JP2004091707A - Method for producing heat-resistant polyamide resin composition - Google Patents
Method for producing heat-resistant polyamide resin composition Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/2053—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the additives only being premixed with a liquid phase
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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
- C08G69/04—Preparatory processes
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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
- C08G69/08—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from amino-carboxylic acids
- C08G69/14—Lactams
- C08G69/16—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は、自動車や電気製品や事務機器に使用される耐熱性ポリアミド樹脂の製造方法に関する。本発明により製造されたポリアミド樹脂組成物は、品質の耐久性においてバラツキが小さく、信頼性の高い成形品が得られる。
【０００２】
【従来技術】
従来、ポリアミド樹脂の耐熱性改良剤としては、アミン類、フェノール類と銅化合物が発表されている。中でも銅化合物は、ポリアミド樹脂の熱酸化劣化防止剤や光酸化劣化剤として有効であり、特に１５０℃以上の高温で有効であることが知られている。銅化合物が耐熱性改良剤として有効に作用するには、銅化合物がポリアミド中に高度に分散し、アミド基に配位することが必要であると考えられている。しかし、一般に銅化合物は固体状であるため、コンパウンド工程で耐熱性改良剤として微量の銅化合物をポリアミド樹脂に均一に分散させることが極めて困難であり、銅化合物がポリアミド中に高度に分散できていないため、成形品毎、または成形品の部分部分により強度などの耐久性能にバラツキが生じ、耐熱性改良効果の信頼性が低いという問題があった。この解決のために、銅化合物を微粉化してから添加する方法や、必要量より銅化合物を多量に配合するなどの対策がなされていた。しかし、銅化合物は有害性がある点から、微粉化や多量に配合する方法は問題のある方法であった。一方、近年部品の軽薄短小化が進み、微細な部品や成形品表面の耐久性能についても信頼性の高い材料の要求があり、品質耐久性能に関するバラツキの小さいポリアミド組成物が求められている。
【０００３】
【発明が解決しようとする課題】
本発明は、コンパウンド工程や成形工程で銅化合物をポリアミド樹脂に均一に分散させ、耐久性能のバラツキが小さく信頼性の高い成形体が得られるポリアミド樹脂組成物を製造することを課題としている。
【０００４】
【課題を解決するための手段】
前記課題を解決するために、本発明者らは鋭意研究を重ねた結果、本発明を完成するに到った。即ち、本発明は、銅化合物を予めカプロラクタムに溶解した後、該溶液をポリアミド樹脂に配合することを特徴とする耐熱ポリアミド樹脂組成物の製造方法である。更には、銅化合物をカプロラクタムに溶解した後、該溶液に水を加え水溶液にし、該水溶液をポリアミド樹脂に配合することを特徴とする耐熱性ポリアミド樹脂の製造方法である。
【０００５】
【発明の実施の形態】
本発明におけるポリアミド樹脂とは、分子中に酸アミド結合（−ＣＯＮＨ−）を有するものであり、具体的には、ε−カプロラクタム、６−アミノカプロン酸、ω−エナントラクタム、７−アミノヘプタン酸、１１−アミノウンデカン酸、９−アミノノナン酸、α−ピロリドン、α−ピペリドンなどから得られる重合体または共重合体：ヘキサメチレンジアミン、ノナメチレンジアミン、ウンデカメチレンジアミン、ドデカメチレンジアミン、メタキシリレンジアミンなどのジアミンとテレフタル酸、イソフタル酸、アジピン酸、セバシン酸などのジカルボン酸とを重縮合して得られる重合体または共重合体もしくはこれらのブレンド物等を例示することができるが、これらに限定されるものではない。
【０００６】
上記のポリアミド樹脂のうち、平均分子量９０００〜３００００のものが好ましい。又ポリアミド樹脂のアミノ末端基、カルボキシル末端基は強化剤のカップリング剤、及びポリアミド樹脂以外の反応性基を有するポリマーと反応し結合するためアミノ末端基量、カルボキシル末端基量は多い方が好ましい。又使用するカップリング剤の種類、量及びポリアミド樹脂以外の反応性基を有するポリマーの反応性基の種類、量により両末端基量のバランスを変更してもよい。
【０００７】
本発明に使用される銅化合物としては、塩化銅、臭化銅、沃化銅、酢酸銅、銅アセチルアセトナート、炭酸銅、ほうふっ化銅、クエン酸銅、水酸化銅、硝酸銅、硫酸銅、蓚酸銅などが挙げられる。特に、分解温度が高い塩化銅、臭化銅、沃化銅、酢酸銅やこれらの水和物などが好ましい。ポリアミド樹脂への添加濃度は銅化合物の種類によるが、ポリアミド樹脂１００重量部に対して銅原子として０．００１〜０．１重量部が好ましい。
