JPH032392B2

JPH032392B2 -

Info

Publication number: JPH032392B2
Application number: JP59182765A
Authority: JP
Inventors: Hironobu Kawasaki; Sadayuki Yakabe
Original assignee: Asahi Chemical Industry Co Ltd
Current assignee: Asahi Chemical Industry Co Ltd
Priority date: 1984-09-03
Filing date: 1984-09-03
Publication date: 1991-01-14
Also published as: JPS6160754A

Description

[Detailed description of the invention]

〔産業上の利用分野〕本発明は、道路凍結防止剤（塩化カルシウム）
に対する抵抗性を有し、優れた機械的特性と耐熱
性を兼ね備えた、自動車部品成形材料として有用
なガラス繊維強化ポリアミド樹脂組成物を提供す
るものである。〔従来の技術〕ガラス繊維強化ナイロン66はその強靭性、耐熱
性、耐油性等を生かして、自動車の部品分野に利
用されているが、ナイロン66の重大な欠点の一つ
に金属ハロゲン化物によつて環境応力亀裂が生じ
ることがあげられる。例えば自動車部品であるラ
ジエータータンク、キヤニスター、シリンダーヘ
ツドカバー等には強度、耐熱性、耐油性に優れる
ナイロン66類が多く使用されているが、特に道路
凍結防止剤として用いられる塩化カルシウムによ
り、成形品に亀裂（クラツク）を生じ、成形品の
劣化を引き起こすため、厳しく対応策が求められ
ている。従来より、ナイロン66の金属ハロゲン化物に対
する抵抗性を改善するため、研究がなされてお
り、ナイロン66に高級脂肪族ポリアミドを配合す
ることが効果的であることが知られている（特開
昭57−80448、特開昭57−80449）。しかし、ナイロン66に高級脂肪族ポリアミドを
単に配合しものは、ナイロン66と高級脂肪族ポリ
アミドとの相溶性が損なわれる為に機械的特性、
特に落錘衝撃強度が充分でなく、厳しい信頼性が
要求される自動車部品材料としては満足されるも
のではなかつた。〔発明が解決しようとする問題点〕本発明者らは、さらにこの問題を改善すべく鋭
意検討した結果、ナイロン66〔Ａ〕に高級脂肪族
ポリアミド〔Ｂ〕を配合するに際し、さらに高級
脂肪族ポリアミド〔Ｃ〕を配合することによつ
て、ナイロン66〔Ａ〕と高級脂肪族ポリアミド
〔Ｂ〕の相溶性が良好になることを見い出し、本
発明を完成させたものである。即ち本発明は、道路凍結防止剤（塩化カルシウ
ム）に対する抵抗性を有し、優れた機械的特性と
耐熱性を兼ね備え、改良された落錘強度を有する
自動車部品成形材料として、有用なガラス繊維強
化ポリアミド樹脂組成物を提供するためになされ
たものである。〔問題点を解決するための手段及び作用〕本発明はナイロン66〔Ａ〕、ポリマー主鎖中のメ
チレン基数とアミド基の比（CH₂／NHCO）が
６〜11である高級脂肪族ポリアミド〔Ｂ〕及びポ
リマー主鎖中のメチレン基数とアミド基数の比
（CH₂／NHCO）がナイロン66〔Ａ〕と高級脂肪
族ポリアミド〔Ｂ〕との間にある高級脂肪族ポリ
アミド〔Ｃ〕からなるポリアミド樹脂組成物であ
