JPH01185364A - Reinforced polyamide composition - Google Patents
Reinforced polyamide compositionInfo
- Publication number
- JPH01185364A JPH01185364A JP815188A JP815188A JPH01185364A JP H01185364 A JPH01185364 A JP H01185364A JP 815188 A JP815188 A JP 815188A JP 815188 A JP815188 A JP 815188A JP H01185364 A JPH01185364 A JP H01185364A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- present
- amine
- agent
- phenylenediamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 26
- 239000004952 Polyamide Substances 0.000 title claims description 8
- 229920002647 polyamide Polymers 0.000 title claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 25
- 150000001412 amines Chemical class 0.000 claims abstract description 19
- 230000003712 anti-aging effect Effects 0.000 claims description 21
- 239000012744 reinforcing agent Substances 0.000 claims description 20
- -1 Polytetramethylene Polymers 0.000 claims description 6
- GVNWZKBFMFUVNX-UHFFFAOYSA-N Adipamide Chemical compound NC(=O)CCCCC(N)=O GVNWZKBFMFUVNX-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 abstract description 6
- 239000003963 antioxidant agent Substances 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 4
- 230000003078 antioxidant effect Effects 0.000 abstract description 3
- 239000011521 glass Substances 0.000 abstract description 3
- 150000002484 inorganic compounds Chemical class 0.000 abstract description 2
- 229910010272 inorganic material Inorganic materials 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 239000000047 product Substances 0.000 description 16
- 239000003365 glass fiber Substances 0.000 description 15
- 238000000465 moulding Methods 0.000 description 13
- 229920003189 Nylon 4,6 Polymers 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 8
- 239000010687 lubricating oil Substances 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 239000000654 additive Substances 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000000740 bleeding effect Effects 0.000 description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- 235000011116 calcium hydroxide Nutrition 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 239000011342 resin composition Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XQVWYOYUZDUNRW-UHFFFAOYSA-N N-Phenyl-1-naphthylamine Chemical compound C=1C=CC2=CC=CC=C2C=1NC1=CC=CC=C1 XQVWYOYUZDUNRW-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- VETPHHXZEJAYOB-UHFFFAOYSA-N 1-n,4-n-dinaphthalen-2-ylbenzene-1,4-diamine Chemical compound C1=CC=CC2=CC(NC=3C=CC(NC=4C=C5C=CC=CC5=CC=4)=CC=3)=CC=C21 VETPHHXZEJAYOB-UHFFFAOYSA-N 0.000 description 1
- PYSRRFNXTXNWCD-UHFFFAOYSA-N 3-(2-phenylethenyl)furan-2,5-dione Chemical compound O=C1OC(=O)C(C=CC=2C=CC=CC=2)=C1 PYSRRFNXTXNWCD-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- UZARQBVTRHEUOB-UHFFFAOYSA-N 4-n-cyclohexylbenzene-1,4-diamine Chemical compound C1=CC(N)=CC=C1NC1CCCCC1 UZARQBVTRHEUOB-UHFFFAOYSA-N 0.000 description 1
- UUNBFTCKFYBASS-UHFFFAOYSA-N C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC Chemical compound C(CCCCCCC)C=1C(=C(C=CC1)NC1=CC=CC=C1)CCCCCCCC UUNBFTCKFYBASS-UHFFFAOYSA-N 0.000 description 1
- 229920000271 Kevlar® Polymers 0.000 description 1
- UTGQNNCQYDRXCH-UHFFFAOYSA-N N,N'-diphenyl-1,4-phenylenediamine Chemical compound C=1C=C(NC=2C=CC=CC=2)C=CC=1NC1=CC=CC=C1 UTGQNNCQYDRXCH-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N N-phenyl aniline Natural products C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920000147 Styrene maleic anhydride Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 239000004761 kevlar Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002557 mineral fiber Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
ａ、産業上の利用分野
本発明は、特に自動車、２輪車などのトランスミツ：／
：ｌン、デフ、エンジン機構部などの潤滑油中で使用さ
れるプラスチック保持器を形成するために有用なプラス
チック組成物に関し、さらに詳しくはポリテトラメチレ
ンアジパミドと補強剤からなる配合物に特定量のアミン
系老化防止剤を添加してなる組成物であり、耐熱性、耐
油性、機械的特性さらに成形収縮率、吸水性の寸法変化
・そり変形量等の寸法安定性の優れた補強剤含有ポリア
ミド組成物に関する。[Detailed Description of the Invention] a. Field of Industrial Application The present invention is particularly applicable to transmissions such as automobiles and two-wheeled vehicles.