【０００８】
予めカプロラクタムと溶解する際の銅化合物の形態としては、微粉末状である方が好ましいが、本発明においては、予めカプロラクタムに溶解してから添加するので必ずしも微粉末にしなくてもよい。この点は本発明のメリットのひとつである。一方、従来の固体状態の銅化合物を直接ポリアミド樹脂に添加する場合は、ポリアミド樹脂に均一に分散させるために５μｍ以下の微粉末に加工する必要があり、コスト面や取扱いの点で問題がある。
【０００９】
本発明に使用されるカプロラクタムは特に限定されず、工業的に製造されているものが使用できる。
本発明に使用される水は純水や蒸留水が好ましいが、これらに限定されず一般的な工業用水も使用できる。
【００１０】
銅化合物をカプロラクタムへの溶解する方法としては、溶融状態のラクタムに所定量の銅化合物を加え混合溶解する方法が挙げられる。カプロラクタムへの添加濃度は銅化合物の種類によるが、カプロラクタム１００重量部に対して０．１〜５０重量部が好ましい。このとき他の安定剤を同時に混合することもできる。
【００１１】
ポリアミド樹脂に銅化合物のカプロラクタム溶液又はカプロラクタム水溶液を配合する方法としては、銅化合物を溶解したカプロラクタム溶液を７０℃以上の溶融状態に保持してポリアミド樹脂のコンパウンド作製時や成形加工時に加える方法が挙げられる。カプロラクタム溶液を７０℃以下に冷却後、固体状態で粉末化してポリアミド樹脂のコンパウンド作製時や成形加工時に配合することもできる。
【００１２】
またこの銅化合物を含むカプロラクタムに２０℃以上の熱湯を加え安定な水溶液にすることができる。この水溶液の融点は濃度により調節ができる。融点を室温以下に調節して液状で配合するとポリアミド樹脂表面に均一に分散できるので好ましい。水溶液の濃度としては特に限定されないが、カプロラクタム１０〜９９重量％好ましくは、特に３０〜８５重量％が好ましい。
【００１３】
水溶液の融点が室温以上の場合、融点以上に加熱して液状として、コンパウンド時の予備混合に使用すると、本発明の目的が同様に効果的に達成される。
カプロラクタムに溶解、またカプロラクタムと水に溶解すると本発明が達成される理由は、明確ではないが銅化合物はカプロラクタムに配位し分子状に分散しやすいことと、カプロラクタムや水は、ポリアミド樹脂に分子分散しやすいため、結果的に銅化合物がポリアミド樹脂に分子状に配位しやすいためと考察される。
【００１４】
本発明により製造された耐熱性ポリアミド樹脂組成物には、他にガラス繊維、炭素繊維、ウイスカー、アラミド繊維やポリフェニレンサルファイド繊維などの繊維状強化材やタルク、クレイ、シリカ、ワラストナイト、炭酸カルシュームなどのミネラルフィラー、ポリエステル樹脂、ポリオレフィン、ポリフェニレンエーテル樹脂、ＡＢＳ樹脂などのポリマー、高級脂肪酸塩、高級脂肪酸、高級脂肪酸エステル、低分子量ポリオレフィンなどの離型剤、ヒンダードフェノール、チオエーテル、ホスファイト系などの熱安定剤、ベンゾフェノン系、トリアゾール系、ヒンダードアミン系などの光安定剤を配合することができる。またカーボンブラックや顔料などを配合することができる。
【００１５】
本発明による耐熱性ポリアミド樹脂は、構成成分を単軸押出機や二軸押出機やニーダーなどの装置を用いた溶融混練や、成形時ペレット表面にまぶして使用される。使用される装置や混練条件についての制限は特にない。また成形方法としては、特に制限されないが、射出成形や押出成形されるのが一般的である。
【００１６】
以下実施例を用いて本発明を具体的に説明する。なお、明細書中の評価は以下の方法により測定した。
（１）加熱エージング後の曲げ強さと破壊歪
２６０℃に温度設定された射出成形機と表面温度が８０℃に温度調節されたＩＳＯ２９４−１に規定されたＴＹＰＥ Ｂの金型を使用して、８０ｍｍ×１０ｍｍ×４ｍｍの試験片を成形した。各成形品をランダムに２０本採取し、１６５℃で３０００時間エージングした。処理後のサンプルを２３℃に温度調節された試験室のデシケータ中で２４時保管し状態調節した。万能引張試験機を使用してＩＳＯ１７８に準じて曲げ試験を行い曲げ強さと破壊歪を測定し、２０点の平均値と標準偏差を求めて比較した。標準偏差により耐久性能のバラツキに関する信頼性を評価した。
【００１７】
（実施例１〜８、比較例１〜５）
表１に示したような安定剤配合物を各種銅化合物（ナカライテスク（株）試薬１級）の所定量を８０℃に温度調節されたカプロラクタム中に加えて、攪拌機で溶融混合し８０℃にて銅化合物のカプロラクタム溶液を作製して貯蔵した。あるいは、この溶融混合体１００重量部に８０℃の熱湯３０重量部を加えて攪拌機で混合し水溶液として約２５℃の実験室に保管した。以上の操作は、ポリタンク中で実施した。
【００１８】
２０℃の恒温槽中で測定した相対粘度（溶媒：９６重量％硫酸、ポリマー濃度：１ｇ／ｄｌ）が３．１であるポリアミド６樹脂６５重量部または相対粘度が３．２のポリアミド６６樹脂６５重量部と平均粒径４μｍのタルク３５重量部と沃化カリウム０．２重量部、前記銅化合物のカプロラクタム溶液またはカプロラクタム水溶液を配合量が銅原子に換算して約０．０１０重量％になるように予備混合した後、２６０℃に温度調節された３０ｍｍφの２軸押出機のホッパーに投入し、溶融混練押出しし、ペレット状のポリアミド樹脂コンパウンドを得た。
【００１９】
比較例として、表２に示したような銅化合物を配合しない例や、銅化合物をカプロラクタムに溶融混合することなく粉末状態で直接予備混合しポリアミド樹脂コンパウンドを得た。