つて、該ポリアミド樹脂組成物100重量部中に
〔Ａ〕の量が20〜80重量部、〔Ｂ〕の量が10〜79重
量部、〔Ｃ〕の量が１〜20重量部であるポリアミ
ド樹脂組成物40〜90重量％とガラス繊維60〜10重
量％とからなる道路凍結防止剤に対して抵抗性を
有する自動車部品用成形材料に関するものであ
る。本発明組成の特徴は上述のごとく、ナイロン66
〔Ａ〕、高級脂肪族ポリアミド〔Ｂ〕、高級脂肪族
ポリアミド〔Ｃ〕の３成分組成にある。本発明で
言う〔Ａ〕と〔Ｂ〕はいずれも同じポリアミドで
あり、例えばナイロン66とナイロン612であり、
両者には相溶性があり、両者のブレンド物には物
性上の問題があるとは思えなかつた。しかし実用
的な評価を進めてみると、落錘衝撃性において、
特に低温での落錘衝撃性に問題があることが判つ
た。本発明者等はこの改善策を鋭意検討して、驚
くべきことに〔Ａ〕、〔Ｂ〕、〔Ｃ〕の組み合せすな
わち、ポリマー主鎖中のメチレン基数とアミド基
数の比（CH₂／NHCO）の異なるポリアミドの
組合せが有効であることを見い出した。本発明のガラス繊維強化ポリアミド樹脂組成物
はナイロン66〔Ａ〕、高級脂肪族ポリアミド〔Ｂ〕
及び高級脂肪族ポリアミド〔Ｃ〕によりなる混合
ポリアミド樹脂にガラス繊維を配合したものであ
るが、高級脂肪族ポリアミド〔Ｂ〕と高級脂肪族
ポリアミド〔Ｃ〕の種別は、ポリマー主鎖中のメ
チレン基数とアミド基数の比（CH₂／NHCO）
で行うことができる。本発明で用いるナイロン66Aは特に制限はな
く、その結晶性を大きく損なわない範囲で他のポ
リアミド形成モノマーとの共重合体であつてもよ
い。本発明で用いる高級脂肪族ポリアミド〔Ｂ〕は
ポリマー主鎖中のメチレン基数とアミド基数の比
（CH₂／NHCO）が６〜11であるポリアミドであ
り、かかるポリアミドとしては、ナイロン11、ナ
イロン12、ナイロン69、ナイロン610、ナイロン
612、ナイロン613等があげられ、その結晶性を損
なわない範囲で他のポリアミド形成モノマーとの
共重合体であつてよい。ナイロン610、ナイロン
612が好ましい。更にナイロン612が最も好まし
い。本発明に用いる高級脂肪族ポリアミド〔Ｃ〕は
ポリマー主鎖中のメチレン基数とアミド基数の比
（CH₂／NHCO）がナイロン66〔Ａ〕と高級脂肪
族ポリアミド〔Ｂ〕のそれとの中間にあつて、高
級脂肪族ポリアミド〔Ｂ〕が特定されることで限
定されるもであり、〔Ｂ〕とＣとの特定例として
は〔Ｂ〕がナイロン６１０であれば〔Ｃ〕はナイ
ロン69であり、〔Ｂ〕がナイロン612であれば
〔Ｃ〕はナイロン69又はナイロン610等であり、
〔Ｂ〕がナイロン613であれば〔Ｃ〕はナイロン
69、ナイロン610、ナイロン612等であり、Ｂがナ
イロン11であれば〔Ｃ〕はナイロン69、ナイロン
610、ナイロン612、ナイロン613等であり、Ｂが
ナイロン12であれば、Ｃはナイロン69、ナイロン
610、ナイロン612、ナイロン613、ナイロン11等
である。これらの脂肪族ポリアミド〔Ｃ〕は、その結晶
性を損なわない範囲で他のポリアミド形成モノマ
ーとの共重合体であつてもよい。〔Ｂ〕において、ポリマー主鎖中のメチレン基
数とアミド基数の比が６未満の場合には金属ハロ
ゲン化物に対する抵抗性の改善が充分でなく、
又、〔Ｂ〕においてメチレン基数とアミド基数の
比が12以上の場合、〔Ｃ〕においてその比が〔Ａ〕
と〔Ｂ〕のそれとの間をはずれる場合は、いずれ
