WO2017131008A1 - Heat-resistant polyamide resin composition - Google Patents
Heat-resistant polyamide resin composition Download PDFInfo
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- WO2017131008A1 WO2017131008A1 PCT/JP2017/002470 JP2017002470W WO2017131008A1 WO 2017131008 A1 WO2017131008 A1 WO 2017131008A1 JP 2017002470 W JP2017002470 W JP 2017002470W WO 2017131008 A1 WO2017131008 A1 WO 2017131008A1
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- polyamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to a polyamide resin composition, and more particularly to a polyamide resin composition having excellent heat aging resistance.
- Polyamide resins have been widely used in various parts such as automobile parts, electrical and electronic parts, and industrial machine parts because they have excellent characteristics such as mechanical properties, chemical resistance and molding processability.
- Polyamide resins are a class of resins that are relatively excellent in heat aging resistance, but deterioration due to the action of heat and light is inevitable.
- As a method for improving heat aging resistance copper halide, potassium halide, oxazole compounds, etc. are heated.
- a method of adding as a stabilizer has been known for a long time (for example, Patent Document 1).
- polyamide resins are used for parts that are exposed to a high temperature environment of about 140 ° C. in the field of automobile parts, electrical and electronic parts.
- the environmental temperature in the engine room has increased with the increase in engine output and the density of parts in recent years, and unprecedented heat aging resistance has been demanded. .
- Patent Document 2 a method of blending fine elemental iron with polyamide
- Patent Document 3 a method of blending finely dispersed metal powder with polyamide
- Patent Document 4 a method of blending a heat stabilizer such as copper iodide and potassium iodide and a complex oxide such as iron trioxide (including iron (II) oxide)
- Patent Document 5 a method of blending a heat stabilizer such as copper iodide and potassium iodide and a complex oxide such as iron trioxide (including iron (II) oxide)
- Patent Document 2 and Patent Document 3 there is a risk of catching fire during the production of the composition, and the production is not easy.
- the method of Patent Document 4 the effect is exhibited only with a very limited composition.
- the method of Patent Document 5 is inferior in heat aging resistance and stability of mechanical strength, and there is room for improvement in the current situation.
- An object of the present invention is to provide a polyamide resin composition that can exhibit stable heat aging resistance even under a high temperature environment of about 200 ° C., is excellent in mechanical strength, and is easy to manufacture.
- the present invention is as follows. [1] 0.1 to 10 parts by mass of a metal salt of acetic acid with respect to 100 parts by mass of the polyamide resin, and the metal of the metal salt is an alkali metal, an alkaline earth metal, a group VB, a group VIB of the periodic table, A polyamide resin composition, wherein the polyamide resin composition is at least one selected from Group VIIB and Group VIIIB transition metals. [2] The polyamide resin composition according to [1], wherein the metal salt of acetic acid is at least one selected from lithium acetate, calcium acetate, sodium acetate, and iron acetate. [3] The polyamide resin composition according to [1] or [2], wherein a molded product obtained by injection molding of the polyamide resin composition has a tensile strength retention after heat treatment at 200 ° C. for 1000 hours of 80% or more. object.
- the polyamide resin composition of the present invention is used for automobiles and electrical / electronic parts that require little deterioration in mechanical properties and high heat aging resistance even when exposed to a high temperature (200 ° C. or higher) environment for a long period of time.
- a possible polyamide resin composition is used for automobiles and electrical / electronic parts that require little deterioration in mechanical properties and high heat aging resistance even when exposed to a high temperature (200 ° C. or higher) environment for a long period of time.
- the polyamide resin in the present invention is not particularly limited.
- a ring-opening polymerization product of cyclic lactam a polycondensation product of aminocarboxylic acid, a polycondensation product of dibasic acid and diamine, and a copolymer thereof.
- polycaproamide polyamide 6
- polyhexamethylene adipamide polyamide 66
- polytetramethylene adipamide polyamide 46
- polyhexamethylene sebacamide polyamide 610
- Aliphatic polyamides such as polyhexamethylene dodecamide (polyamide 612), poly-lauryl lactam (polyamide 12), poly-11-aminoundecanoic acid (polyamide 11), poly (metaxylene adipamide) (polyamide MXD6)
- Poly (hexamethylene terephthalamide) polyamide 6T
- poly (f Aliphatic-aromatic polyamides such as samethylene isophthalamide) (polyamide 6I), poly (nonamethylene terephthalamide) (polyamide 9T), poly (tetramethylene isophthalamide) (polyamide 4I), and copolymers and mixtures thereof Can be mentioned.
- Particularly suitable polyamides for the present invention include polyamide 6, polyamide 66, polyamide 6/66 copolymer, polyamide 66 / 6T copolymer, polyamide 6T / 12 copolymer, polyamide 6T / 11 copolymer, polyamide 6T / 6I copolymer, polyamide 6T / 6I / 12 copolymer, polyamide 6T / 610 copolymer, and polyamide 6T / 6I / 6 copolymer.
- the molecular weight of such a polyamide resin is not particularly limited, but a polyamide resin having a relative viscosity of 1.7 to 4.5 measured at 25 ° C. in 98% (98% by mass) sulfuric acid at a concentration of 1% by mass is used. It is preferable.
- the relative viscosity of the polyamide resin is more preferably 2.0 to 4.0, still more preferably 2.0 to 3.5.
- the metal of the metal salt of acetic acid in the present invention is at least one selected from alkali metals, alkaline earth metals, transition metals of Group VB, VIB, VIIB, and VIIIB of the periodic table.
- alkali metal include lithium, sodium, and potassium.
- alkaline earth metal include magnesium and calcium.
- transition metals of Group VB, VIB, VIIB, and VIIIB of the periodic table include vanadium, chromium, manganese, and iron.
- Specific compounds include lithium acetate, calcium acetate, sodium acetate, iron acetate and the like.
- the iron acetate is preferably iron (II) acetate.
- the metal is preferably at least one selected from alkali metals and alkaline earth metals, and more preferably alkali metals.
- at least one selected from lithium acetate, calcium acetate, and sodium acetate is preferable, and at least one selected from lithium acetate and sodium acetate is more preferable.
- the content of the metal salt of acetic acid is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin. Part. If the amount is less than 0.1 parts by mass, there is almost no effect of developing heat aging resistance, and if it exceeds 10 parts by mass, the effect of developing heat aging property will not increase any further. If the metal salt of acetic acid is 10 parts by mass or less, unlike metal particles or metal oxide particles, there is little adverse effect on mechanical properties, and in particular, glass fiber breakage can be suppressed even in glass fiber reinforced compositions. Therefore, the mechanical properties are hardly deteriorated.
- the metal salt of acetic acid has an oxygen scavenging effect near the surface layer of the polyamide resin, and the oxidative deterioration of the polyamide resin. It is thought that it is because it can suppress.
- a known heat stabilizer can also be used in combination with the resin composition of the present invention.
- Examples of the copper compound that can be used in the present invention include copper acetate, copper iodide, copper bromide, copper chloride, copper fluoride, copper laurate, and copper stearate. These copper compounds may be used alone or in combination. Copper acetate, copper iodide, copper bromide and copper chloride are preferred, and cupric bromide is particularly preferably used.
- the addition amount of the copper compound is preferably 0.0001 to 1 part by mass as copper in the copper compound with respect to 100 parts by mass of the polyamide resin.
- a more preferable addition amount is 0.0005 to 1 part by mass, a further preferable addition amount is 0.0005 to 0.03 part by mass, and a particularly preferable addition amount is 0.0005 to 0.02 part by mass. is there.
- a copper compound when adding a copper compound, it is preferable to use an alkali metal halide compound such as potassium iodide or potassium bromide in combination. By using together, precipitation of copper can be prevented.
- a method for adding the copper compound it may be added at any stage of the production of the polyamide resin, and the addition method is not limited. For example, a method of adding to a raw material salt aqueous solution of polyamide, a method of injecting and adding to a molten polyamide in the middle of melt polymerization, and after blending a granulated polyamide pellet and the copper compound powder or masterbatch after polymerization Any of a method of melt kneading using an extruder, a molding machine or the like may be used.
- an auxiliary stabilizer such as a hindered phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant, an amine antioxidant, or a light stabilizer is added. Can do.
- hindered phenol antioxidant can be used alone or in combination.
- phenols having two or more functional groups are preferable, and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245)
- IRGANOX245 triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate]
- the blending amount (content) is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin. 2 parts by mass. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
- the phosphorus antioxidant is at least one selected from inorganic and organic phosphorus antioxidants.
- inorganic phosphorus antioxidants include hypophosphites such as sodium hypophosphite and phosphites.
- organic phosphorus antioxidant commercially available organic phosphorus antioxidants such as phosphites can be used, but organic phosphorus-containing compounds that do not generate phosphoric acid by thermal decomposition are preferable. As such organic phosphorus-containing compounds, known compounds can be used.
- the blending amount (content) is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. If the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is insufficient. On the other hand, if the amount exceeds 3 parts by mass, flashing may occur in the molded product. In the present invention, it is preferable to use inorganic and organic phosphorus antioxidants in combination because the amount of the antioxidant can be reduced.
- amine-based antioxidant that can be used in the present invention
- known compounds can be used.
- Secondary arylamines can also be mentioned as amine-based antioxidants.
- secondary arylamine is meant an amine compound containing two carbon radicals chemically bonded to a nitrogen atom, wherein at least one, preferably both carbon radicals are aromatic.
- the blending amount (content) is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyamide resin. Part. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
- sulfur-based antioxidant that can be used in the present invention, known compounds can be used.