【００２０】
表１に実施例と比較例で得たポリアミド樹脂コンパウンドペレットから射出成形体を得て、上記加熱エージング後の曲げ強さと破壊歪を測定し、その結果を表１と表２に示した。
表１と表２から明らかなとおり、実施例の本発明の方法で得たポリアミド樹脂組成物の成形体の加熱エージング後の曲げ強さと破壊歪のバラツキは、比較例３〜５の成形体の加熱エージング後の曲げ強さと破壊歪のバラツキに比べて極めて小さい。
【００２１】
【表１】
【発明の効果】
本発明によれば、コンパウンド工程や成形工程で熱安定剤である銅化合物をポリアミド樹脂に均一かつ高度に分散させることができ、耐久性能のバラツキが小さく信頼性の高い成形体が得られるポリアミド樹脂組成物を製造することできる。したがって、耐久性能について高い信頼性が要求される分野においてでも好適に使用できる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing a heat-resistant polyamide resin used for automobiles, electric appliances, and office equipment. The polyamide resin composition produced according to the present invention has a small variation in the durability of the quality, and a highly reliable molded product can be obtained.
[0002]
[Prior art]
Conventionally, amines, phenols and copper compounds have been disclosed as heat resistance improvers for polyamide resins. Among them, a copper compound is known to be effective as a thermal oxidative deterioration inhibitor or a photooxidative deterioration agent for a polyamide resin, and is particularly effective at a high temperature of 150 ° C. or higher. It is considered that the copper compound needs to be highly dispersed in the polyamide and coordinate to the amide group in order for the copper compound to effectively act as a heat resistance improving agent. However, since the copper compound is generally in a solid state, it is extremely difficult to uniformly disperse a trace amount of the copper compound as a heat resistance improving agent in the polyamide resin in the compounding step, and the copper compound is highly dispersed in the polyamide. Therefore, there is a problem that durability performance such as strength is varied for each molded article or a part of the molded article, and the reliability of the heat resistance improving effect is low. In order to solve this problem, measures have been taken such as adding a copper compound after pulverizing it or adding a larger amount of the copper compound than required. However, since the copper compound is harmful, the method of pulverizing and blending in a large amount has been problematic. On the other hand, in recent years, parts have become lighter, thinner and smaller, and there has been a demand for a material having high reliability with respect to the durability performance of fine parts and molded products, and a polyamide composition having a small variation in quality and durability has been demanded.