: Concerning plastic compositions useful for forming plastic retainers for use in lubricating oils such as lubricants, differentials, engine mechanisms, etc., and more particularly to formulations of polytetramethylene adipamide and reinforcing agents. This is a composition made by adding a specific amount of amine-based anti-aging agent, and it is reinforced with excellent heat resistance, oil resistance, mechanical properties, and dimensional stability such as molding shrinkage rate, water absorption, dimensional change, warping amount, etc. The present invention relates to a polyamide composition containing an agent.
ｂ、従来の技術
ポリアミド樹脂等のプラスチックは各種の優れた特性を
有することから、構造材料として各種用途への実用化が
期待されている。b. Prior Art Since plastics such as polyamide resins have various excellent properties, they are expected to be put into practical use as structural materials for various purposes.
しかし、自動車、２輪車などのトランスミッション、デ
フ、エンジン機構部などでは、使用温度条件が定常的に
は８０°Ｃ程度であるか、走行条件、環境及び車の形式
などにより１２０〜１３０°Ｃ１場合によっては１５０
°Ｃ以１−の温度にまで達する場合がある。このような
用途に於い−Ｃは、一般にプラスチック成形品を高温ト
に於いて使用すること、各種の添加剤が含まれζいる潤
滑油に接触することにより、プラスチ・ツク成形品に悪
影響を与え、プうスヂンク成形品の強度低下、変形外観
性の低下等の原因となる。これ等の欠点を改善する方法
として、例えばガラス繊維を添加する方法がよく用いら
れるが、この方法では耐熱性、機械的特性、寸法安定性
等は改善されるが、耐油性や長期熱安定性を同時に改善
するには未だいたっていない。However, in transmissions, differentials, engine mechanisms, etc. of automobiles, motorcycles, etc., the operating temperature is normally around 80°C, or 120 to 130°C depending on driving conditions, environment, and type of car. 150 in some cases
Temperatures up to 1°C or higher may be reached. In such applications, -C generally has a negative impact on plastic molded products due to the use of plastic molded products at high temperatures and when they come into contact with lubricating oils containing various additives. This causes a decrease in the strength and deformed appearance of the molded product. As a method to improve these drawbacks, for example, adding glass fiber is often used, but although this method improves heat resistance, mechanical properties, dimensional stability, etc., oil resistance and long-term thermal stability It has not yet been possible to simultaneously improve the
Ｃ９発明が解決しようとする問題点
そこで、本発明者らは、ポリテトラメチレンアジパミド
（以下、ナイロン４６と称する）の上記問題を改良する
ために鋭意検討した結果、ナイロン４６に特定量の補強
剤を混合し、かつアミン系老化防止剤を、好ましくはジ
アリール−ｐ−フェニレンジアミン系老化防止剤を配合
した樹脂組成物は、耐熱性、耐油性、機械的特性さらに
成形収縮率、寸法安定性等の物性バランスが優れること
を見出し、本発明に到達した。C9 Problems to be Solved by the Invention Therefore, the present inventors conducted intensive studies to improve the above-mentioned problems of polytetramethylene adipamide (hereinafter referred to as nylon 46), and as a result, the present inventors added a specific amount of polytetramethylene adipamide (hereinafter referred to as nylon 46) to nylon 46. A resin composition containing a reinforcing agent and an amine-based anti-aging agent, preferably a diaryl-p-phenylenediamine-based anti-aging agent, has excellent heat resistance, oil resistance, mechanical properties, mold shrinkage rate, and dimensional stability. It was discovered that the balance of physical properties such as properties is excellent, and the present invention was achieved.
ｄ０問題点を解決するための手段
本発明は、ナイロン４６．２０〜９０重ｆｆｉ％及び補
強剤１０〜８０重量％からなる組成物１００重量部に対
し、アミン系老化防止剤０．１〜５重量部を配合するこ
とを特徴とする補強剤含有ポリアミド組成物を提供する
ものである。Means for Solving the d0 Problems The present invention uses 0.1 to 5 parts by weight of an amine anti-aging agent to 100 parts by weight of a composition consisting of 46.20 to 90% by weight of nylon and 10 to 80% by weight of a reinforcing agent. The object of the present invention is to provide a polyamide composition containing a reinforcing agent, characterized in that the reinforcing agent is blended in parts by weight.
本発明に用いるナイロン４６は下記式
％式％
で示される繰り返し構造単位から実質的になるポリアミ
ドであり、その製造法については、例えば特開昭５６−
１４９４３０号、同５６−１４９４３１号、同５８−８
３０２９号、同６０−２８８４３号などに述べられてい
る方法を挙げることができる。Nylon 46 used in the present invention is a polyamide consisting essentially of repeating structural units represented by the following formula %.