の場合も〔Ａ〕と〔Ｂ〕と〔Ｃ〕の相溶性が損な
われ、組成物の性質が損なわれる。本発明の構成
ポリマーは好ましくは、ナイロン66、ナイロン
610及びナイロン69、又はナイロン66、ナイロン
612およびナイロン610の３種類のポリアミドの組
み合せである。本発明の構成ポリマーであるナイロン66〔Ａ〕、
高級脂肪族ポリアミド〔Ｂ〕及び高級脂肪族ポリ
アミド〔Ｃ〕の配合割合は第１図に示される。第
１図の三角組成図において各頂点は〔Ａ〕、〔Ｂ〕、
〔Ｃ〕が各々100重量部であり、イ，ロ，ハ，ニ，
ホ、で囲まれた範囲が本発明のポリマー組成を表
している。第１図の三角組成図において、ナイロン66
〔Ａ〕、高級脂肪族ポリアミド〔Ｂ〕、及び高級脂
肪族ポリアミド〔Ｃ〕の混合物100重量部中に
〔Ａ〕を20〜80重量部（好ましくは30〜70重量部）
と限定した理由は、配合量が前記下限より少ない
と、ナイロン66〔Ａ〕の本来有する機械的性質を
低下させるからであり、また前記上限より多いと
金属ハロゲン化物（塩化カルシウム）による環境
応力亀裂に対する抵抗性が解決されないからであ
る。同様に〔Ｂ〕を10〜79重量部（好ましくは30
〜70重量部）と限定した理由は、配合量が前記下
限よりも少ない場合には、金属ハロゲン化物によ
る環境応力亀裂に対する抵抗性が解決されないか
らであり、また配合量が前記上限よりも多い場合
は、ナイロン66〔Ａ〕の本来有する機械的性質を
損なうからである。さらに〔Ｃ〕を１〜20重量部
（好ましくは５〜10重量部）と限定した理由は、
配合量が前記下限より少ない場合、〔Ｃ〕の配合
効果である〔Ａ〕と〔Ｂ〕との相溶性改善効果が
認められず、落錘衝撃強度向上への寄与が不充分
であり、また配合量が前記上限よりも多い場合、
〔Ｃ〕の配合による量的効果が認められないから
である。本発明に使用されるガラス繊維は、通常のガラ
ス繊維強化樹脂に使用されるものであり、ガラス
繊維の形状には特に制限はなく、配合する段階で
は長繊維タイプから短繊維タイプのものまで任意
の形状のものが使用可能である。ガラス繊維の配合割合は強化樹脂の用途によつ
て任意に選べるが、通常は最終的に得られるガラ
ス繊維強化ポリアミド樹脂組成物に対してガラス
繊維として、10〜60重量％、好ましくは25〜45重
量％の範囲である。ガラス繊維の配合量が10重量％より少ないとき
は機械的性質の充分な改善効果が得られない。ま
たガラス繊維の配合量が60重量％を超える場合に
は、組成物の溶融時の流動性が低下し、押出し成
形、射出成形が悪くなる。本発明の組成物は、ナイロン66〔Ａ〕、高級脂肪
族ポリアミド〔Ｂ〕、高級脂肪族脂ポリアミド
〔Ｃ〕、及びガラス繊維をドライブレンドした後、
常用の単軸または二軸押出機のような押出機で溶
融ブレンドすることによつて得られる。また別の
方法として、〔Ａ〕とガラス繊維を、〔Ｂ〕とガラ
ス繊維を、〔Ｃ〕とガラス繊維をそれぞれ溶融混
合し、通常の方法でペレツト化したものを射出成
形でブレンドすることでも得られる。以上本発明の自動車部品用成形材料について詳
述したが、本発明の目的を損なわない範囲におい
て、これら組成物にさらに他の樹脂ポリマー、無
機充填剤、着色剤、酸化劣化防止剤、熱安定剤、
紫外線吸収剤、帯電防止剤、滑剤、可塑剤、難燃
剤などを目的に応じて添加することができる。〔実施例〕以下、実施例により本発明をさらに詳しく説明
する。各実施例における機械的性質、耐不凍液性及び