[0003]
[Problems to be solved by the invention]
It is an object of the present invention to produce a polyamide resin composition in which a copper compound is uniformly dispersed in a polyamide resin in a compounding step or a molding step, and a highly reliable molded article having a small variation in durability is obtained.
[0004]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have completed the present invention. That is, the present invention is a method for producing a heat-resistant polyamide resin composition, which comprises dissolving a copper compound in caprolactam in advance and then blending the solution with a polyamide resin. Further, there is provided a method for producing a heat-resistant polyamide resin, comprising dissolving a copper compound in caprolactam, adding water to the solution to form an aqueous solution, and blending the aqueous solution with the polyamide resin.
[0005]
BEST MODE FOR CARRYING OUT THE INVENTION
The polyamide resin in the present invention has an acid amide bond (—CONH—) in the molecule, and specifically includes ε-caprolactam, 6-aminocaproic acid, ω-enantholactam, 7-aminoheptanoic acid, Polymers or copolymers obtained from 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidone, etc .: hexamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, metaxylylenediamine Such as a polymer or copolymer obtained by polycondensation of a diamine such as terephthalic acid, isophthalic acid, adipic acid, and a dicarboxylic acid such as sebacic acid, or a blend thereof, but is not limited thereto. It is not done.
[0006]
Among the above polyamide resins, those having an average molecular weight of 9000 to 30,000 are preferred. In addition, since the amino terminal group and the carboxyl terminal group of the polyamide resin react with and bind to the coupling agent of the reinforcing agent and the polymer having a reactive group other than the polyamide resin, the amount of the amino terminal group and the amount of the carboxyl terminal group are preferably larger. . Further, the balance of the amounts of both terminal groups may be changed depending on the type and amount of the coupling agent used and the type and amount of the reactive group of the polymer having a reactive group other than the polyamide resin.
[0007]
Examples of the copper compound used in the present invention include copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper carbonate, copper borofluoride, copper citrate, copper hydroxide, copper nitrate, and sulfuric acid. Copper and copper oxalate are exemplified. In particular, copper chloride, copper bromide, copper iodide, copper acetate, hydrates thereof, and the like having a high decomposition temperature are preferable. The addition concentration to the polyamide resin depends on the type of the copper compound, but is preferably 0.001 to 0.1 part by weight as a copper atom with respect to 100 parts by weight of the polyamide resin.
[0008]
The form of the copper compound to be dissolved in advance with caprolactam is preferably in the form of fine powder. However, in the present invention, the copper compound is dissolved in caprolactam in advance and then added. This is one of the advantages of the present invention. On the other hand, when a conventional solid-state copper compound is directly added to a polyamide resin, it is necessary to process the powder into a fine powder of 5 μm or less in order to uniformly disperse the compound in the polyamide resin, which is problematic in terms of cost and handling. .
[0009]
The caprolactam used in the present invention is not particularly limited, and those produced industrially can be used.
The water used in the present invention is preferably pure water or distilled water, but is not limited thereto, and general industrial water can also be used.
[0010]
As a method of dissolving a copper compound in caprolactam, a method of adding a predetermined amount of a copper compound to a lactam in a molten state and mixing and dissolving the same is exemplified. The concentration added to caprolactam depends on the type of copper compound, but is preferably 0.1 to 50 parts by weight based on 100 parts by weight of caprolactam. At this time, other stabilizers can be mixed at the same time.
[0011]
As a method of blending a caprolactam solution of a copper compound or an aqueous solution of caprolactam with a polyamide resin, a method in which a caprolactam solution in which a copper compound is dissolved is kept at a melting state of 70 ° C. or more and added at the time of compounding or molding processing of the polyamide resin. Can be After the caprolactam solution is cooled to 70 ° C. or lower, it may be pulverized in a solid state and blended at the time of preparing a polyamide resin compound or at the time of molding.