No. 149430, No. 56-149431, No. 58-8
Examples include methods described in No. 3029 and No. 60-28843.
本発明で用いるナイロン４６の相対粘度（ηｒｅ１ ：
３０°Ｃで９７％硫酸１００−中のポリマー１ｇの溶液
で測定）は、好ましくは１．５以上、さらに好ましくは
２．５〜５であり、本発明の組成物中のナイロン４６の
使用割合は、２０〜９０重量％、好ましくは３５〜８５
重量％であり、さらに好ましくは５０〜８５重量％であ
る。２０重量％未満では成形加工性、成形外観が著しく
低下し、一方９０重量％を越えると耐衝撃性、剛性、耐
熱性、寸法安定性の改良が十分でなく好ましくない。Relative viscosity (ηre1:
(measured in a solution of 1 g of polymer in 100% 97% sulfuric acid at 30° C.) is preferably greater than or equal to 1.5, more preferably from 2.5 to 5, and the proportion of nylon 46 used in the composition of the invention is 20 to 90% by weight, preferably 35 to 85% by weight.
% by weight, more preferably 50 to 85% by weight. If it is less than 20% by weight, molding processability and molded appearance will be significantly deteriorated, while if it exceeds 90% by weight, improvements in impact resistance, rigidity, heat resistance, and dimensional stability will not be sufficient.
本発明に適用される補強剤としては、有機物、無機物な
ど種々のものが使用できるが、機械的特性などの点から
繊維状もしくはウィスカー状のものが好ましく、これら
の例としては各種金属繊維、石綿などの鉱物繊維、ガラ
スや岩石からの珪酸塩繊維、ケブラーなどの有機繊維な
どがある。これらのうち特に好ましいものは熱可塑性樹
脂や熱硬化性樹脂の補強剤として、一般に用いられてい
るガラス繊維である。ガラス繊維のうち、好ましいのは
直径３〜２０μｍ程度の連続長繊維のストランドから作
られたガラスチョツプドストランドで、通常平均長さが
的 ５ｍｍ以上、更に好ましくは１〜２０關、特に好ま
しくは２〜１０ｍｍのものである。Various reinforcing agents such as organic and inorganic substances can be used as the reinforcing agent in the present invention, but fibrous or whisker-like reinforcing agents are preferable from the viewpoint of mechanical properties. Examples of these include various metal fibers, asbestos, etc. These include mineral fibers such as, silicate fibers from glass and rocks, and organic fibers such as Kevlar. Among these, particularly preferred is glass fiber, which is generally used as a reinforcing agent for thermoplastic resins and thermosetting resins. Among the glass fibers, preferred are chopped glass strands made from strands of continuous filaments with a diameter of about 3 to 20 μm, usually with an average length of 5 mm or more, more preferably 1 to 20 μm, and particularly preferred. It is 2 to 10 mm.
また、本発明で使用する補強剤の組成及び製造方法には
特に制限はなく、」−記形状のものであればいかなるも
のでもよいが、好ましくは脂肪族系の表面処理剤で処理
したものを用いると、ペレット化時に起こる熱劣化によ
るペレットの着色の問題が改善され、−段と優れた品質
のものが得られる。Furthermore, there are no particular restrictions on the composition and manufacturing method of the reinforcing agent used in the present invention, and any reinforcing agent may be used as long as it has the shape shown in the figure, but it is preferable to use one that has been treated with an aliphatic surface treatment agent. When used, the problem of discoloration of pellets due to thermal deterioration that occurs during pelletization is improved, and pellets of much superior quality can be obtained.
なお、本発明でガラス繊維を使用する場合、そのガラス
繊維の平均の長さが０．５ｍｍより長いとナイロン４６
の耐衝撃性、耐熱性、剛性、寸法安定性の改良の点で好
ましい。In addition, when using glass fiber in the present invention, if the average length of the glass fiber is longer than 0.5 mm, nylon 46
It is preferred in terms of improved impact resistance, heat resistance, rigidity, and dimensional stability.
本発明のポリアミド樹脂組成物において、補強剤の使用
量は重量組成比で１０〜８０重量％、好ましくは１５〜
７５重量％、さらに好ましくは１５〜５０重量％である
。補強剤の配合量が１０重量％未満であると耐衝撃性、
耐熱性、剛性、寸法安定性の改良効果が小さく、また８
０重量％を越えると成形加工性や成形外観が低下する。In the polyamide resin composition of the present invention, the amount of reinforcing agent used is 10 to 80% by weight, preferably 15 to 80% by weight.