- the blending amount (content) is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
- the light stabilizer that can be used in the present invention is preferably one or more hindered amine type light stabilizers (HALS).
- HALS is a compound derived from a substituted piperidine compound, in particular a compound derived from an alkyl-substituted piperidinyl or piperazinone compound, and an alkoxy-substituted piperidinyl compound.
- a known compound can be used.
- a mixture of secondary arylamine and HALS can be used.
- Preferred embodiments comprise at least two co-stabilizers, at least one selected from secondary arylamines and at least one selected from the group of HALS.
- the total blending amount is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 3 parts per 100 parts by mass of the polyamide resin. Part by mass. If the amount is less than 0.5 parts by mass, the effect of improving the heat aging resistance is insufficient. On the other hand, if the amount exceeds 10 parts by mass, the effect may be saturated or blooming may occur on the surface of the molded product.
- the strength, rigidity, heat resistance and the like can be significantly improved by adding a filler.
- a filler include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastonite, glass flake, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, oxidation Examples thereof include titanium and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.
- the blending amount (content) is preferably 5 to 140 parts by weight, particularly preferably 5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
- ultraviolet absorbers for example, resorcinol, salicylate, benzotriazole, benzophenone, etc.
- lubricants and mold release agents for example, nucleating agents, plasticizers, and the like within a range not impairing the object of the present invention.
- One or more conventional additives such as an antistatic agent and a colorant containing a dye / pigment can be added up to about 5 parts by mass with respect to 100 parts by mass of the polyamide resin.
- the polyamide resin composition of the present invention can contain each of the components described above, but in the composition excluding the filler, 90% by mass or more in total of the polyamide resin and the metal salt of acetic acid. It is preferable to occupy 95% by mass or more.
- the method for incorporating the metal salt of acetic acid and other additives in the present invention into the polyamide resin is not particularly limited, and may be performed by any method. For example, after all the components are premixed, the method is kneaded in an extruder or kneader, or the other components are kneaded and blended with pellets obtained by kneading any number of components in advance in an extruder or kneader. Is mentioned.
- the tensile strength retention after heat treatment at 200 ° C. for 1000 hours of a molded product obtained by injection molding of the polyamide resin composition of the present invention can be 80% or more.
- the molded product is a test piece molded in accordance with the description in the following example section, and the heat treatment is a process performed in the procedure described in the following example section.
- the tensile strength retention is the retention of the tensile strength after the heat treatment relative to the tensile strength of the test piece before the heat treatment.
- the tensile strength retention is more preferably 85% or more.
- the polyamide resin composition of the present invention can be formed into a molded body by a so-called hollow method represented by injection molding, extrusion molding, thermoforming, compression molding, blow molding, die slide molding or the like.
- these molded products can be formed into molded products by secondary processing, for example, welding methods including vibration welding, hot plate welding, ultrasonic welding, and the like.
- it is an injection-molded or blow-molded body, and a molded body by secondary processing thereof.
- Examples of uses of the molded article of the polyamide resin composition of the present invention include, in the automobile and vehicle fields, for example, a cylinder head cover, an engine cover, an intercooler housing, a valve, an end cap, a caster, a trolley part, etc.
- intake pipes air ducts
- intake system parts such as intake manifolds, connectors, gears, fan wheels, coolant storage containers, housings or housing parts for heat exchangers, radiators, thermostats, coolants and water pumps, Heater, fastening element, oil pan, exhaust system such as muffler and catalytic converter housing, timing chain belt front cover, gear box, bearing, gasoline cap, seat parts, headrest, door handle, wire Such as over parts, and the like.
- circuit board components housings, films, conductors, switches, terminal strips, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, memories, bolts, coil bobbins , Plugs, plug parts, mechatronic parts, cooking equipment, washing machine, refrigerator, air conditioner and other home appliance parts, sensors and the like.
- Heat aging test The test piece was heat-treated in a recirculation air oven (manufactured by Nagano Kagaku Kikai Co., Ltd., hot air circulation dryer NH-401S) according to the procedure detailed in ISO2578. The specimens were removed from the oven at 200 ° C. environment for a predetermined test time (500 hours, 1000 hours), cooled to room temperature and sealed in an aluminum lined bag until ready for testing. Subsequently, the tensile strength and the tensile elongation at break were measured according to ISO527-1,2. The average value obtained from three test pieces was adopted.
- the retention rate of tensile strength and tensile elongation at break is the retention rate after heat treatment for 500 hours and 1000 hours when the initial value without heat treatment is 100%.
- Examples 1 to 7, Comparative Examples 1 to 7 The resin compositions described as Examples and Comparative Examples were prepared by blending the above raw materials at the ratios (mass ratios) shown in Table 1 using a twin-screw extruder (STS35 manufactured by Coperion Co., Ltd.), and melt-kneading them. To obtain pellets (diameter: about 2.5 mm ⁇ length: about 2.5 mm). The obtained pellets were used after drying at 100 ° C. for 4 hours or more in a hot air circulation dryer. The evaluation results are shown in Table 1.
- Examples 1 to 7 have high initial tensile strength (before heat treatment) and tensile elongation at break, and the tensile strength retention after heat treatment at 200 ° C. for 500 hours and 1000 hours is a high value of 80% or more.
- the tensile rupture elongation retention rate is as high as 70% or more.
- Comparative Example 6 is a case where only a phenolic antioxidant and cupric bromide were added, but the tensile strength retention rate and tensile fracture elongation retention rate after 1000 hours at 200 ° C. ⁇ 500 hours were greatly reduced. is doing.
- Comparative Example 1 is a case where the amount of metal acetate added is small, but the tensile strength retention rate and tensile fracture elongation retention rate after 200 ° C. ⁇ 500 hours and 1000 hours are significantly reduced.
- Comparative Examples 2, 3, 4, 5, and 7 are cases where iron oxide (II), iron oxide (III), iron chloride (II), phthalocyanine iron (II), and aluminum acetate were added, respectively. ⁇ The tensile strength retention and tensile rupture elongation retention after 500 hours and 1000 hours are significantly reduced.
- the polyamide resin composition obtained according to the present invention has an environment at 200 ° C. because the heat aging resistance in a high temperature environment of about 200 ° C. can be easily and stably improved. It can be used for parts of automobiles and electrical / electronic products that may be exposed to
Abstract
The present invention provides a polyamide resin composition that exhibits a stable heat aging resistance even under a high-temperature environment of about 200ºC, that also possesses superior mechanical strength, and that is easily manufactured. The polyamide resin composition is characterized in that 0.1-10 parts by mass of a metal salt of acetic acid is contained therein with respect to 100 parts by mass of the polyamide resin, and that the metal of the metal salt is at least one type of metal selected from alkaline metals, alkaline earth metals, and transition metals of the VB group, the VIB group, the VIIB group, and the VIIIB group in the periodic table.
Description
本発明は、ポリアミド樹脂組成物に関し、詳しくは耐熱老化性に優れたポリアミド樹脂組成物に関する。
The present invention relates to a polyamide resin composition, and more particularly to a polyamide resin composition having excellent heat aging resistance.
ポリアミド樹脂は、機械的特性を始めとして、耐薬品性及び成形加工性などに優れた特性を有するため、従来より自動車部品、電気電子部品、工業機械部品などの各種部品に広く利用されている。ポリアミド樹脂は、比較的耐熱老化性に優れる部類の樹脂ではあるが、熱及び光の作用による劣化は不可避であり、耐熱老化性向上法として、ハロゲン化銅、ハロゲン化カリウム、オキサゾール化合物などを熱安定剤として添加する方法が古くから知られている（例えば、特許文献１）。
Polyamide resins have been widely used in various parts such as automobile parts, electrical and electronic parts, and industrial machine parts because they have excellent characteristics such as mechanical properties, chemical resistance and molding processability. Polyamide resins are a class of resins that are relatively excellent in heat aging resistance, but deterioration due to the action of heat and light is inevitable. As a method for improving heat aging resistance, copper halide, potassium halide, oxazole compounds, etc. are heated. A method of adding as a stabilizer has been known for a long time (for example, Patent Document 1).
これらの技術により、ポリアミド樹脂は、自動車部品や電気、電子部品の分野において、１４０℃程度の高温環境下に曝される用途の部品に用いられている。
しかしながら、例えば自動車のエンジンルームに関して、近年、エンジン出力の増加、部品の高密度化などに伴い、エンジンルーム内の環境温度が高くなり、これまでにない耐熱老化性が求められるようになっている。 With these techniques, polyamide resins are used for parts that are exposed to a high temperature environment of about 140 ° C. in the field of automobile parts, electrical and electronic parts.
However, for example, in the engine room of an automobile, the environmental temperature in the engine room has increased with the increase in engine output and the density of parts in recent years, and unprecedented heat aging resistance has been demanded. .
しかしながら、例えば自動車のエンジンルームに関して、近年、エンジン出力の増加、部品の高密度化などに伴い、エンジンルーム内の環境温度が高くなり、これまでにない耐熱老化性が求められるようになっている。 With these techniques, polyamide resins are used for parts that are exposed to a high temperature environment of about 140 ° C. in the field of automobile parts, electrical and electronic parts.
However, for example, in the engine room of an automobile, the environmental temperature in the engine room has increased with the increase in engine output and the density of parts in recent years, and unprecedented heat aging resistance has been demanded. .