[0012]
Hot water of 20 ° C. or more can be added to caprolactam containing the copper compound to make a stable aqueous solution. The melting point of this aqueous solution can be adjusted by the concentration. It is preferable to adjust the melting point to room temperature or lower and mix it in a liquid state, since it can be uniformly dispersed on the surface of the polyamide resin. The concentration of the aqueous solution is not particularly limited, but is preferably 10 to 99% by weight of caprolactam, more preferably 30 to 85% by weight.
[0013]
When the melting point of the aqueous solution is equal to or higher than room temperature, the object of the present invention can be similarly effectively achieved when the aqueous solution is heated to a temperature equal to or higher than the melting point to form a liquid and used for premixing during compounding.
It is not clear why the present invention is achieved by dissolving in caprolactam, or dissolving in caprolactam and water. This is considered to be because the copper compound is easily dispersed, and as a result, the copper compound is easily molecularly coordinated with the polyamide resin.
[0014]
In addition to the glass fiber, carbon fiber, whisker, fibrous reinforcing material such as aramid fiber and polyphenylene sulfide fiber, talc, clay, silica, wollastonite, calcium carbonate Mineral fillers such as polyester resins, polyolefins, polyphenylene ether resins, polymers such as ABS resins, release agents such as higher fatty acid salts, higher fatty acids, higher fatty acid esters, low molecular weight polyolefins, hindered phenols, thioethers, phosphites, etc. And a light stabilizer such as a benzophenone-based, triazole-based, or hindered amine-based light stabilizer. In addition, carbon black and pigments can be blended.
[0015]
The heat-resistant polyamide resin according to the present invention is used by melting and kneading the constituent components using a device such as a single-screw extruder, a twin-screw extruder, or a kneader, or by spraying on the surface of a pellet during molding. There are no particular restrictions on the equipment used and kneading conditions. The molding method is not particularly limited, but is generally injection molding or extrusion molding.
[0016]
Hereinafter, the present invention will be described specifically with reference to Examples. The evaluation in the specification was measured by the following method.
(1) Using an injection molding machine whose temperature is set to 260 ° C. and a mold of TYPE B specified in ISO294-1 whose surface temperature is controlled to 80 ° C. A test piece of 80 mm × 10 mm × 4 mm was formed. Twenty molded articles were randomly collected and aged at 165 ° C. for 3000 hours. The treated sample was stored in a desiccator in a test room adjusted to 23 ° C. for 24 hours and conditioned. Using a universal tensile tester, a bending test was performed in accordance with ISO178 to measure the bending strength and the breaking strain, and an average value and a standard deviation at 20 points were obtained and compared. The reliability regarding the variation in durability performance was evaluated by the standard deviation.
[0017]
(Examples 1 to 8, Comparative Examples 1 to 5)
A predetermined amount of various copper compounds (Nacalai Tesque Co., Ltd., reagent grade 1) was added to a stabilizer compound as shown in Table 1 in caprolactam temperature-controlled to 80 ° C., melt-mixed with a stirrer, and heated to 80 ° C. A caprolactam solution of the copper compound was prepared and stored. Alternatively, 30 parts by weight of 80 ° C. hot water was added to 100 parts by weight of the molten mixture, mixed with a stirrer, and stored as an aqueous solution in a laboratory at about 25 ° C. The above operation was performed in a plastic tank.
[0018]
65 parts by weight of a polyamide 6 resin having a relative viscosity of 3.1 (solvent: 96% by weight sulfuric acid, polymer concentration: 1 g / dl) or polyamide 66 resin 65 having a relative viscosity of 3.2 measured in a thermostat at 20 ° C. Parts by weight, 35 parts by weight of talc having an average particle size of 4 μm, 0.2 parts by weight of potassium iodide, and a caprolactam solution of the copper compound or an aqueous solution of caprolactam in an amount of about 0.010% by weight in terms of copper atoms. Then, the mixture was put into a hopper of a twin screw extruder having a temperature of 260 ° C. and adjusted to 260 ° C. and melt-kneaded and extruded to obtain a pellet-shaped polyamide resin compound.
[0019]
As a comparative example, a polyamide resin compound was obtained by directly premixing the copper compound in a powder state without melt-mixing the caprolactam with the copper compound as shown in Table 2 or without mixing the copper compound.