It is 75% by weight, more preferably 15 to 50% by weight. When the amount of reinforcing agent is less than 10% by weight, impact resistance,
The effect of improving heat resistance, rigidity, and dimensional stability is small, and
If it exceeds 0% by weight, molding processability and molded appearance deteriorate.
本発明の組成物を用いて射出成形などにより、その条件
を調節することにより成形物が得られる。A molded article can be obtained by injection molding or the like using the composition of the present invention and adjusting the conditions.
補強剤としてガラス繊維を用いた場合、該成形物中のガ
ラス繊維長が平均で、好ましくは０．０５〜０． ６ｍ
ｍ、さらに好ましくは０．１〜０．４ｍｍのものである
。また、標準偏差で０．１〜０．５ｍｍあることが好ま
しく、さらに好ましくは０．１〜０．３ｍｍのものであ
る。When glass fiber is used as a reinforcing agent, the average length of the glass fiber in the molded product is preferably 0.05 to 0. 6m
m, more preferably 0.1 to 0.4 mm. Moreover, it is preferable that the standard deviation is 0.1 to 0.5 mm, and more preferably 0.1 to 0.3 mm.
また成形物中のガラス繊維の長さ／直径の比（アスペク
ト比）は３〜５０が好ましく、さらに好ましくは５〜４
０、特に好ましくは１０〜３０である。The length/diameter ratio (aspect ratio) of the glass fibers in the molded product is preferably 3 to 50, more preferably 5 to 4.
0, particularly preferably 10-30.
成形物中のガラス繊維長が平均で０．０５ｍｍより短い
とナイロン４６の耐衝撃性、剛性、寸法安定性が低下す
る傾向にあり、また０、６ｍｍ以上であると成形外観が
低下する。If the glass fiber length in the molded product is shorter than 0.05 mm on average, the impact resistance, rigidity, and dimensional stability of nylon 46 tend to decrease, and if it is 0.6 mm or more, the molded appearance deteriorates.
さらに、成形物中のガラス繊維長の標準偏差は０．１ｍ
ｍより小さいと耐衝撃性、剛性、耐熱性、寸法安定性な
どと成形品の表面外観との物性バランスが（ずれ好まし
くない。また０、５ｍｍを越えた場合も上記物性バラン
スがくずれ、目的とする成形物が得られ難い。Furthermore, the standard deviation of the glass fiber length in the molded product is 0.1 m.
If it is smaller than m, the physical property balance between impact resistance, rigidity, heat resistance, dimensional stability, etc. and the surface appearance of the molded product will be undesirable.If it exceeds 0.5 mm, the above physical property balance will be disrupted, and it will not meet the purpose. It is difficult to obtain a molded product.
成形物中のガラス繊維の寸法を本発明の範囲内に調整す
る方法としては、成形時の射出速度、スクリューの回転
、成形温度の成形条件、成形金型のゲートサイズ等を適
宜調整することで目的の寸法とすることができる。The dimensions of the glass fibers in the molded product can be adjusted within the scope of the present invention by appropriately adjusting the injection speed during molding, the rotation of the screw, the molding conditions such as molding temperature, the gate size of the mold, etc. It can be of any desired size.
さらに、本発明に使用するアミン系老化防止剤としでは
、Ｎ、 Ｎ’ −ジフェニル−ｐ−フェニレンジアミン
、Ｎ、Ｎ’ −ジー２−ナフチル−ｐ−フェニレンジア
ミン等のジアリール−ｐ−フェニレンジアミン系老化防
止剤、Ｎ−フェニル−Ｎ′−イソプロピル−ｐ−フェニ
レンジアミン、Ｎ−フェニル−Ｎ’−（１，３−ジメチ
ルブチル）−ｐ−フェニレンジアミン、Ｎ−フェニル−
Ｎ’ −シクロへキシル−ｐ−フェニレンジアミン等の
アリールアルキル−ｐ−フェニレンジアミン系老化防止
剤、アルキレ−ティラドジフェニルアミド、４．４′−
ジ−オクチルジフェニルアミン等のジフェニルアミン系
老化防止剤、およびその他のアミン系老化防止剤として
フェニル−１−ナフチルアミン、２−メルカプトベンズ
イミダゾール、２゜２．４−トリメチル−１，２−ジノ
飄イドロキノリンのポリマー等が挙げられるが、これら
のアミン系老化防止剤のうち芳香族系アミンが好ましく
、ジアリール−ｐ−フェニレンジアミン系老化防止剤が
特に効果が著しい。上記老化防止剤は単独で使用しても
よいし、混合したものであってもよい。Furthermore, as the amine-based antiaging agent used in the present invention, diaryl-p-phenylenediamine-based agents such as N,N'-diphenyl-p-phenylenediamine, N,N'-di-2-naphthyl-p-phenylenediamine, etc. Antiaging agent, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)-p-phenylenediamine, N-phenyl-
Arylalkyl-p-phenylenediamine type anti-aging agents such as N'-cyclohexyl-p-phenylenediamine, alkylene-tiradodiphenylamide, 4.4'-
Diphenylamine-based anti-aging agents such as di-octyl diphenylamine, and other amine-based anti-aging agents such as polymers of phenyl-1-naphthylamine, 2-mercaptobenzimidazole, and 2゜2,4-trimethyl-1,2-dinohydroquinoline. Among these amine-based antioxidants, aromatic amines are preferred, and diaryl-p-phenylenediamine-based antioxidants are particularly effective. The above anti-aging agents may be used alone or in combination.
