JPH0465104B2

JPH0465104B2 -

Info

Publication number: JPH0465104B2
Application number: JP58042233A
Authority: JP
Inventors: Sadayuki Yakabe; Ikutoshi Nakajima
Original assignee: Asahi Chemical Industry Co Ltd
Current assignee: Asahi Chemical Industry Co Ltd
Priority date: 1983-03-16
Filing date: 1983-03-16
Publication date: 1992-10-19
Also published as: JPS59168058A

Description

[Detailed description of the invention]

本発明は強化ポリアミド成形品の製造方法に関
する。詳しくは、ポリアミド樹脂が本来有する優
れた性質のなかで、特に機械的性質及び熱的性質
に優れ、さらに反り変形が少なく寸法安定性の良
好な成形品を供する強化ポリアミド成形品の製造
方法に関する。従来ポリアミド樹脂は、その機械的性質、耐熱
性、電気特性、摺動特性を生かして、多くの分野
に使用されている。殊に最近は自動車の軽量化、
工程合理化等から、エンジン廻りの高い温度雰囲
気下の自動車部品に、金属に代って用いられるよ
うになった。かかる用途においては上記した機械
的性質及び熱的性質を極力向上させんがため、ガ
ラス繊維で強化した組成物が好ましい。しかしな
がら、該組成物ではよく知られているように、ガ
ラス繊維の配向に基づく問題、つまり成形収縮の
異方性の為、成形品に反り変形が発生する問題が
ある。この問題への対処として、ガラス繊維に併せて
鉱石粉末等の無機充填剤をポリアミドに配合する
ことが提案されている。この提案に従い、通常行
なわれている方法、つまりポリアミド粒状体、ガ
ラス繊維のチヨツプドストランド及び鉱物粉末等
の無機充填剤を混合して、溶融混練して強化組成
物を得た。しかしながらこのようにして得た強化
組成物はガラス繊維を用いたことの効果を充分発
揮することができない。つまり、このようにして
得られた強化組成物は確かに成形品の反り変形は
改善されるものの、引張破断強度、曲げ強度、耐
衝撃強度等の機械的強度が低く、かかる性質を強
く要求する分野には耐え得ない。本発明者等は上記欠点を改善すべく鋭意研究の
結果、ガラス繊維強化ポリアミドの有する機械的
強度を低下させることなく、反り変形の問題を改
善できる成形品の製造方法を見い出し、本発明に
至つたのである。すなわち、本発明者等はガラス
繊維と鉱石粉末等の無機充填剤で強化されたポリ
アミド成形品を得るのに、ガラス繊維、鉱石粉末
等の無機充填剤及びポリアミド粒状体を混合して
溶融混練する常法に代えて、予めガラス繊維配合
ポリアミド組成物粒状体と鉱石粉末配合ポリアミ
ド組成物粒状体とを用意し、これを所定の割合に
混合する方法が上記した問題を改善することを見
い出した。更に本発明者等はこの発明において、
鉱石粉末等の無機充填剤がマイカであるとき、本
発明の効果が著しく発現するとを見出したのであ
る。すなわち、本発明はガラス繊維を10〜60重量％
含有したガラス繊維配合ポリアミド組成物粒状体
とマイカを10〜60重量％含有したマイカ配合ポリ
アミド組成物粒状体とを混合してなる強化ポリア
ミド成形品の製造方法に関するものである。以下本発明を更に詳しく説明する。本発明に係るポリアミドは、ジアミンとジカル
ボン酸との縮合重合で得られるナイロン66、ナイ
ロン69、ナイロン610，ナイロン612、ラクタムの
開環重合で得られるナイロン６、ナイロン12、ω
−アミノカルボン酸の自己重縮合で得られるナイ
ロン７、ナイロン11及びこれらの共重合物、ブレ
ンド物等である。就中、ナイロン66、ナイロン
610、ナイロン612及びナイロン６が好ましいが、
ナイロン66が最も好ましい。本発明に用いるガラス繊維はポリアミドの補強
材として用いられるものであれば良く、ガラス繊
維の形状には特に制限はない。つまり長繊維タイ
プ（ガラスロービング）から短繊維タイプ（チヨ
ツプドストランド、ミルドフアイバー）のものま
で任意の形状のものである。なかでも、チヨツプ
ドストランドが最も好ましい。本発明で言うマイカとは通常雲母と称するもの