これに対して、ポリアミドに微粒元素鉄を配合する方法（特許文献２）、ポリアミドに微粒分散化金属粉末を配合する方法（特許文献３）、融点が異なる２種類のポリアミド混合物に銅化合物と酸化鉄を配合する方法（特許文献４）、沃化銅と沃化カリウムなどの熱安定剤と四三酸化鉄（酸化鉄（ＩＩ）を含む）などの複合酸化物とを配合する方法（特許文献５）などが提案され、２００℃程度の高温環境下でも耐熱老化性に優れているとされている。
しかしながら、特許文献２や特許文献３の方法では、組成物の製造中に発火する危険性があり製造が容易でなく、特許文献４の方法では、非常に限定された組成でしか効果が発現しない欠点があり、特許文献５の方法では、耐熱老化性や機械的強度の安定性が劣ることがあり、それぞれ改善の余地があるのが現状である。 In contrast, a method of blending fine elemental iron with polyamide (Patent Document 2), a method of blending finely dispersed metal powder with polyamide (Patent Document 3), and a copper compound and oxidation in two types of polyamide mixtures having different melting points A method of blending iron (Patent Document 4), a method of blending a heat stabilizer such as copper iodide and potassium iodide and a complex oxide such as iron trioxide (including iron (II) oxide) (Patent Document) 5) etc. are proposed, and it is said that it is excellent in heat aging resistance even in a high temperature environment of about 200 ° C.
However, in the methods of Patent Document 2 and Patent Document 3, there is a risk of catching fire during the production of the composition, and the production is not easy. In the method of Patent Document 4, the effect is exhibited only with a very limited composition. There are drawbacks, and the method of Patent Document 5 is inferior in heat aging resistance and stability of mechanical strength, and there is room for improvement in the current situation.
しかしながら、特許文献２や特許文献３の方法では、組成物の製造中に発火する危険性があり製造が容易でなく、特許文献４の方法では、非常に限定された組成でしか効果が発現しない欠点があり、特許文献５の方法では、耐熱老化性や機械的強度の安定性が劣ることがあり、それぞれ改善の余地があるのが現状である。 In contrast, a method of blending fine elemental iron with polyamide (Patent Document 2), a method of blending finely dispersed metal powder with polyamide (Patent Document 3), and a copper compound and oxidation in two types of polyamide mixtures having different melting points A method of blending iron (Patent Document 4), a method of blending a heat stabilizer such as copper iodide and potassium iodide and a complex oxide such as iron trioxide (including iron (II) oxide) (Patent Document) 5) etc. are proposed, and it is said that it is excellent in heat aging resistance even in a high temperature environment of about 200 ° C.
However, in the methods of Patent Document 2 and Patent Document 3, there is a risk of catching fire during the production of the composition, and the production is not easy. In the method of Patent Document 4, the effect is exhibited only with a very limited composition. There are drawbacks, and the method of Patent Document 5 is inferior in heat aging resistance and stability of mechanical strength, and there is room for improvement in the current situation.
本発明は、２００℃程度の高温環境下でも安定した耐熱老化性を発現でき、また、機械的強度にも優れ、製造が容易なポリアミド樹脂組成物を提供することを目的とする。
An object of the present invention is to provide a polyamide resin composition that can exhibit stable heat aging resistance even under a high temperature environment of about 200 ° C., is excellent in mechanical strength, and is easy to manufacture.
本発明者等は上述の問題を解決するため鋭意研究を重ねた結果、本発明に到達した。
即ち本発明は、以下の通りである。
［１］ ポリアミド樹脂１００質量部に対して、酢酸の金属塩を０．１～１０質量部含有し、前記金属塩の金属がアルカリ金属、アルカリ土類金属、周期表のＶＢ族、ＶＩＢ族、ＶＩＩＢ族、ＶＩＩＩＢ族の遷移金属から選ばれる少なくとも１種であることを特徴とするポリアミド樹脂組成物。
［２］ 前記酢酸の金属塩が、酢酸リチウム、酢酸カルシウム、酢酸ナトリウム、及び酢酸鉄から選ばれる少なくとも１種である［１］に記載のポリアミド樹脂組成物。
［３］ 前記ポリアミド樹脂組成物を射出成形して得られる成形品の２００℃、１０００時間の熱処理後の引張強度保持率が８０％以上である［１］または［２］に記載のポリアミド樹脂組成物。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is as follows.
[1] 0.1 to 10 parts by mass of a metal salt of acetic acid with respect to 100 parts by mass of the polyamide resin, and the metal of the metal salt is an alkali metal, an alkaline earth metal, a group VB, a group VIB of the periodic table, A polyamide resin composition, wherein the polyamide resin composition is at least one selected from Group VIIB and Group VIIIB transition metals.
[2] The polyamide resin composition according to [1], wherein the metal salt of acetic acid is at least one selected from lithium acetate, calcium acetate, sodium acetate, and iron acetate.
[3] The polyamide resin composition according to [1] or [2], wherein a molded product obtained by injection molding of the polyamide resin composition has a tensile strength retention after heat treatment at 200 ° C. for 1000 hours of 80% or more. object.
即ち本発明は、以下の通りである。
［１］ ポリアミド樹脂１００質量部に対して、酢酸の金属塩を０．１～１０質量部含有し、前記金属塩の金属がアルカリ金属、アルカリ土類金属、周期表のＶＢ族、ＶＩＢ族、ＶＩＩＢ族、ＶＩＩＩＢ族の遷移金属から選ばれる少なくとも１種であることを特徴とするポリアミド樹脂組成物。
［２］ 前記酢酸の金属塩が、酢酸リチウム、酢酸カルシウム、酢酸ナトリウム、及び酢酸鉄から選ばれる少なくとも１種である［１］に記載のポリアミド樹脂組成物。
［３］ 前記ポリアミド樹脂組成物を射出成形して得られる成形品の２００℃、１０００時間の熱処理後の引張強度保持率が８０％以上である［１］または［２］に記載のポリアミド樹脂組成物。 The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems.
That is, the present invention is as follows.
[1] 0.1 to 10 parts by mass of a metal salt of acetic acid with respect to 100 parts by mass of the polyamide resin, and the metal of the metal salt is an alkali metal, an alkaline earth metal, a group VB, a group VIB of the periodic table, A polyamide resin composition, wherein the polyamide resin composition is at least one selected from Group VIIB and Group VIIIB transition metals.
[2] The polyamide resin composition according to [1], wherein the metal salt of acetic acid is at least one selected from lithium acetate, calcium acetate, sodium acetate, and iron acetate.
[3] The polyamide resin composition according to [1] or [2], wherein a molded product obtained by injection molding of the polyamide resin composition has a tensile strength retention after heat treatment at 200 ° C. for 1000 hours of 80% or more. object.
本発明のポリアミド樹脂組成物は、高温（２００℃以上）環境下に長期間曝される場合でも、機械的特性の低下が小さく、高い耐熱老化性が要求される自動車、電気電子部品用として利用可能なポリアミド樹脂組成物である。
The polyamide resin composition of the present invention is used for automobiles and electrical / electronic parts that require little deterioration in mechanical properties and high heat aging resistance even when exposed to a high temperature (200 ° C. or higher) environment for a long period of time. A possible polyamide resin composition.
以下に本発明を具体的に説明する。
本発明におけるポリアミド樹脂としては、特に限定されるものではないが、例えば、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物、二塩基酸とジアミンとの重縮合物、これらの共重合物などが挙げられ、具体的にはポリカプロアミド（ポリアミド６）、ポリヘキサメチレンアジパミド（ポリアミド６６）、ポリテトラメチレンアジパミド（ポリアミド４６）、ポリヘキサメチレンセバカミド（ポリアミド６１０）、ポリヘキサメチレンドデカミド（ポリアミド６１２）、ポリ－ラウリルラクタム（ポリアミド１２）、ポリ－１１－アミノウンデカン酸（ポリアミド１１）等の脂肪族ポリアミド、ポリ（メタキシレンアジパミド）（ポリアミドＭＸＤ６）、ポリ（ヘキサメチレンテレフタルアミド）（ポリアミド６Ｔ）、ポリ（ヘキサメチレンイソフタルアミド）（ポリアミド６Ｉ）、ポリ（ノナメチレンテレフタルアミド）（ポリアミド９Ｔ）、ポリ（テトラメチレンイソフタルアミド）（ポリアミド４Ｉ）などの脂肪族－芳香族ポリアミド、およびこれらの共重合体や混合物を挙げることができる。特に本発明に好適なポリアミドとしてはポリアミド６、ポリアミド６６、ポリアミド６／６６共重合体、ポリアミド６６／６Ｔ共重合体、ポリアミド６Ｔ／１２共重合体、ポリアミド６Ｔ／１１共重合体、ポリアミド６Ｔ／６Ｉ共重合体、ポリアミド６Ｔ／６Ｉ／１２共重合体、ポリアミド６Ｔ／６１０共重合体、ポリアミド６Ｔ／６Ｉ／６共重合体を挙げることができる。 The present invention will be specifically described below.
The polyamide resin in the present invention is not particularly limited. For example, a ring-opening polymerization product of cyclic lactam, a polycondensation product of aminocarboxylic acid, a polycondensation product of dibasic acid and diamine, and a copolymer thereof. Specifically, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610) Aliphatic polyamides such as polyhexamethylene dodecamide (polyamide 612), poly-lauryl lactam (polyamide 12), poly-11-aminoundecanoic acid (polyamide 11), poly (metaxylene adipamide) (polyamide MXD6), Poly (hexamethylene terephthalamide) (polyamide 6T), poly (f Aliphatic-aromatic polyamides such as samethylene isophthalamide) (polyamide 6I), poly (nonamethylene terephthalamide) (polyamide 9T), poly (tetramethylene isophthalamide) (polyamide 4I), and copolymers and mixtures thereof Can be mentioned. Particularly suitable polyamides for the present invention include polyamide 6, polyamide 66, polyamide 6/66 copolymer, polyamide 66 / 6T copolymer, polyamide 6T / 12 copolymer, polyamide 6T / 11 copolymer, polyamide 6T / 6I copolymer, polyamide 6T / 6I / 12 copolymer, polyamide 6T / 610 copolymer, and polyamide 6T / 6I / 6 copolymer.