−７＝
また、必要に応じてアミン系以外の老化防止剤も併用し
てもよい。-7= Additionally, anti-aging agents other than amine type may be used in combination, if necessary.
上記成分（ナイロン４６及び補強剤の合計量）１００重
量部に対して、アミン系老化防止剤は０゜１〜５．０重
量部、好ましくは０．２〜３重量部゛″
配合することにより、高温下の潤滑油中での熱劣化特性
が著しく改良され優れた品質のものが得られる。これ等
アミン系老化防止剤の配合量が０゜１重量部未満では、
高温下での潤滑油中での熱劣化特性の改良効果が小さく
、一方、５重量部を越えると成形加工性や成形外観が低
下する。さらに、本発明に於いては特定の無機物、すな
わちＣａ（ＯＨ）２又はＭｇＯを、好ましくは０．１〜
５重量部、更に好ましくは０．２〜２重量部配合するこ
とにより、高温下の潤滑油中での耐油性が一段と優れた
品質のものが得られる。各種潤滑油中には種々の添加剤
が混合されており、中でも清浄分散剤、極圧剤、摩擦調
整剤等に酸性物質が数多く含まれ、これらが高温下のポ
リマーの劣化を促進している。これ等添加剤の補足剤と
して、上記Ｃａ （ＯＨ）２及び／又はＭｇＯが有効に
働くため、Ｃａ （ＯＨ）２又はＭｇＯをアミン系老化
防止剤を併用することで、さらに優れた効果が得られる
。For 100 parts by weight of the above components (total amount of nylon 46 and reinforcing agent), the amount of the amine anti-aging agent is 0.1 to 5.0 parts by weight, preferably 0.2 to 3 parts by weight.
By blending them, the thermal deterioration characteristics in lubricating oil at high temperatures are significantly improved, and products of excellent quality can be obtained. If the amount of these amine anti-aging agents is less than 0.1 parts by weight,
The effect of improving thermal deterioration characteristics in lubricating oil at high temperatures is small, and on the other hand, if it exceeds 5 parts by weight, moldability and molded appearance deteriorate. Furthermore, in the present invention, a specific inorganic substance, namely Ca(OH)2 or MgO, is preferably added to
By blending 5 parts by weight, more preferably 0.2 to 2 parts by weight, a product with even better oil resistance in lubricating oil at high temperatures can be obtained. Various additives are mixed into various lubricating oils, and among them, many acidic substances are included in detergent dispersants, extreme pressure agents, friction modifiers, etc., and these accelerate the deterioration of polymers at high temperatures. . Since the above-mentioned Ca(OH)2 and/or MgO work effectively as a supplement to these additives, even better effects can be obtained by using Ca(OH)2 or MgO together with an amine-based anti-aging agent. It will be done.
本発明の組成物は必要に応じて下記に示すポリマー成分
を含有することができる。The composition of the present invention may contain the following polymer components as necessary.
例えば、ポリブタジェン、ブタジェン−スチレン共重合
体、アクリルゴム、エチレン−プロピレン共重合体、Ｅ
ＰＤＭ、スチレン−ブタジェンブロック共重合体、ポリ
プロピレン、ブタジェン−アクリロニトリル共重合体、
スチレン−無水マレイン酸共重合体などである。For example, polybutadiene, butadiene-styrene copolymer, acrylic rubber, ethylene-propylene copolymer, E
PDM, styrene-butadiene block copolymer, polypropylene, butadiene-acrylonitrile copolymer,
Examples include styrene-maleic anhydride copolymer.
その他必要に応じて安定剤、滑剤、染顔料等を添加する
ことができる。Other stabilizers, lubricants, dyes and pigments, etc. may be added as necessary.