金属ハロゲン化物による環境応力亀裂性の測定
は、以下のようにして行つた。〔1〕機械的性質の測定 (1) 引張強度：ASTM Ｄ−638に準じた。 (2) 落錘衝撃強度：デユポン式衝撃試験機（撃心φ1/2inch）を用い、飽和吸水状態
の試験片の破壊率50％の衝撃エネルギーを求
めた。〔2〕耐不凍液性の測定不凍液（日産純正ロングライフクーラント）
の50％水溶液を140℃に加熱し、その中に試験
片を浸漬した後の引張強度保持率（浸漬時間５
時間後の引張強度に対する）を求めた。〔3〕金属ハロゲン化物による環境応力亀裂の測
定。飽和吸水状態の矩形試験片を一定応力で曲げ
た状態に保ち、30重量％塩化カルシウム水溶液
を塗布し、100℃で２時間、熱風オーブン中に
放置した後取出し、試験片表面状態を観察し
た。（−）はクラツク発生なし（＋）→（＋＋＋）となるほどクラツク発生
激しい。〔4〕相対粘度（ηr） JIS−K6810に基づいて、硫酸溶液で測定し
た。実施例１ペレツト状のナイロン66（相対粘度ηr＝2.85）
60重量部とペレツト状のナイロン612（相対粘度ηr
＝2.10）30重量部とペレツト状のナイロン610（相
対粘度ηr＝2.50）10重量部と市販のガラス短繊維
（３mm長チヨツプドストランドタイプ）50重量部
とをタンプラー型混合機にてブレンドした後70mm
φ単軸押出機に供給し、押出温度280℃で押出し
造粒し、ポリアミド組成物を得た。得られたガラ
ス繊維強化ポリアミド組成物を射出成形機を用い
て、280℃の温度で物性測定用試験片に成形し、
諸物性を測定した。その結果を第１表に示す。比較例１実施例１と同じナイロン66及びナイロン612を
ナイロン66／ナイロン612の重量比で60／40の割
合に混合し、該混合ポリアミド樹脂100重量部に
対し、実施例１と同じガラス繊維を50重量部配合
したのち、実施例１と同様に諸物性を測定した。
その結果を第１表に示す。実施例２実施例１と同じナイロン66 30重量部と、実施
例１と同じナイロン610 65重量部とペレツト状の
ナイロン69（相対粘度ηr＝2.49）５重量部と実施
例１と同じガラス繊維50重量部とをブレンドした
後、実施例１と同様の方法で組成物を得た。実施
例１と同様に諸物性を測定した。その結果を第１
表に示す。比較例２実施例１と同じナイロン66及びナイロン610を
ナイロン66／ナイロン610の重量比で30／70の割
合に混合し、該混合ポリアミド樹脂100重量部に
対し、実施例１と同じガラス繊維を50重量部配合
したのち、実施例１と同様に諸物性を測定した。
その結果を第１表に示す。比較例３ナイロン69 ５重量部の代わりにナイロン６（相
対粘度ηr＝2.30）５重量部を用いた以外は実施例
２と同様配合割合として組成物を得たのち、実施
例１と同様に諸物性を測定した。その結果を第１
表に示す。比較例４実施例１と同じナイロン66、ナイロン612、及
びナイロン610をナイロン66／ナイロン612／ナイ
ロン610の重量比で60／10／30の割合に混合し、
該混合ポリアミド樹脂100重量部に対し、実施例
１と同じガラス繊維を50重量部配合したのち、実
施例１と同様に諸物性を測定した。その結果を第
１表に示す。 [Industrial Application Field] The present invention is a road antifreeze agent (calcium chloride).