[0020]
In Table 1, injection molded articles were obtained from the polyamide resin compound pellets obtained in Examples and Comparative Examples, and the bending strength and breaking strain after the heat aging were measured. The results are shown in Tables 1 and 2.
As is clear from Tables 1 and 2, the variation in bending strength and breaking strain after heat aging of the molded article of the polyamide resin composition obtained by the method of the present invention in Examples is different from those of Comparative Examples 3 to 5. It is extremely small compared to the variation in bending strength and breaking strain after heat aging.
[0021]
[Table 1]
【The invention's effect】
ADVANTAGE OF THE INVENTION According to this invention, the copper compound which is a heat stabilizer can be disperse | distributed to a polyamide resin uniformly and highly in a compounding process and a molding process, and the dispersion of durability performance is small, and the polyamide resin with high reliability is obtained. A composition can be manufactured. Therefore, it can be suitably used even in a field where high reliability is required for durability performance.
Claims (2)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2002256952A JP4235878B2 (en) | 2002-09-02 | 2002-09-02 | Method for producing heat-resistant polyamide resin composition |
| AU2003261873A AU2003261873A1 (en) | 2002-09-02 | 2003-09-01 | Method for producing polyamide resin composition excellent in durability at high temperature |
| PCT/JP2003/011159 WO2004022632A1 (en) | 2002-09-02 | 2003-09-01 | Method for producing polyamide resin composition excellent in durability at high temperature |
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| JP2002256952A JP4235878B2 (en) | 2002-09-02 | 2002-09-02 | Method for producing heat-resistant polyamide resin composition |
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| JP2004091707A true JP2004091707A (en) | 2004-03-25 |
| JP4235878B2 JP4235878B2 (en) | 2009-03-11 |
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| JP2002256952A Expired - Fee Related JP4235878B2 (en) | 2002-09-02 | 2002-09-02 | Method for producing heat-resistant polyamide resin composition |
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| AU (1) | AU2003261873A1 (en) |
| WO (1) | WO2004022632A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014520190A (en) * | 2011-06-24 | 2014-08-21 | アルケマ フランス | Compositions comprising semi-aromatic polyamides and their use, especially for reflectors with light-emitting diodes |
| WO2021149674A1 (en) * | 2020-01-24 | 2021-07-29 | 東洋紡株式会社 | Method for producing polyamide resin composition |
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| JPS417346B1 (en) * | 1962-11-24 | 1966-04-21 | ||
| JPS4520775B1 (en) * | 1965-08-27 | 1970-07-15 | ||
| JPS51114447A (en) * | 1975-04-01 | 1976-10-08 | Asahi Chem Ind Co Ltd | A process for preparing a thermoplastic composition colored by inorgan ic pigments |
| DE3600890A1 (en) * | 1986-01-15 | 1987-07-16 | Bayer Ag | METHOD FOR PRODUCING STABILIZED POLYAMIDES |
| JP3440485B2 (en) * | 1993-03-08 | 2003-08-25 | 東レ株式会社 | Method for producing polyamide pellets |
| JPH06263898A (en) * | 1993-03-10 | 1994-09-20 | Kanebo Ltd | Production of heat-resistant polyamide resin composition |
| JP3296140B2 (en) * | 1995-06-01 | 2002-06-24 | 東レ株式会社 | Method for producing polyamide resin particles containing heat-resistant agent |
| TW531549B (en) * | 1999-05-20 | 2003-05-11 | Ind Tech Res Inst | Method for producing thermoplastic nanocomposite |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2014520190A (en) * | 2011-06-24 | 2014-08-21 | アルケマ フランス | Compositions comprising semi-aromatic polyamides and their use, especially for reflectors with light-emitting diodes |
| WO2021149674A1 (en) * | 2020-01-24 | 2021-07-29 | 東洋紡株式会社 | Method for producing polyamide resin composition |
| JPWO2021149674A1 (en) * | 2020-01-24 | 2021-07-29 | ||
| JP6996666B2 (en) | 2020-01-24 | 2022-01-17 | 東洋紡株式会社 | Method for manufacturing polyamide resin composition |
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| AU2003261873A1 (en) | 2004-03-29 |
| WO2004022632A1 (en) | 2004-03-18 |
| JP4235878B2 (en) | 2009-03-11 |
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