本発明はその優れた性質を有することから、特に自動車
、２輪車などのトランスミッション、デフ、エンジン機
構部などのプラスチック保持器として有用である。Since the present invention has excellent properties, it is particularly useful as a plastic retainer for transmissions, differentials, engine mechanisms, etc. of automobiles, two-wheeled vehicles, etc.
ｅ、実施例
以下、本発明を実施例、比較例を用いて具体的に説明す
る。なお、実施例、比較例において「部」及び「％」は
特に断わりのない限り全て「重量部」及び「重量％」を
示す。また、成形条件、成形品形状、成形品の性能評価
方法は下記方法に従った。e. Examples Hereinafter, the present invention will be specifically explained using Examples and Comparative Examples. In Examples and Comparative Examples, all "parts" and "%" refer to "parts by weight" and "% by weight" unless otherwise specified. In addition, the molding conditions, the shape of the molded product, and the performance evaluation method of the molded product were in accordance with the following methods.
（成形条件）
シリンダー温度 ２９０〜３１０°Ｃ金型温度
８０〜１２０°Ｃ
射出圧力 １００〜８００ｋｇ／ｃ１１！射出時間
１〜５ｓｅｃ
冷却時間 １０〜５０ｓｅｃ
スクリュー回転 ５０〜２５ Ｏｒｐｍゲートサ
イズ
０．５Ｘ２ｍｍ〜１．７Ｘ３．８ｍｍ
ランナーサイズ ８ｍｍ
なお、成形機は日精プラスチック株式会社製ＰＳ４ＯＥ
型 射出成形機を使用した。(Molding conditions) Cylinder temperature 290-310°C Mold temperature
80~120°C Injection pressure 100~800kg/c11! injection time
1~5sec Cooling time 10~50sec Screw rotation 50~25 Orpm Gate size 0.5X2mm~1.7X3.8mm Runner size 8mm The molding machine is PS4OE manufactured by Nissei Plastics Co., Ltd.
Mold An injection molding machine was used.
（評価方法）
■ 荷重たわみ温度（ＨＤＴ）：ＡＳＴＭ Ｄ６４８
、荷重１８．６ｋｇ／ｃＪ、アニールなし■ 引張強度
、引張伸び：ＡＳＴＭ Ｄ６３８、引張速度 ５０ｍ
ｍ／ｍｉｎ
■ アイゾツト衝撃強度：ＡＳＴＭ Ｄ２５６．２３
℃、ノツチつき
■ 成形収縮率：成形後２４時間後の流れ方向の寸法変
化を測定。テストピース、１／２″Ｘ１／８″′×５”
■ 成形外観：厚み１．６ｍｍの配向プレートの外観を
目視評価
◎：光沢があり表面が平滑である
○：光沢はやや劣るが表面は平滑である△：光沢はな（
表面がややザラザラしている×：光沢もなく表面はザラ
ザラである
■ 高温耐油テスト：シェルスパイラックスＥＰ−９０
（ギアーオイル）
＊ １５０℃×３００時間浸漬
実施例１〜６
直径的１３μｍの連続長繊維のストランドから作られた
平均の長さ３ｍｍのチョツプドストランド（旭ファイバ
ーグラス■製０３−ＭＡ−ＦＴ２）、ナイロン４６（相
対粘度：ηｒｅｌ ３． ５） 、アミン系老化防止剤
、及びその他の添加剤を表−１に示した割合で同時にタ
ンブラ−で混合し、次に押出機を用いて３００〜３３０
℃のシリンダー温度条件で溶融混合した。その混合物を
射出成形機により成形し、テストピースを作製した。(Evaluation method) ■ Load deflection temperature (HDT): ASTM D648
, load 18.6 kg/cJ, no annealing ■ Tensile strength, tensile elongation: ASTM D638, tensile speed 50 m
m/min ■ Izot impact strength: ASTM D256.23
℃, with notch■ Molding shrinkage rate: Measure the dimensional change in the flow direction 24 hours after molding. Test piece, 1/2″X1/8″′×5″ ■ Molding appearance: Visually evaluate the appearance of the oriented plate with a thickness of 1.6mm ◎: Glossy and smooth surface ○: Slightly inferior gloss but surface Smooth △: Glossy (
The surface is a little rough ×: The surface is rough without gloss ■ High temperature oil resistance test: Shell Spirax EP-90
(Gear oil) * 150°C x 300 hours immersion Examples 1 to 6 Chopped strands with an average length of 3 mm made from strands of continuous fibers with a diameter of 13 μm (manufactured by Asahi Fiberglass 03-MA-FT2) ), nylon 46 (relative viscosity: ηrel 3.5), an amine anti-aging agent, and other additives were simultaneously mixed in a tumbler in the proportions shown in Table 1, and then mixed using an extruder to 330
Melt mixing was carried out under cylinder temperature conditions of °C. The mixture was molded using an injection molding machine to produce a test piece.