The present invention provides a glass fiber-reinforced polyamide resin composition useful as a molding material for automobile parts, which has both excellent mechanical properties and heat resistance. [Prior art] Glass fiber reinforced nylon 66 is used in the automotive parts field due to its toughness, heat resistance, oil resistance, etc. However, one of the major drawbacks of nylon 66 is that it is susceptible to metal halides. As a result, environmental stress cracks may occur. For example, nylon 66, which has excellent strength, heat resistance, and oil resistance, is often used in automobile parts such as radiator tanks, canisters, and cylinder head covers. Strict countermeasures are required because cracks occur in the molded product and cause deterioration of the molded product. Research has been conducted to improve the resistance of nylon 66 to metal halides, and it is known that blending higher aliphatic polyamides with nylon 66 is effective (Japanese Patent Laid-Open No. 57 -80448, JP-A-57-80449). However, simply blending higher aliphatic polyamide with nylon 66 impairs the compatibility between nylon 66 and higher aliphatic polyamide, resulting in poor mechanical properties.
In particular, the falling weight impact strength was insufficient, and the material was not satisfactory as an automobile parts material that required strict reliability. [Problems to be Solved by the Invention] As a result of intensive studies to further improve this problem, the present inventors found that when blending higher aliphatic polyamide [B] with nylon 66 [A], higher aliphatic polyamide [B] The present invention was completed by discovering that by blending polyamide [C], the compatibility between nylon 66 [A] and higher aliphatic polyamide [B] can be improved. That is, the present invention provides a glass fiber-reinforced material useful as a molding material for automobile parts, which has resistance to road deicing agents (calcium chloride), has excellent mechanical properties and heat resistance, and has improved falling weight strength. This was made to provide a polyamide resin composition. [Means and effects for solving the problems] The present invention uses nylon 66 [A], a higher aliphatic polyamide in which the ratio of the number of methylene groups to amide groups in the main chain of the polymer (CH ₂ /NHCO) is from 6 to 11. B] and a polyamide consisting of a higher aliphatic polyamide [C] in which the ratio of the number of methylene groups to the number of amide groups in the polymer main chain (CH ₂ /NHCO) is between that of nylon 66 [A] and the higher aliphatic polyamide [B]. A resin composition in which the amount of [A] is 20 to 80 parts by weight, the amount of [B] is 10 to 79 parts by weight, and the amount of [C] is 1 to 20 parts by weight in 100 parts by weight of the polyamide resin composition. The present invention relates to a molding material for automobile parts that is resistant to road antifreeze agents and is composed of 40 to 90% by weight of a polyamide resin composition and 60 to 10% by weight of glass fibers. As mentioned above, the characteristics of the composition of the present invention are as follows.
It has a three-component composition of [A], higher aliphatic polyamide [B], and higher aliphatic polyamide [C]. In the present invention, [A] and [B] are both the same polyamide, for example, nylon 66 and nylon 612,
The two were compatible, and a blend of the two did not seem to have any problems in terms of physical properties. However, when we proceeded with practical evaluation, in terms of falling weight impact resistance,
It was found that there was a problem with drop weight impact resistance, especially at low temperatures. The present inventors diligently studied this improvement measure and surprisingly found that the combination of [A], [B], and [C], that is, the ratio of the number of methylene groups to the number of amide groups in the polymer main chain (CH ₂ /NHCO ) have been found to be effective in combination with different polyamides. The glass fiber reinforced polyamide resin composition of the present invention is made of nylon 66 [A] and higher aliphatic polyamide [B].