本発明におけるポリアミド樹脂としては、特に限定されるものではないが、例えば、環状ラクタムの開環重合物、アミノカルボン酸の重縮合物、二塩基酸とジアミンとの重縮合物、これらの共重合物などが挙げられ、具体的にはポリカプロアミド（ポリアミド６）、ポリヘキサメチレンアジパミド（ポリアミド６６）、ポリテトラメチレンアジパミド（ポリアミド４６）、ポリヘキサメチレンセバカミド（ポリアミド６１０）、ポリヘキサメチレンドデカミド（ポリアミド６１２）、ポリ－ラウリルラクタム（ポリアミド１２）、ポリ－１１－アミノウンデカン酸（ポリアミド１１）等の脂肪族ポリアミド、ポリ（メタキシレンアジパミド）（ポリアミドＭＸＤ６）、ポリ（ヘキサメチレンテレフタルアミド）（ポリアミド６Ｔ）、ポリ（ヘキサメチレンイソフタルアミド）（ポリアミド６Ｉ）、ポリ（ノナメチレンテレフタルアミド）（ポリアミド９Ｔ）、ポリ（テトラメチレンイソフタルアミド）（ポリアミド４Ｉ）などの脂肪族－芳香族ポリアミド、およびこれらの共重合体や混合物を挙げることができる。特に本発明に好適なポリアミドとしてはポリアミド６、ポリアミド６６、ポリアミド６／６６共重合体、ポリアミド６６／６Ｔ共重合体、ポリアミド６Ｔ／１２共重合体、ポリアミド６Ｔ／１１共重合体、ポリアミド６Ｔ／６Ｉ共重合体、ポリアミド６Ｔ／６Ｉ／１２共重合体、ポリアミド６Ｔ／６１０共重合体、ポリアミド６Ｔ／６Ｉ／６共重合体を挙げることができる。 The present invention will be specifically described below.
The polyamide resin in the present invention is not particularly limited. For example, a ring-opening polymerization product of cyclic lactam, a polycondensation product of aminocarboxylic acid, a polycondensation product of dibasic acid and diamine, and a copolymer thereof. Specifically, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610) Aliphatic polyamides such as polyhexamethylene dodecamide (polyamide 612), poly-lauryl lactam (polyamide 12), poly-11-aminoundecanoic acid (polyamide 11), poly (metaxylene adipamide) (polyamide MXD6), Poly (hexamethylene terephthalamide) (polyamide 6T), poly (f Aliphatic-aromatic polyamides such as samethylene isophthalamide) (polyamide 6I), poly (nonamethylene terephthalamide) (polyamide 9T), poly (tetramethylene isophthalamide) (polyamide 4I), and copolymers and mixtures thereof Can be mentioned. Particularly suitable polyamides for the present invention include polyamide 6, polyamide 66, polyamide 6/66 copolymer, polyamide 66 / 6T copolymer, polyamide 6T / 12 copolymer, polyamide 6T / 11 copolymer, polyamide 6T / 6I copolymer, polyamide 6T / 6I / 12 copolymer, polyamide 6T / 610 copolymer, and polyamide 6T / 6I / 6 copolymer.
このようなポリアミド樹脂の分子量は特に制限はないが、９８％（９８質量％）硫酸中、濃度１質量％、２５℃で測定する相対粘度が１．７～４．５のポリアミド樹脂を使用することが好ましい。ポリアミド樹脂の相対粘度は、より好ましくは、２．０～４．０、さらに好ましくは２．０～３．５である。
The molecular weight of such a polyamide resin is not particularly limited, but a polyamide resin having a relative viscosity of 1.7 to 4.5 measured at 25 ° C. in 98% (98% by mass) sulfuric acid at a concentration of 1% by mass is used. It is preferable. The relative viscosity of the polyamide resin is more preferably 2.0 to 4.0, still more preferably 2.0 to 3.5.
本発明における酢酸の金属塩の金属は、アルカリ金属、アルカリ土類金属、周期表のＶＢ族、ＶＩＢ族、ＶＩＩＢ族、ＶＩＩＩＢ族の遷移金属から選ばれる少なくとも１種である。アルカリ金属としては、リチウム、ナトリウム、カリウムなどが挙げられる。アルカリ土類金属としては、マグネシウム、カルシウムなどが挙げられる。周期表のＶＢ族、ＶＩＢ族、ＶＩＩＢ族、ＶＩＩＩＢ族の遷移金属としては、バナジウム、クロム、マンガン、鉄などが挙げられる。具体的な化合物では、酢酸リチウム、酢酸カルシウム、酢酸ナトリウム、酢酸鉄などが挙げられる。酢酸鉄は酢酸鉄（ＩＩ）が好ましい。
前記金属は、アルカリ金属、アルカリ土類金属から選ばれる少なくとも１種であることが好ましく、アルカリ金属であることがより好ましい。具体的な化合物では、酢酸リチウム、酢酸カルシウム、酢酸ナトリウムから選ばれる少なくとも１種が好ましく、酢酸リチウム、酢酸ナトリウムから選ばれる少なくとも１種がより好ましい。 The metal of the metal salt of acetic acid in the present invention is at least one selected from alkali metals, alkaline earth metals, transition metals of Group VB, VIB, VIIB, and VIIIB of the periodic table. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Examples of transition metals of Group VB, VIB, VIIB, and VIIIB of the periodic table include vanadium, chromium, manganese, and iron. Specific compounds include lithium acetate, calcium acetate, sodium acetate, iron acetate and the like. The iron acetate is preferably iron (II) acetate.
The metal is preferably at least one selected from alkali metals and alkaline earth metals, and more preferably alkali metals. In a specific compound, at least one selected from lithium acetate, calcium acetate, and sodium acetate is preferable, and at least one selected from lithium acetate and sodium acetate is more preferable.
前記金属は、アルカリ金属、アルカリ土類金属から選ばれる少なくとも１種であることが好ましく、アルカリ金属であることがより好ましい。具体的な化合物では、酢酸リチウム、酢酸カルシウム、酢酸ナトリウムから選ばれる少なくとも１種が好ましく、酢酸リチウム、酢酸ナトリウムから選ばれる少なくとも１種がより好ましい。 The metal of the metal salt of acetic acid in the present invention is at least one selected from alkali metals, alkaline earth metals, transition metals of Group VB, VIB, VIIB, and VIIIB of the periodic table. Examples of the alkali metal include lithium, sodium, and potassium. Examples of the alkaline earth metal include magnesium and calcium. Examples of transition metals of Group VB, VIB, VIIB, and VIIIB of the periodic table include vanadium, chromium, manganese, and iron. Specific compounds include lithium acetate, calcium acetate, sodium acetate, iron acetate and the like. The iron acetate is preferably iron (II) acetate.
The metal is preferably at least one selected from alkali metals and alkaline earth metals, and more preferably alkali metals. In a specific compound, at least one selected from lithium acetate, calcium acetate, and sodium acetate is preferable, and at least one selected from lithium acetate and sodium acetate is more preferable.
本発明において、酢酸の金属塩の含有量は、ポリアミド樹脂１００質量部に対して、０．１～１０質量部、好ましくは０．１～５質量部、より好ましくは、０．５～３質量部である。０．１質量部未満では、耐熱老化性の発現効果がほとんどなく、１０質量部を超えても耐熱老化性の発現効果がそれ以上に増大することはない。前記酢酸の金属塩は、１０質量部以下であれば、金属粒子や金属酸化物粒子などとは異なり機械的特性への悪影響は少なく、特にガラス繊維強化組成物においてもガラス繊維の破損を抑制できるため、機械的特性を低下させることはほとんどない。
本発明における前記酢酸の金属塩の耐熱老化性向上効果が発現する理由については不明であるが、前記酢酸の金属塩がポリアミド樹脂の表層付近で、酸素の捕捉効果があり、ポリアミド樹脂の酸化劣化を抑制できるためではないかと考えられる。 In the present invention, the content of the metal salt of acetic acid is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin. Part. If the amount is less than 0.1 parts by mass, there is almost no effect of developing heat aging resistance, and if it exceeds 10 parts by mass, the effect of developing heat aging property will not increase any further. If the metal salt of acetic acid is 10 parts by mass or less, unlike metal particles or metal oxide particles, there is little adverse effect on mechanical properties, and in particular, glass fiber breakage can be suppressed even in glass fiber reinforced compositions. Therefore, the mechanical properties are hardly deteriorated.
Although it is unclear why the effect of improving the heat aging resistance of the metal salt of acetic acid in the present invention is present, the metal salt of acetic acid has an oxygen scavenging effect near the surface layer of the polyamide resin, and the oxidative deterioration of the polyamide resin. It is thought that it is because it can suppress.
本発明における前記酢酸の金属塩の耐熱老化性向上効果が発現する理由については不明であるが、前記酢酸の金属塩がポリアミド樹脂の表層付近で、酸素の捕捉効果があり、ポリアミド樹脂の酸化劣化を抑制できるためではないかと考えられる。 In the present invention, the content of the metal salt of acetic acid is 0.1 to 10 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0.5 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin. Part. If the amount is less than 0.1 parts by mass, there is almost no effect of developing heat aging resistance, and if it exceeds 10 parts by mass, the effect of developing heat aging property will not increase any further. If the metal salt of acetic acid is 10 parts by mass or less, unlike metal particles or metal oxide particles, there is little adverse effect on mechanical properties, and in particular, glass fiber breakage can be suppressed even in glass fiber reinforced compositions. Therefore, the mechanical properties are hardly deteriorated.