得られたテストピースについて上記の評価方法で各物性
の評価を行ない表−１に示す結果を得た。Each physical property of the obtained test piece was evaluated using the above evaluation method, and the results shown in Table 1 were obtained.
表−１に示した結果から、本発明の成形品は本発明の目
的とする物性のものが得られていることがわかる。From the results shown in Table 1, it can be seen that the molded article of the present invention has the physical properties targeted by the present invention.
比較例１は実施例１で使用したガラス繊維、ナイロン４
６（相対粘度：ηｒｅｌ ３． ５）を用いて表−１に
示した組成比率で樹脂組成物を調整し、その物性を実施
例１と同様の方法で評価した。その結果を表−１に示す
。比較例１はガラス繊維量が本発明の範囲未満の成形物
であり、耐熱性、機械的強度、耐衝撃性、寸法安定性及
び高温耐油性がいずれも十分でない。Comparative Example 1 is the glass fiber and nylon 4 used in Example 1.
6 (relative viscosity: ηrel 3.5) to prepare a resin composition at the composition ratio shown in Table 1, and its physical properties were evaluated in the same manner as in Example 1. The results are shown in Table-1. Comparative Example 1 is a molded product with an amount of glass fiber below the range of the present invention, and has insufficient heat resistance, mechanical strength, impact resistance, dimensional stability, and high temperature oil resistance.
比較例２は、ガラス繊維量が本発明の範囲を越えている
組成物を用いたものであり、成形加工性や成形外観及び
高温耐油性が劣る。Comparative Example 2 uses a composition in which the amount of glass fiber exceeds the range of the present invention, and is inferior in molding processability, molded appearance, and high-temperature oil resistance.
比較例３は、本発明のアミン系老化防止剤以外の他の老
化防止剤（フェノール系）を用いたもので、本発明の目
的とする高温耐油性が劣る。Comparative Example 3 uses an anti-aging agent (phenol-based) other than the amine-based anti-aging agent of the present invention, and is inferior in high-temperature oil resistance, which is the objective of the present invention.
比較例４〜５は、アミン系老化防止剤量が本発明の範囲
外の組成物であり、成形外観、機械的強度、衝撃強度が
劣り目的とする物性が得られない。Comparative Examples 4 and 5 are compositions in which the amount of the amine antioxidant is outside the range of the present invention, and the molded appearance, mechanical strength, and impact strength are poor, and the desired physical properties cannot be obtained.
比較例６は、ナイロン４６以外の他のポリアミド樹脂を
用いた組成物であり、本発明の組成物に競べ、耐熱性、
機械的強度、耐衝撃性や高温耐油性が劣り好ましくない
。Comparative Example 6 is a composition using a polyamide resin other than nylon 46, which is comparable to the composition of the present invention, and has heat resistance,
Mechanical strength, impact resistance, and high-temperature oil resistance are poor, making it undesirable.
比較例７は、老化防止剤がアミン系でない場合（フェノ
ール系）であり、耐衝撃性、高温耐油性が劣る。Comparative Example 7 is a case where the anti-aging agent is not amine-based (phenol-based), and the impact resistance and high-temperature oil resistance are poor.
ｆ０発明の効果
本発明の補強剤含有ポリアミド組成物は、ナイロン４６
に特定量のガラス繊維及び特定量のアミン系老化防止剤
を配合したものであり、耐熱性、機械的強度、耐衝撃性
、成形外観及び高温耐油性の物性バランスが高水準にあ
る。f0 Effects of the Invention The reinforcing agent-containing polyamide composition of the present invention has nylon 46
It contains a specific amount of glass fiber and a specific amount of amine anti-aging agent, and has a high level of physical property balance of heat resistance, mechanical strength, impact resistance, molded appearance, and high temperature oil resistance.
したがって本発明の組成物は、優れた物性バランスを有
することから、自動車や２輪車等のトランスミッション
、デフ、エンジン機構部等の高温下で潤滑油にさらされ
るプラスチック用保持器（ベアリングリテーナ−）をは
じめ、優れた物性バランスを有する各種部品の成形品を
提供するものであり、産業上の利用価値は極めて大きい
。Therefore, since the composition of the present invention has an excellent balance of physical properties, it can be used in plastic retainers (bearing retainers) that are exposed to lubricating oil at high temperatures, such as transmissions, differentials, and engine mechanisms of automobiles and motorcycles. It provides molded products of various parts with an excellent balance of physical properties, and has extremely high industrial value.