and higher aliphatic polyamide [C], in which glass fibers are blended, and the types of higher aliphatic polyamide [B] and higher aliphatic polyamide [C] are determined by the number of methylene groups in the polymer main chain. and the ratio of the number of amide groups (CH ₂ /NHCO)
It can be done with Nylon 66A used in the present invention is not particularly limited, and may be a copolymer with other polyamide-forming monomers as long as its crystallinity is not significantly impaired. The higher aliphatic polyamide [B] used in the present invention is a polyamide in which the ratio of the number of methylene groups to the number of amide groups in the polymer main chain (CH ₂ /NHCO) is 6 to 11. Such polyamides include nylon 11, nylon 12 , nylon 69, nylon 610, nylon
612, nylon 613, etc., and may be a copolymer with other polyamide-forming monomers as long as the crystallinity is not impaired. Nylon 610, nylon
612 is preferred. Furthermore, nylon 612 is most preferred. The higher aliphatic polyamide [C] used in the present invention has a ratio of the number of methylene groups to the number of amide groups (CH ₂ /NHCO) in the polymer main chain between that of nylon 66 [A] and that of the higher aliphatic polyamide [B]. Therefore, it is limited by specifying the higher aliphatic polyamide [B], and as an example of specifying [B] and C, if [B] is nylon 610, [C] is nylon 69. , if [B] is nylon 612, [C] is nylon 69 or nylon 610, etc.
If [B] is nylon 613, [C] is nylon
69, nylon 610, nylon 612, etc., and if B is nylon 11, [C] is nylon 69, nylon
610, nylon 612, nylon 613, etc., and if B is nylon 12, C is nylon 69, nylon
610, nylon 612, nylon 613, nylon 11, etc. These aliphatic polyamides [C] may be copolymers with other polyamide-forming monomers as long as their crystallinity is not impaired. In [B], when the ratio of the number of methylene groups to the number of amide groups in the polymer main chain is less than 6, the resistance to metal halides is not sufficiently improved;
In addition, if the ratio of the number of methylene groups to the number of amide groups in [B] is 12 or more, the ratio in [C] is [A]
If there is a difference between [A], [B], and [C], the compatibility of [A], [B], and [C] will be impaired, and the properties of the composition will be impaired. The constituent polymers of the present invention are preferably nylon 66, nylon
610 and nylon 69, or nylon 66, nylon
It is a combination of three types of polyamides: 612 and nylon 610. Nylon 66 [A], which is a constituent polymer of the present invention,
The blending ratios of higher aliphatic polyamide [B] and higher aliphatic polyamide [C] are shown in FIG. In the triangular composition diagram in Figure 1, each vertex is [A], [B],
[C] is 100 parts by weight each, A, B, C, D,
The range surrounded by (e) and (e) represents the polymer composition of the present invention. In the triangular composition diagram in Figure 1, nylon 66
20 to 80 parts by weight (preferably 30 to 70 parts by weight) of [A] in 100 parts by weight of a mixture of [A], higher aliphatic polyamide [B], and higher aliphatic polyamide [C].
The reason for this limitation is that if the amount is less than the above lower limit, the inherent mechanical properties of nylon 66 [A] will deteriorate, and if it is more than the above upper limit, environmental stress cracking due to metal halide (calcium chloride) will occur. This is because the resistance to Similarly, add [B] to 10 to 79 parts by weight (preferably 30 parts by weight).
~70 parts by weight) is because if the blending amount is less than the above lower limit, the resistance to environmental stress cracking due to metal halides will not be solved, and if the blending amount is higher than the above upper limit This is because nylon 66 [A] impairs its inherent mechanical properties. Furthermore, the reason for limiting [C] to 1 to 20 parts by weight (preferably 5 to 10 parts by weight) is as follows.
If the blending amount is less than the above lower limit, the effect of improving the compatibility between [A] and [B], which is the blending effect of [C], will not be recognized, and the contribution to improving the falling weight impact strength will be insufficient, and If the blending amount is more than the above upper limit,
This is because no quantitative effect was observed due to the addition of [C]. The glass fibers used in the present invention are those used in ordinary glass fiber-reinforced resins, and there are no particular restrictions on the shape of the glass fibers, and at the blending stage, they can be arbitrarily selected from long fiber types to short fiber types. Can be used in the shape of . The blending ratio of glass fiber can be arbitrarily selected depending on the use of the reinforced resin, but it is usually 10 to 60% by weight, preferably 25 to 45% by weight of glass fiber, based on the final glass fiber reinforced polyamide resin composition. % by weight. When the amount of glass fiber blended is less than 10% by weight, sufficient improvement in mechanical properties cannot be obtained. Furthermore, if the blending amount of glass fiber exceeds 60% by weight, the fluidity of the composition during melting decreases, making extrusion molding and injection molding difficult. The composition of the present invention is prepared by dry blending nylon 66 [A], higher aliphatic polyamide [B], higher aliphatic polyamide [C], and glass fiber.