Although it is unclear why the effect of improving the heat aging resistance of the metal salt of acetic acid in the present invention is present, the metal salt of acetic acid has an oxygen scavenging effect near the surface layer of the polyamide resin, and the oxidative deterioration of the polyamide resin. It is thought that it is because it can suppress.
本発明の樹脂組成物には、前記の酢酸の金属塩以外に、公知の熱安定剤も併用して使用することができる。
In addition to the above-mentioned acetic acid metal salt, a known heat stabilizer can also be used in combination with the resin composition of the present invention.
本発明で用いることができる銅化合物としては、酢酸銅、沃化銅、臭化銅、塩化銅、フッ化銅、ラウリン酸銅、ステアリン酸銅等を挙げることができる。これらの銅化合物は単独で用いても良く、また併用しても良い。酢酸銅、沃化銅、臭化銅、塩化銅が好ましく、臭化第二銅が特に好ましく使用される。銅化合物の添加量は、ポリアミド樹脂１００質量部に対して、銅化合物中の銅として０．０００１～１質量部であることが好ましい。０．０００１質量部未満では、高温雰囲気かつ紫外線照射下のより厳しい環境下における変色防止効果が不十分であり、１質量部より多いと、前記の厳しい環境下における変色防止の効果が頭打ちになり、さらには金型や押出し機や成形機のスクリュー、シリンダー等を腐蝕する等の問題を発生する懸念がある。より好ましい添加量は、０．０００５～１質量部であり、さらに好ましい添加量は、０．０００５～０．０３質量部であり、特に好ましい添加量は、０．０００５～０．０２質量部である。
Examples of the copper compound that can be used in the present invention include copper acetate, copper iodide, copper bromide, copper chloride, copper fluoride, copper laurate, and copper stearate. These copper compounds may be used alone or in combination. Copper acetate, copper iodide, copper bromide and copper chloride are preferred, and cupric bromide is particularly preferably used. The addition amount of the copper compound is preferably 0.0001 to 1 part by mass as copper in the copper compound with respect to 100 parts by mass of the polyamide resin. If the amount is less than 0.0001 parts by mass, the effect of preventing discoloration in a high temperature atmosphere and a severer environment under ultraviolet irradiation is insufficient, and if the amount is more than 1 part by mass, the effect of preventing discoloration in the severe environment will reach its peak. Furthermore, there is a concern that problems such as corrosion of molds, screws, cylinders, etc. of extruders and molding machines may occur. A more preferable addition amount is 0.0005 to 1 part by mass, a further preferable addition amount is 0.0005 to 0.03 part by mass, and a particularly preferable addition amount is 0.0005 to 0.02 part by mass. is there.
また、銅化合物を添加する場合には、沃化カリウム、臭化カリウム等のハロゲン化アルカリ金属化合物を併用することが好ましい。併用により、銅の析出を防止することができる。銅化合物の添加方法としては、ポリアミド樹脂の製造の任意の段階において添加しても良く、その添加方法は限定されない。例えば、ポリアミドの原料塩水溶液に添加する方法、溶融重合の途中で溶融ポリアミド中に注入添加する方法、重合を終了して造粒したポリアミドペレットと該銅化合物の粉体またはマスターバッチをブレンドした後に押出し機や成形機等を用いて溶融混練する方法等のいずれであっても良い。
In addition, when adding a copper compound, it is preferable to use an alkali metal halide compound such as potassium iodide or potassium bromide in combination. By using together, precipitation of copper can be prevented. As a method for adding the copper compound, it may be added at any stage of the production of the polyamide resin, and the addition method is not limited. For example, a method of adding to a raw material salt aqueous solution of polyamide, a method of injecting and adding to a molten polyamide in the middle of melt polymerization, and after blending a granulated polyamide pellet and the copper compound powder or masterbatch after polymerization Any of a method of melt kneading using an extruder, a molding machine or the like may be used.
さらに、本発明においてには、ヒンダードフェノール系酸化防止剤、リン系酸化防止剤、硫黄系酸化防止剤、アミン系酸化防止剤などの酸化防止剤、光安定剤といった補助安定剤を配合することができる。
Furthermore, in the present invention, an auxiliary stabilizer such as a hindered phenol antioxidant, a phosphorus antioxidant, a sulfur antioxidant, an amine antioxidant, or a light stabilizer is added. Can do.
ヒンダードフェノール系酸化防止剤としては、公知の化合物が使用可能である。これらの化合物は単独で、あるいは組み合わせて使用することができる。このようなヒンダードフェノール系酸化防止剤の中でも、２官能以上のフェノールが好ましく、トリエチレングリコール－ビス〔３－（３－ｔｅｒｔ－ブチル－５－メチル－４－ヒドロキシフェニル）プロピオネート〕（ＩＲＧＡＮＯＸ２４５）などのセミヒンダードタイプが変色しにくさの点で好ましい。
Known compounds can be used as the hindered phenol antioxidant. These compounds can be used alone or in combination. Among such hindered phenolic antioxidants, phenols having two or more functional groups are preferable, and triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (IRGANOX245) A semi-hindered type such as is preferable in terms of difficulty in discoloration.
ヒンダードフェノール系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、効果が飽和に達したり、成形品表面へのブルーミングが生じることがある。
When a hindered phenol-based antioxidant is blended, the blending amount (content) is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the polyamide resin. 2 parts by mass. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
リン系酸化防止剤としては、無機系及び有機系のリン系酸化防止剤から選ばれる少なくとも一種である。無機リン系酸化防止剤としては、次亜リン酸ナトリウムなどの次亜リン酸塩、亜リン酸塩などが挙げられる。
有機リン系酸化防止剤としては、ホスファイト系の市販されている有機リン系酸化防止剤を用いることができるが、熱分解でリン酸を生成しない有機系リン含有化合物が好ましい。かかる有機系リン含有化合物としては、公知の化合物が使用可能である。 The phosphorus antioxidant is at least one selected from inorganic and organic phosphorus antioxidants. Examples of inorganic phosphorus antioxidants include hypophosphites such as sodium hypophosphite and phosphites.
As the organic phosphorus antioxidant, commercially available organic phosphorus antioxidants such as phosphites can be used, but organic phosphorus-containing compounds that do not generate phosphoric acid by thermal decomposition are preferable. As such organic phosphorus-containing compounds, known compounds can be used.
有機リン系酸化防止剤としては、ホスファイト系の市販されている有機リン系酸化防止剤を用いることができるが、熱分解でリン酸を生成しない有機系リン含有化合物が好ましい。かかる有機系リン含有化合物としては、公知の化合物が使用可能である。 The phosphorus antioxidant is at least one selected from inorganic and organic phosphorus antioxidants. Examples of inorganic phosphorus antioxidants include hypophosphites such as sodium hypophosphite and phosphites.
As the organic phosphorus antioxidant, commercially available organic phosphorus antioxidants such as phosphites can be used, but organic phosphorus-containing compounds that do not generate phosphoric acid by thermal decomposition are preferable. As such organic phosphorus-containing compounds, known compounds can be used.
リン系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、成形品にフラッシュが生じることがある。
本発明では、無機系及び有機系のリン系酸化防止剤を併用すると、酸化防止剤の配合量を少なくすることができるので好ましい。 When a phosphorus-based antioxidant is blended, the blending amount (content) is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. If the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is insufficient. On the other hand, if the amount exceeds 3 parts by mass, flashing may occur in the molded product.
In the present invention, it is preferable to use inorganic and organic phosphorus antioxidants in combination because the amount of the antioxidant can be reduced.
本発明では、無機系及び有機系のリン系酸化防止剤を併用すると、酸化防止剤の配合量を少なくすることができるので好ましい。 When a phosphorus-based antioxidant is blended, the blending amount (content) is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. If the amount is less than 0.05 parts by mass, the effect of preventing thermal discoloration is insufficient. On the other hand, if the amount exceeds 3 parts by mass, flashing may occur in the molded product.
In the present invention, it is preferable to use inorganic and organic phosphorus antioxidants in combination because the amount of the antioxidant can be reduced.
本発明で用いることができるアミン系酸化防止剤としては、公知の化合物が使用可能である。また、第２級アリールアミンもアミン系酸化防止剤として挙げることができる。第２級アリールアミンとは、窒素原子に化学結合した炭素ラジカル２個を含有するアミン化合物であって、少なくとも１つ、好ましくは両方の炭素ラジカルが芳香族である、アミン化合物を意味する。
As the amine-based antioxidant that can be used in the present invention, known compounds can be used. Secondary arylamines can also be mentioned as amine-based antioxidants. By secondary arylamine is meant an amine compound containing two carbon radicals chemically bonded to a nitrogen atom, wherein at least one, preferably both carbon radicals are aromatic.
アミン系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、効果が飽和に達したり、成形品表面へのブルーミングが生じることがある。
When the amine-based antioxidant is blended, the blending amount (content) is preferably 0.05 to 3 parts by mass, more preferably 0.1 to 2 parts by mass with respect to 100 parts by mass of the polyamide resin. Part. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
本発明において用いることができる硫黄系酸化防止剤としては、公知の化合物が使用可能である。
As the sulfur-based antioxidant that can be used in the present invention, known compounds can be used.
