合物构成的成形品为构成成分的成形体
JP7279634B2 (ja) 2018-03-29 2023-05-23 東洋紡株式会社 半芳香族ポリアミド樹脂、及びその製造方法
KR20200139185A (ko) * 2018-03-29 2020-12-11 도요보 가부시키가이샤 반방향족 폴리아미드 수지 및 그의 제조 방법
CN112204075A (zh) * 2018-03-29 2021-01-08 东洋纺株式会社 半芳香族聚酰胺树脂及其制造方法
JPWO2019189145A1 (ja) * 2018-03-29 2021-02-12 東洋紡株式会社 半芳香族ポリアミド樹脂、及びその製造方法
WO2019189145A1 (fr) 2018-03-29 2019-10-03 東洋紡株式会社 Résine de polyamide semi-aromatique et son procédé de production
KR102658406B1 (ko) 2018-03-29 2024-04-16 도요보 엠씨 가부시키가이샤 반방향족 폴리아미드 수지 및 그의 제조 방법
WO2020122170A1 (fr) 2018-12-14 2020-06-18 東洋紡株式会社 Résine de polyamide semi-aromatique et procédé pour sa production
KR20210102280A (ko) 2018-12-14 2021-08-19 도요보 가부시키가이샤 반방향족 폴리아미드 수지 및 그의 제조 방법
WO2021059901A1 (fr) * 2019-09-27 2021-04-01 東洋紡株式会社 Composition de resine polyamide semi-aromatique renforcee inorganique
WO2021065205A1 (fr) * 2019-09-30 2021-04-08 東洋紡株式会社 Composition de resine polyamide semi-aromatique renforcee inorganique
CN114585688A (zh) * 2019-11-29 2022-06-03 东洋纺株式会社 半芳香族聚酰胺树脂组合物、及金属镀敷成形体
WO2021235348A1 (fr) * 2020-05-18 2021-11-25 宇部興産株式会社 Résine de polyamide, composition contenant ladite résine de polyamide et corps moulé contenant ladite résine de polyamide et composition

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