It is obtained by melt blending in an extruder, such as a conventional single or twin screw extruder. Another method is to melt and mix [A] with glass fibers, [B] with glass fibers, and [C] with glass fibers, pelletize them using the usual method, and then blend them by injection molding. can get. Although the molding material for automobile parts of the present invention has been described in detail above, these compositions may further include other resin polymers, inorganic fillers, colorants, oxidative deterioration inhibitors, and heat stabilizers, to the extent that the object of the present invention is not impaired. ,
Ultraviolet absorbers, antistatic agents, lubricants, plasticizers, flame retardants, etc. can be added depending on the purpose. [Example] Hereinafter, the present invention will be explained in more detail with reference to Examples. Mechanical properties, antifreeze resistance, and environmental stress cracking resistance due to metal halides in each example were measured as follows. [1] Measurement of mechanical properties (1) Tensile strength: According to ASTM D-638. (2) Falling weight impact strength: Using a Dupont impact tester (center of impact φ1/2 inch), the impact energy at a 50% failure rate of a test piece in a saturated water absorption state was determined. [2] Antifreeze resistance measurement Antifreeze (Nissan genuine long life coolant)
Tensile strength retention after heating a 50% aqueous solution of
) was determined for the tensile strength after time. [3] Measurement of environmental stress cracking caused by metal halides. A rectangular test piece in a saturated water absorption state was kept bent under a constant stress, coated with a 30% by weight calcium chloride aqueous solution, left in a hot air oven at 100°C for 2 hours, then taken out and the surface condition of the test piece was observed. (-) means no cracks occur.The more the transition from (+) to (+++) is, the more cracks occur. [4] Relative viscosity (ηr) Measured using a sulfuric acid solution based on JIS-K6810. Example 1 Nylon 66 in pellet form (relative viscosity ηr=2.85)
60 parts by weight of nylon 612 in pellet form (relative viscosity ηr
= 2.10) 30 parts by weight, 10 parts by weight of pelleted nylon 610 (relative viscosity ηr = 2.50), and 50 parts by weight of commercially available short glass fibers (3 mm long chopped strand type) were blended in a tampler type mixer. 70mm after
The mixture was supplied to a φ single-screw extruder and extruded and granulated at an extrusion temperature of 280°C to obtain a polyamide composition. The obtained glass fiber reinforced polyamide composition was molded into a test piece for measuring physical properties at a temperature of 280°C using an injection molding machine.
Various physical properties were measured. The results are shown in Table 1. Comparative Example 1 The same nylon 66 and nylon 612 as in Example 1 were mixed at a weight ratio of nylon 66/nylon 612 of 60/40, and the same glass fiber as in Example 1 was added to 100 parts by weight of the mixed polyamide resin. After blending 50 parts by weight, various physical properties were measured in the same manner as in Example 1.
The results are shown in Table 1. Example 2 30 parts by weight of the same nylon 66 as in Example 1, 65 parts by weight of the same nylon 610 as in Example 1, 5 parts by weight of pellet-like nylon 69 (relative viscosity ηr=2.49), and 50 parts by weight of the same glass fiber as in Example 1. After blending parts by weight, a composition was obtained in the same manner as in Example 1. Various physical properties were measured in the same manner as in Example 1. The result is the first
Shown in the table. Comparative Example 2 The same nylon 66 and nylon 610 as in Example 1 were mixed at a weight ratio of nylon 66/nylon 610 of 30/70, and the same glass fiber as in Example 1 was added to 100 parts by weight of the mixed polyamide resin. After blending 50 parts by weight, various physical properties were measured in the same manner as in Example 1.