硫黄系酸化防止剤を配合する場合、その配合量（含有量）は、ポリアミド樹脂１００質量部に対して、０．０５～３質量部であることが好ましく、より好ましくは０．１～２質量部である。０．０５質量部未満では、熱変色防止効果が不十分であり、一方、３質量部を超えると、効果が飽和に達したり、成形品表面へのブルーミングが生じることがある。
When a sulfur-based antioxidant is blended, the blending amount (content) is preferably 0.05 to 3 parts by weight, more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the polyamide resin. Part. If it is less than 0.05 part by mass, the effect of preventing thermal discoloration is insufficient, while if it exceeds 3 parts by mass, the effect may reach saturation or blooming on the surface of the molded product may occur.
本発明において用いることができる光安定剤は、１種または複数種のヒンダードアミン型光安定剤（ＨＡＬＳ）であることが好ましい。
好ましくは、ＨＡＬＳは、置換ピペリジン化合物から誘導される化合物、特にアルキル置換ピペリジニルまたはピペラジノン化合物、およびアルコキシ置換ピペリジニル化合物から誘導される化合物である。かかる化合物としては、公知の化合物が使用可能である。 The light stabilizer that can be used in the present invention is preferably one or more hindered amine type light stabilizers (HALS).
Preferably, HALS is a compound derived from a substituted piperidine compound, in particular a compound derived from an alkyl-substituted piperidinyl or piperazinone compound, and an alkoxy-substituted piperidinyl compound. As such a compound, a known compound can be used.
好ましくは、ＨＡＬＳは、置換ピペリジン化合物から誘導される化合物、特にアルキル置換ピペリジニルまたはピペラジノン化合物、およびアルコキシ置換ピペリジニル化合物から誘導される化合物である。かかる化合物としては、公知の化合物が使用可能である。 The light stabilizer that can be used in the present invention is preferably one or more hindered amine type light stabilizers (HALS).
Preferably, HALS is a compound derived from a substituted piperidine compound, in particular a compound derived from an alkyl-substituted piperidinyl or piperazinone compound, and an alkoxy-substituted piperidinyl compound. As such a compound, a known compound can be used.
本発明においては、第２級アリールアミンとＨＡＬＳとの混合物を使用することができる。好ましい実施形態は、少なくとも１つが第２級アリールアミンから選択され、少なくとも１つがＨＡＬＳの群から選択される、少なくとも２種類の補助安定剤を含む。補助安定剤混合物を配合する場合、その全配合量（全含有量）は、ポリアミド樹脂１００質量部に対して、０．５～１０質量部であることが好ましく、より好ましくは０．５～３質量部である。０．５質量部未満では、耐熱老化性を向上する効果が不足し、一方、１０質量部を超えると効果が飽和したり、成形品表面へブルーミングすることがある。
In the present invention, a mixture of secondary arylamine and HALS can be used. Preferred embodiments comprise at least two co-stabilizers, at least one selected from secondary arylamines and at least one selected from the group of HALS. When the auxiliary stabilizer mixture is blended, the total blending amount (total content) is preferably 0.5 to 10 parts by mass, more preferably 0.5 to 3 parts per 100 parts by mass of the polyamide resin. Part by mass. If the amount is less than 0.5 parts by mass, the effect of improving the heat aging resistance is insufficient. On the other hand, if the amount exceeds 10 parts by mass, the effect may be saturated or blooming may occur on the surface of the molded product.
本発明においては、さらに、充填材を添加することにより強度、剛性、耐熱性などを大幅に向上させることができる。このような充填材としては、ガラス繊維、炭素繊維、金属繊維、アラミド繊維、アスベスト、チタン酸カリウムウィスカ、ワラストナイト、ガラスフレーク、ガラスビーズ、タルク、マイカ、クレー、炭酸カルシウム、硫酸バリウム、酸化チタンおよび酸化アルミニウムなどが挙げられ、なかでもチョップドストランドタイプのガラス繊維が好ましく用いられる。
これらを配合する場合、その配合量（含有量）は、熱可塑性樹脂１００質量部に対して５～１４０質量部が好ましく、特に好ましくは５～１００質量部である。 In the present invention, the strength, rigidity, heat resistance and the like can be significantly improved by adding a filler. Such fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastonite, glass flake, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, oxidation Examples thereof include titanium and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.
When these are blended, the blending amount (content) is preferably 5 to 140 parts by weight, particularly preferably 5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
これらを配合する場合、その配合量（含有量）は、熱可塑性樹脂１００質量部に対して５～１４０質量部が好ましく、特に好ましくは５～１００質量部である。 In the present invention, the strength, rigidity, heat resistance and the like can be significantly improved by adding a filler. Such fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whisker, wollastonite, glass flake, glass beads, talc, mica, clay, calcium carbonate, barium sulfate, oxidation Examples thereof include titanium and aluminum oxide. Among them, chopped strand type glass fibers are preferably used.
When these are blended, the blending amount (content) is preferably 5 to 140 parts by weight, particularly preferably 5 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic resin.
また、本発明のポリアミド樹脂組成物に対して、本発明の目的を損なわない範囲で紫外線吸収剤（例えばレゾルシノール、サリシレート、ベンゾトリアゾール、ベンゾフェノンなど）、滑剤および離型剤、核剤、可塑剤、帯電防止剤、および染料・顔料を含む着色剤などの通常の添加剤の１種以上をポリアミド樹脂１００質量部に対して５質量部程度まで添加することができる。
本発明のポリアミド樹脂組成物は、上記で説明した各成分を含有することが可能であるが、上記充填材を除いた組成物において、ポリアミド樹脂と酢酸の金属塩の合計で９０質量％以上を占めることが好ましく、９５質量％以上を占めることがより好ましい。 Further, with respect to the polyamide resin composition of the present invention, ultraviolet absorbers (for example, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents, nucleating agents, plasticizers, and the like within a range not impairing the object of the present invention. One or more conventional additives such as an antistatic agent and a colorant containing a dye / pigment can be added up to about 5 parts by mass with respect to 100 parts by mass of the polyamide resin.
The polyamide resin composition of the present invention can contain each of the components described above, but in the composition excluding the filler, 90% by mass or more in total of the polyamide resin and the metal salt of acetic acid. It is preferable to occupy 95% by mass or more.
本発明のポリアミド樹脂組成物は、上記で説明した各成分を含有することが可能であるが、上記充填材を除いた組成物において、ポリアミド樹脂と酢酸の金属塩の合計で９０質量％以上を占めることが好ましく、９５質量％以上を占めることがより好ましい。 Further, with respect to the polyamide resin composition of the present invention, ultraviolet absorbers (for example, resorcinol, salicylate, benzotriazole, benzophenone, etc.), lubricants and mold release agents, nucleating agents, plasticizers, and the like within a range not impairing the object of the present invention. One or more conventional additives such as an antistatic agent and a colorant containing a dye / pigment can be added up to about 5 parts by mass with respect to 100 parts by mass of the polyamide resin.
The polyamide resin composition of the present invention can contain each of the components described above, but in the composition excluding the filler, 90% by mass or more in total of the polyamide resin and the metal salt of acetic acid. It is preferable to occupy 95% by mass or more.
本発明における前記酢酸の金属塩及び他の添加剤をポリアミド樹脂に含有させる方法は、特に制限されるものではなく、任意の方法で行われる。例えば全成分を予備混合した後、押出機やニーダ中で混練する方法や、予め任意の数成分を押出機やニーダ中で混練して得たペレットに、更に他の成分を混練配合する方法などが挙げられる。
The method for incorporating the metal salt of acetic acid and other additives in the present invention into the polyamide resin is not particularly limited, and may be performed by any method. For example, after all the components are premixed, the method is kneaded in an extruder or kneader, or the other components are kneaded and blended with pellets obtained by kneading any number of components in advance in an extruder or kneader. Is mentioned.
本発明のポリアミド樹脂組成物を射出成形して得られる成形品の２００℃、１０００時間の熱処理後の引張強度保持率は、８０％以上とすることができる。前記成形品は、下記実施例の項に記載に準じて成形された試験片であり、前記熱処理は、下記実施例の項に記載の手順で行う処理である。引張強度保持率は、熱処理前の試験片の引張強度に対する熱処理後の引張強度の保持率である。引張強度保持率は、８５％以上であることがより好ましい。
The tensile strength retention after heat treatment at 200 ° C. for 1000 hours of a molded product obtained by injection molding of the polyamide resin composition of the present invention can be 80% or more. The molded product is a test piece molded in accordance with the description in the following example section, and the heat treatment is a process performed in the procedure described in the following example section. The tensile strength retention is the retention of the tensile strength after the heat treatment relative to the tensile strength of the test piece before the heat treatment. The tensile strength retention is more preferably 85% or more.
本発明のポリアミド樹脂組成物は、射出成形、押出成形、熱成形、圧縮成形、または、ブロー成形、ダイスライド成形などに代表された、いわゆる中空工法などにより成形体にすることができる。また、それら成形体を二次加工、例えば振動溶着、熱板溶着、超音波溶着などを含む溶着工法など、によっても成形体とすることができる。好ましくは、射出成形またはブロー成形体であり、その二次加工による成形体である。
The polyamide resin composition of the present invention can be formed into a molded body by a so-called hollow method represented by injection molding, extrusion molding, thermoforming, compression molding, blow molding, die slide molding or the like. Moreover, these molded products can be formed into molded products by secondary processing, for example, welding methods including vibration welding, hot plate welding, ultrasonic welding, and the like. Preferably, it is an injection-molded or blow-molded body, and a molded body by secondary processing thereof.