特許出願人 日本合成ゴム株式会社
手続補正書（自発）
１．事件の表示
昭和６３年特許願第８１５１号
２、発明の名称
補強剤含有ポリアミド組成物
３、補正をする者
事件との関係 特許出願人
住 所 東京都中央区築地二丁目１１番２４号電話（
０３）５４１−４１１１■
４、補正の対象
明細書の「発明の詳細な説明」の欄
５、補正の内容
（１）明細書第９頁第１３行目のｒＣａ （ＯＨ）２又
はＭｇＯを」とあるを
ｒｃａ （ＯＨ）２ 、ＭｇＯ等のアルカリ無機化合物
を」に訂正する。Patent applicant: Japan Synthetic Rubber Co., Ltd. Procedural amendment (voluntary) 1. Description of the case Patent Application No. 8151 No. 8151 of 1988 2, Name of the invention Polyamide composition containing reinforcing agent 3, Person making the amendment Relationship to the case Patent applicant Address 2-11-24 Tsukiji, Chuo-ku, Tokyo Telephone (
03) 541-4111 ■ 4. "Detailed Description of the Invention" column 5 of the specification to be amended, contents of the amendment (1) "rCa(OH)2 or MgO on page 9, line 13 of the specification" Correct the statement to "alkaline inorganic compounds such as rca (OH)2 and MgO."
（２）明細書第１２頁の下から第４行目と第３行目の間
に次の文章を挿入する。(2) Insert the following sentence between the fourth and third lines from the bottom of page 12 of the specification.
「■ ブリード性：１００℃沸水中に１００時間浸漬後
、添加剤のブリード性
を目視評価
０１表面変化なし
０１表面に極く少しブリードが見られる△；表面にブリ
ードが見られる
×；表面のブリード著しい 」（３）明細書
第１２頁下から第３行目の「実施例１〜６」とあるを「
実施例１〜１１」に訂正する。"■ Bleeding property: After 100 hours of immersion in 100°C boiling water, visually evaluate the additive's bleedability. 01 No surface change 01 Very slight bleed observed on the surface △; Bleeding observed on the surface ×; Bleeding on the surface (3) The phrase “Examples 1 to 6” in the third line from the bottom of page 12 of the specification has been changed to “
Corrected to ``Examples 1 to 11''.
（４）明細書第１６頁の表−１を次のとおりとする。(4) Table 1 on page 16 of the specification is as follows.
Claims (2)
及び補強剤１０〜８０重量％からなる組成物１００重量
部に対し、アミン系老化防止剤０．１〜５重量部を配合
することを特徴とする補強剤含有ポリアミド組成物。(1) Polytetramethylene adipamide 20-90% by weight
A reinforcing agent-containing polyamide composition, characterized in that 0.1 to 5 parts by weight of an amine anti-aging agent is blended to 100 parts by weight of a composition containing 10 to 80% by weight of a reinforcing agent.
ンジアミン系であることを特徴とする特許請求の範囲第
（１）項記載の補強剤含有ポリアミド組成物。(2) The reinforcing agent-containing polyamide composition according to claim (1), wherein the amine-based antiaging agent is diaryl-p-phenylenediamine-based.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP815188A JPH01185364A (en) | 1988-01-18 | 1988-01-18 | Reinforced polyamide composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP815188A JPH01185364A (en) | 1988-01-18 | 1988-01-18 | Reinforced polyamide composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01185364A true JPH01185364A (en) | 1989-07-24 |
Family
ID=11685316
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP815188A Pending JPH01185364A (en) | 1988-01-18 | 1988-01-18 | Reinforced polyamide composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01185364A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0586985A1 (en) * | 1992-09-04 | 1994-03-16 | BASF Aktiengesellschaft | Stabilized Polyamide/Polyphenylene ether mouldings |
| WO2024105886A1 (en) * | 2022-11-18 | 2024-05-23 | 三菱電機株式会社 | Composite resin composition, molded article, and method for producing composite resin composition |
-
1988
- 1988-01-18 JP JP815188A patent/JPH01185364A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0586985A1 (en) * | 1992-09-04 | 1994-03-16 | BASF Aktiengesellschaft | Stabilized Polyamide/Polyphenylene ether mouldings |
| WO2024105886A1 (en) * | 2022-11-18 | 2024-05-23 | 三菱電機株式会社 | Composite resin composition, molded article, and method for producing composite resin composition |
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