The results are shown in Table 1. Comparative Example 3 A composition was prepared in the same manner as in Example 2 except that 5 parts by weight of nylon 6 (relative viscosity ηr = 2.30) was used instead of 5 parts by weight of nylon 69, and then various procedures were carried out in the same manner as in Example 1. Physical properties were measured. The result is the first
Shown in the table. Comparative Example 4 The same nylon 66, nylon 612, and nylon 610 as in Example 1 were mixed at a weight ratio of nylon 66/nylon 612/nylon 610 of 60/10/30,
After adding 50 parts by weight of the same glass fiber as in Example 1 to 100 parts by weight of the mixed polyamide resin, various physical properties were measured in the same manner as in Example 1. The results are shown in Table 1.

〔Effect of the invention〕

本発明のガラス繊維強化ポリアミド樹脂組成物
は、道路凍結防止剤（塩化カルシウム）に対する
抵抗性に加えて、優れた機械的特性、特に落錘衝
撃強度に優れ、かつ自動車の不凍液に対する耐薬
品性に優れているため、厳しい信頼性を要求する
自動車部品の成形材料として用いることができ
る。 The glass fiber-reinforced polyamide resin composition of the present invention has excellent mechanical properties, particularly excellent falling weight impact strength, in addition to resistance to road antifreeze agents (calcium chloride), and chemical resistance to automotive antifreeze. Because of its excellent properties, it can be used as a molding material for automobile parts that require strict reliability.

[Brief explanation of the drawing]

第１図は、本発明のガラス繊維強化ポリアミド
樹脂組成物の構成成分であるナイロン66〔Ａ〕、高
級脂肪族ポリアミド〔Ｂ〕、及び高級脂肪族ポリ
アミド〔Ｃ〕のポリマー成分組成を示すグラフで
ある。 FIG. 1 is a graph showing the polymer component compositions of nylon 66 [A], higher aliphatic polyamide [B], and higher aliphatic polyamide [C], which are the constituent components of the glass fiber reinforced polyamide resin composition of the present invention. be.

Claims

[Scope of Claims] 1. Nylon 66 [A], higher aliphatic polyamide [B] having a ratio of methylene groups in the polymer main chain (CH ₂ /NHCO) of 6 to 11, and the number of methylene groups in the polymer main chain. Ratio of amide groups (CH ₂ /NHCO)
is nylon 66 [A] and higher aliphatic polyamide [B]
A polyamide resin composition consisting of a higher aliphatic polyamide [C] between The amount of 10 to 79 parts by weight [C] is 1
A molding material for automobile parts having resistance to a road antifreeze agent, comprising 40 to 90% by weight of a polyamide resin composition of ~20 parts by weight and 60 to 10% by weight of glass fibers. 2 Higher aliphatic polyamide [B] is nylon 610
, higher aliphatic polyamide [C] is nylon
69. The molding material for automobile parts according to claim 1, which is No. 69. 3 Higher aliphatic polyamide [B] is nylon 612
, higher aliphatic polyamide [C] is nylon
610, the molding material for automobile parts according to claim 1. 4 Higher aliphatic polyamide [B] is nylon 612
, higher aliphatic polyamide [C] is nylon
69. The molding material for automobile parts according to claim 1, which is No. 69. 5. The molding material according to claim 1, wherein the automobile part is a part to which a road antifreeze agent is attached. 6. The molding material according to claim 1, wherein the automobile part is a radiator tank. 7. The molding material according to claim 1, wherein the automobile part is a canister. 8. The molding material according to claim 1, wherein the automobile part is a cylinder head cover. 9. The molding material according to claim 1, wherein the automobile part is an oil pan.