本発明のポリアミド樹脂組成物の成形体の用途例としては、自動車、車両分野では、例えば、シリンダー・ヘッド・カバー、エンジン・カバー、インタークーラー用のハウジング、バルブ、エンドキャップ、キャスター、トロリー部品など、さらに、吸気管（エア・ダクト）、特に吸気マニホールドなどの吸気系部品、コネクタ、歯車、ファン・ホイール、冷却材貯蔵コンテナー、熱交換器用のハウジングもしくはハウジング部材、ラジエーター、サーモスタット、クーラント及び送水ポンプ、ヒーター、締結エレメント、油受皿、マフラーなどの排気システムおよび触媒コンバータ用ハウジング、タイミングチェーンベルトフロントカバー、ギアボックス、ベアリング、ガソリンキャップ、座席部品、ヘッドレスト、ドアハンドル、ワイパー部品などが挙げられる。
Examples of uses of the molded article of the polyamide resin composition of the present invention include, in the automobile and vehicle fields, for example, a cylinder head cover, an engine cover, an intercooler housing, a valve, an end cap, a caster, a trolley part, etc. In addition, intake pipes (air ducts), especially intake system parts such as intake manifolds, connectors, gears, fan wheels, coolant storage containers, housings or housing parts for heat exchangers, radiators, thermostats, coolants and water pumps, Heater, fastening element, oil pan, exhaust system such as muffler and catalytic converter housing, timing chain belt front cover, gear box, bearing, gasoline cap, seat parts, headrest, door handle, wire Such as over parts, and the like.
電気／電子機器分野では、例えば回路基板の部品、ハウジング、フィルム、コンダクター、スイッチ、ターミナル・ストリップ、リレー、レジスタ、コンデンサ、コイル、ランプ、ダイオード、ＬＥＤ、トランジスタ、コネクタ、コントローラー、メモリ、ボルト、コイルボビン、プラグ、プラグ部品、メカトロニクス部品、調理用機器、洗濯機、冷蔵庫、エアコンなどの家電機器部品、センサーなどが挙げられる。
生活関連、家具建材関連分野では、例えば車椅子、ベビーカー部品、椅子脚、肘掛け、手摺り、窓枠、ドアノブ、などのための部品などが挙げられる。 In the electrical / electronic equipment field, for example, circuit board components, housings, films, conductors, switches, terminal strips, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, memories, bolts, coil bobbins , Plugs, plug parts, mechatronic parts, cooking equipment, washing machine, refrigerator, air conditioner and other home appliance parts, sensors and the like.
In the fields related to daily life and furniture and building materials, for example, there are parts for wheelchairs, stroller parts, chair legs, armrests, handrails, window frames, door knobs, and the like.
生活関連、家具建材関連分野では、例えば車椅子、ベビーカー部品、椅子脚、肘掛け、手摺り、窓枠、ドアノブ、などのための部品などが挙げられる。 In the electrical / electronic equipment field, for example, circuit board components, housings, films, conductors, switches, terminal strips, relays, resistors, capacitors, coils, lamps, diodes, LEDs, transistors, connectors, controllers, memories, bolts, coil bobbins , Plugs, plug parts, mechatronic parts, cooking equipment, washing machine, refrigerator, air conditioner and other home appliance parts, sensors and the like.
In the fields related to daily life and furniture and building materials, for example, there are parts for wheelchairs, stroller parts, chair legs, armrests, handrails, window frames, door knobs, and the like.
以下に実施例を用いて本発明を具体的に説明するが、本発明はこれらに限定されるものではない。なお、実施例に記載された測定値は、以下の方法によった。
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. In addition, the measured value described in the Example was based on the following method.
（１）使用原料
・ポリアミド６：相対粘度ＲＶ＝２．７、集盛社製 ＴＰ－４２０８
・ポリアミド６Ｔ／１２：相対粘度ＲＶ＝２．７ 東洋紡社製（６Ｔ／１２＝６５／３５（モル比））
・酢酸ナトリウム：和光純薬社製
・酢酸リチウム：和光純薬社製
・酢酸カルシウム：和光純薬社製
・酢酸鉄（ＩＩ）：和光純薬社製
・酢酸アルミニウム：和光純薬社製
・塩化鉄（ＩＩ）：和光純薬社製 純度 ９９．０％
・フタロシアニン鉄（ＩＩ）：和光純薬社製 純度９９．０％
・酸化鉄（ＩＩ）：和光純薬社製
・酸化鉄（ＩＩＩ）：和光純薬社製
・フェノール系酸化防止剤：イルガノックス２４５ ＢＡＳＦ社製
・臭化第二銅（銅系安定剤）：和光純薬社製 純度９９．０％
・ガラスファイバー：日本電気硝子社製 Ｔ－２７５Ｈ (1) Raw material used: Polyamide 6: Relative viscosity RV = 2.7, TP-4208 manufactured by Shumori Co.
Polyamide 6T / 12: Relative viscosity RV = 2.7 manufactured by Toyobo Co., Ltd. (6T / 12 = 65/35 (molar ratio))
・ Sodium acetate: Wako Pure Chemical Industries, Ltd. ・ Lithium acetate: Wako Pure Chemical Industries, Ltd. ・ Calcium acetate: Wako Pure Chemical Industries, Ltd. ・ Iron acetate (II): Wako Pure Chemical Industries, Ltd. ・ Aluminum acetate: Wako Pure Chemical Industries, Ltd. Iron (II): Wako Pure Chemical Industries, Ltd. Purity 99.0%
-Phthalocyanine iron (II): Wako Pure Chemical Industries, Ltd. Purity 99.0%
・ Iron oxide (II): Wako Pure Chemical Industries, Ltd. ・ Iron oxide (III): Wako Pure Chemical Industries, Ltd. ・ Phenol antioxidant: Irganox 245, manufactured by BASF Corporation ・ Copper bromide (copper stabilizer): Wako Pure Chemical Industries, Ltd. Purity 99.0%
・ Glass fiber: Nippon Electric Glass Co., Ltd. T-275H
・ポリアミド６：相対粘度ＲＶ＝２．７、集盛社製 ＴＰ－４２０８
・ポリアミド６Ｔ／１２：相対粘度ＲＶ＝２．７ 東洋紡社製（６Ｔ／１２＝６５／３５（モル比））
・酢酸ナトリウム：和光純薬社製
・酢酸リチウム：和光純薬社製
・酢酸カルシウム：和光純薬社製
・酢酸鉄（ＩＩ）：和光純薬社製
・酢酸アルミニウム：和光純薬社製
・塩化鉄（ＩＩ）：和光純薬社製 純度 ９９．０％
・フタロシアニン鉄（ＩＩ）：和光純薬社製 純度９９．０％
・酸化鉄（ＩＩ）：和光純薬社製
・酸化鉄（ＩＩＩ）：和光純薬社製
・フェノール系酸化防止剤：イルガノックス２４５ ＢＡＳＦ社製
・臭化第二銅（銅系安定剤）：和光純薬社製 純度９９．０％
・ガラスファイバー：日本電気硝子社製 Ｔ－２７５Ｈ (1) Raw material used: Polyamide 6: Relative viscosity RV = 2.7, TP-4208 manufactured by Shumori Co.
Polyamide 6T / 12: Relative viscosity RV = 2.7 manufactured by Toyobo Co., Ltd. (6T / 12 = 65/35 (molar ratio))
・ Sodium acetate: Wako Pure Chemical Industries, Ltd. ・ Lithium acetate: Wako Pure Chemical Industries, Ltd. ・ Calcium acetate: Wako Pure Chemical Industries, Ltd. ・ Iron acetate (II): Wako Pure Chemical Industries, Ltd. ・ Aluminum acetate: Wako Pure Chemical Industries, Ltd. Iron (II): Wako Pure Chemical Industries, Ltd. Purity 99.0%
-Phthalocyanine iron (II): Wako Pure Chemical Industries, Ltd. Purity 99.0%
・ Iron oxide (II): Wako Pure Chemical Industries, Ltd. ・ Iron oxide (III): Wako Pure Chemical Industries, Ltd. ・ Phenol antioxidant: Irganox 245, manufactured by BASF Corporation ・ Copper bromide (copper stabilizer): Wako Pure Chemical Industries, Ltd. Purity 99.0%
・ Glass fiber: Nippon Electric Glass Co., Ltd. T-275H
（２）試験方法
・引張強度、引張破断伸度：射出成形機・東芝機械社ＩＳ－１００を用い、シリンダー２８０℃（ポリアミド６Ｔ／１２を用いた場合は３２０℃）に設定し、金型温度９０℃の条件でＩＳＯ５２７－１,２に従って成形品を得た後、ＩＳＯ５２７－１,２に準じて測定した。 (2) Test method / Tensile strength, Tensile strength at break: Injection molding machine / Toshiba Machine Co., Ltd. IS-100, set to cylinder 280 ° C. (320 ° C. when polyamide 6T / 12 is used), mold temperature After obtaining a molded product according to ISO 527-1, 2 at 90 ° C., the measurement was performed according to ISO 527-1, 2.
・引張強度、引張破断伸度：射出成形機・東芝機械社ＩＳ－１００を用い、シリンダー２８０℃（ポリアミド６Ｔ／１２を用いた場合は３２０℃）に設定し、金型温度９０℃の条件でＩＳＯ５２７－１,２に従って成形品を得た後、ＩＳＯ５２７－１,２に準じて測定した。 (2) Test method / Tensile strength, Tensile strength at break: Injection molding machine / Toshiba Machine Co., Ltd. IS-100, set to cylinder 280 ° C. (320 ° C. when polyamide 6T / 12 is used), mold temperature After obtaining a molded product according to ISO 527-1, 2 at 90 ° C., the measurement was performed according to ISO 527-1, 2.
・熱老化試験：ＩＳＯ２５７８に詳述される手順に従って、再循環エアオーブン（ナガノ科学機械製作所製 熱風循環式乾燥機 ＮＨ－４０１Ｓ）において試験片を熱処理した。２００℃環境下で所定の試験時間（５００時間、１０００時間）で、試験片をオーブンから取り出し、室温に冷却し、試験の準備ができるまで、アルミニウム裏張りバッグ内に密閉した。次いで、ＩＳＯ５２７－１,２に従って、引張強度、引張破断伸度を測定した。３つの試験片から得られた平均値を採用した。
Heat aging test: The test piece was heat-treated in a recirculation air oven (manufactured by Nagano Kagaku Kikai Co., Ltd., hot air circulation dryer NH-401S) according to the procedure detailed in ISO2578. The specimens were removed from the oven at 200 ° C. environment for a predetermined test time (500 hours, 1000 hours), cooled to room temperature and sealed in an aluminum lined bag until ready for testing. Subsequently, the tensile strength and the tensile elongation at break were measured according to ISO527-1,2. The average value obtained from three test pieces was adopted.
引張強度および引張破断伸度の保持率は、熱処理なしの初期の値を１００％としたときの５００時間、１０００時間熱処理した後の保持率である。
The retention rate of tensile strength and tensile elongation at break is the retention rate after heat treatment for 500 hours and 1000 hours when the initial value without heat treatment is 100%.
［実施例１～７、比較例１～７］
実施例及び比較例として記載した樹脂組成物は、上記の原材料を、それぞれ二軸押出機（コペリオン社製ＳＴＳ３５）を用いて、表１に記載の割合（質量割合）で配合し、溶融混練してペレット（直径約２．５ｍｍ×長さ約２．５ｍｍ）を得た。得られたペレットは熱風循環式乾燥機にて１００℃×４時間以上乾燥した後に使用した。評価結果を表１に示す。 [Examples 1 to 7, Comparative Examples 1 to 7]
The resin compositions described as Examples and Comparative Examples were prepared by blending the above raw materials at the ratios (mass ratios) shown in Table 1 using a twin-screw extruder (STS35 manufactured by Coperion Co., Ltd.), and melt-kneading them. To obtain pellets (diameter: about 2.5 mm × length: about 2.5 mm). The obtained pellets were used after drying at 100 ° C. for 4 hours or more in a hot air circulation dryer. The evaluation results are shown in Table 1.
実施例及び比較例として記載した樹脂組成物は、上記の原材料を、それぞれ二軸押出機（コペリオン社製ＳＴＳ３５）を用いて、表１に記載の割合（質量割合）で配合し、溶融混練してペレット（直径約２．５ｍｍ×長さ約２．５ｍｍ）を得た。得られたペレットは熱風循環式乾燥機にて１００℃×４時間以上乾燥した後に使用した。評価結果を表１に示す。 [Examples 1 to 7, Comparative Examples 1 to 7]
The resin compositions described as Examples and Comparative Examples were prepared by blending the above raw materials at the ratios (mass ratios) shown in Table 1 using a twin-screw extruder (STS35 manufactured by Coperion Co., Ltd.), and melt-kneading them. To obtain pellets (diameter: about 2.5 mm × length: about 2.5 mm). The obtained pellets were used after drying at 100 ° C. for 4 hours or more in a hot air circulation dryer. The evaluation results are shown in Table 1.
実施例１～７は、初期（熱処理前）の引張強度、引張破断伸度も高く、２００℃×５００時間、１０００時間熱処理後の引張強度保持率はいずれも８０％以上の高い値を示しており、引張破断伸度保持率はいずれも７０％以上の高い値を示している。
比較例６は、フェノール系酸化防止剤及び臭化第二銅のみを添加した場合であるが、２００℃×５００時間、１０００時間後の引張強度保持率、引張破断伸度保持率が大幅に低下している。
比較例１は酢酸金属塩の添加量が少ない場合であるが、２００℃×５００時間、１０００時間後の引張強度保持率、引張破断伸度保持率が大幅に低下している。
比較例２、３、４、５、７はそれぞれ、酸化鉄（ＩＩ）、酸化鉄（ＩＩＩ）、塩化鉄（ＩＩ）、フタロシアニン鉄（ＩＩ）、酢酸アルミニウムを添加した場合であるが、２００℃×５００時間、１０００時間後の引張強度保持率、引張破断伸度保持率が大幅に低下している。 Examples 1 to 7 have high initial tensile strength (before heat treatment) and tensile elongation at break, and the tensile strength retention after heat treatment at 200 ° C. for 500 hours and 1000 hours is a high value of 80% or more. The tensile rupture elongation retention rate is as high as 70% or more.
Comparative Example 6 is a case where only a phenolic antioxidant and cupric bromide were added, but the tensile strength retention rate and tensile fracture elongation retention rate after 1000 hours at 200 ° C. × 500 hours were greatly reduced. is doing.
Comparative Example 1 is a case where the amount of metal acetate added is small, but the tensile strength retention rate and tensile fracture elongation retention rate after 200 ° C. × 500 hours and 1000 hours are significantly reduced.
Comparative Examples 2, 3, 4, 5, and 7 are cases where iron oxide (II), iron oxide (III), iron chloride (II), phthalocyanine iron (II), and aluminum acetate were added, respectively. × The tensile strength retention and tensile rupture elongation retention after 500 hours and 1000 hours are significantly reduced.
比較例６は、フェノール系酸化防止剤及び臭化第二銅のみを添加した場合であるが、２００℃×５００時間、１０００時間後の引張強度保持率、引張破断伸度保持率が大幅に低下している。
比較例１は酢酸金属塩の添加量が少ない場合であるが、２００℃×５００時間、１０００時間後の引張強度保持率、引張破断伸度保持率が大幅に低下している。
比較例２、３、４、５、７はそれぞれ、酸化鉄（ＩＩ）、酸化鉄（ＩＩＩ）、塩化鉄（ＩＩ）、フタロシアニン鉄（ＩＩ）、酢酸アルミニウムを添加した場合であるが、２００℃×５００時間、１０００時間後の引張強度保持率、引張破断伸度保持率が大幅に低下している。 Examples 1 to 7 have high initial tensile strength (before heat treatment) and tensile elongation at break, and the tensile strength retention after heat treatment at 200 ° C. for 500 hours and 1000 hours is a high value of 80% or more. The tensile rupture elongation retention rate is as high as 70% or more.
Comparative Example 6 is a case where only a phenolic antioxidant and cupric bromide were added, but the tensile strength retention rate and tensile fracture elongation retention rate after 1000 hours at 200 ° C. × 500 hours were greatly reduced. is doing.
Comparative Example 1 is a case where the amount of metal acetate added is small, but the tensile strength retention rate and tensile fracture elongation retention rate after 200 ° C. × 500 hours and 1000 hours are significantly reduced.
Comparative Examples 2, 3, 4, 5, and 7 are cases where iron oxide (II), iron oxide (III), iron chloride (II), phthalocyanine iron (II), and aluminum acetate were added, respectively. × The tensile strength retention and tensile rupture elongation retention after 500 hours and 1000 hours are significantly reduced.
本発明によれば、ポリアミド樹脂に２００℃程度の高温環境下での耐熱老化性を簡便に安定的に向上させるこができるため、本発明によって得られたポリアミド樹脂成物は、２００℃の環境に曝される可能性がある、自動車、電気・電子製品の部品用として利用が可能である。
According to the present invention, the polyamide resin composition obtained according to the present invention has an environment at 200 ° C. because the heat aging resistance in a high temperature environment of about 200 ° C. can be easily and stably improved. It can be used for parts of automobiles and electrical / electronic products that may be exposed to
According to the present invention, the polyamide resin composition obtained according to the present invention has an environment at 200 ° C. because the heat aging resistance in a high temperature environment of about 200 ° C. can be easily and stably improved. It can be used for parts of automobiles and electrical / electronic products that may be exposed to
Claims (3)
- ポリアミド樹脂１００質量部に対して、酢酸の金属塩を０．１～１０質量部含有し、前記金属塩の金属がアルカリ金属、アルカリ土類金属、周期表のＶＢ族、ＶＩＢ族、ＶＩＩＢ族、ＶＩＩＩＢ族の遷移金属から選ばれる少なくとも１種であることを特徴とするポリアミド樹脂組成物。 0.1 to 10 parts by mass of a metal salt of acetic acid with respect to 100 parts by mass of polyamide resin, and the metal of the metal salt is an alkali metal, an alkaline earth metal, a group VB, a group VIB, a group VIIB of the periodic table, A polyamide resin composition, which is at least one selected from group VIIIB transition metals.
- 前記酢酸の金属塩が、酢酸リチウム、酢酸カルシウム、酢酸ナトリウム、及び酢酸鉄から選ばれる少なくとも１種である請求項１に記載のポリアミド樹脂組成物。 The polyamide resin composition according to claim 1, wherein the metal salt of acetic acid is at least one selected from lithium acetate, calcium acetate, sodium acetate, and iron acetate.
- 前記ポリアミド樹脂組成物を射出成形して得られる成形品の２００℃、１０００時間の熱処理後の引張強度保持率が８０％以上である請求項１または２に記載のポリアミド樹脂組成物。
The polyamide resin composition according to claim 1 or 2, wherein a molded product obtained by injection molding of the polyamide resin composition has a tensile strength retention of 80% or more after heat treatment at 200 ° C for 1000 hours.
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