で、白雲母〔KAl₂（AlSi₃O₁₀）．（OH）₂〕、ソーダ
雲母、紅雲母、黒雲母〔Ｋ（MgFe）₃（AlSi₃O₁₀）
（OH）₂〕、金雲母〔KMg₃（AlSiO₃O₁₀）（OH）₂〕、
鉄雲母の各種を含むものである。マイカはその表
面を有機シランカツプリング剤で処理したものが
好ましい。本発明に用いるガラス繊維配合ホリアミド組成
物粒状体のガラス繊維含有量は10〜60重量％であ
る。ガラス繊維の配合量が60重量％を越えると、
溶融混合及び造粒が困難であり、又ガラス繊維の
配合の量効果が小さい。又10重量％未満ではガラ
ス繊維の配合の効果が充分でない。本発明に用いるマイカ配合ポリアミド組成物粒
状体のマイカ含有量は10〜60重量％である。マイ
カの配合量が60重量％を越えると、溶融混合及び
造粒が困難であり、又マイカ配合の量効果が小さ
い。又10重量％未満ではマイカの配合の効果が充
分でない。本発明のポリアミド組成物粒状体の製法につい
て述べる。ガラス繊維配合ポリアミド組成物粒状
体の製法を例示する。つまりポリアミドとガラス
繊維とをブレンダーで混合した後、常用の単軸押
出機で溶融混合して、ロープ状となし冷却して造
粒する方法である。又溶融混合にはポリアミドを
予め溶融し、ここにガラス繊維を加える方法もあ
る。マイカ配合のポリアミド組成物粒状体の製法を
例示する。ポリアミドとマイカとをブレンダーで
混合し、常用の単軸押出機で溶融混合して、ロー
プ状となし冷却して造粒する方法である。又溶融
混合にはポリアミドを予め溶融し、ここにマイカ
を加える方法もある。なおここで言う粒状体とは
射出成形及び押出成形に用いられる一般的な原料
形状を示すのであつて形状を限定するものではな
い。つまりこの粒状体は直径３mm長さ３mmの円柱
状の場合もあれば、平均粒径が300μの粉体の場
合もある。この様に別々の工程で得られたガラス繊維配合
ポリアミド組成物粒状体とマイカ配合ポリアミド
組成物粒状体とは所望の混合比に配合され、両者
が混合して成形してなる強化ポリアミド成形品が
得られる。混合法としては、通常の周知の方法が
採用される。例えば、コーンブレンダー、Ｖ型タ
ンブラーブレンダー、ヘンセルミキサー等であ
る。ガラス繊維配合ポリアミド組成物粒状体とマイ
カ配合ポリアミド組成物粒状体との混合比は、強
化ポリアミド成形品の目的に応じて決められる。
本発明の両者が混合してなる強化ポリアミド組成
物中のガラス繊維濃度を(A)重量％、マイカ濃度を
(B)重量％とした時、(A)と(B)との関係は次の２式で
あることが好ましい。 10重量％＜(A)＋(B)＜60重量％かつ１／20＜(A)／(A)＋(B)＜19／20 好ましく６／10＜(A)／(A)＋(B)＜９／10 本発明の成形品の製造方法は、ガラス繊維配合
ポリアミド組成物粒状体とマイカ配合ポリアミド
組成物粒状体の混合物を成形機に供給し成形する
ことにある。成形には射出成形、押出成形等の溶
融成形があるが、その製法は特に限定されない。本発明の製造法によつて得られた強化ポリアミ
ド成形品は従来法のポリアミド、ガラス繊維及び
マイカの三者を同時に溶融混合し、成形する方法
によつて得られたガラス繊維／マイカ／ポリアミ
ド組成物に比べ、機械的強度が著るしく向上す
る。本発明の製造方法で得られる成形品としては、
例えばラジエータータンク、シリンダーヘツドカ
バー、オイルパン、ウオターインレツト、タイミ
ングベルトカバー、ウオターポンプハウジング及
びインペラ等の自動車アンダーフード部品があ
る。なお本発明における成形品には所望に応じて
種々の添加物、例えば熱安定剤、紫外線吸収剤、
酸化劣化防止剤、可塑剤、滑剤、帯電防止剤、染
料、顔料等や他の樹脂ポリマーを本発明の目的を
損なわない範囲に於て加えることができる。以下、具体的な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及び
ソリ変形の測定は次の様にて行つた。〔1〕機械的性質測定に用いる試験片は成形後ただちに恒温室
に置かれたシリカゲル入りのデシケーター中に
24時間放置される。 (1) 引張試験 ASTM−D638に従い、クロスヘツド速度
50mm／mmで行つた。 (2) 曲げ試験 ASTM−D790に従い、クロスヘツド速度
５mm／mmで行つた。 (3) アイゾット衝撃試験 ASTM−D256に従い、試験片にＶノツチ
（0.25mmＲ）切り込みした試験片で行つた。〔2〕ソリ変形試験片として小平板（130×110×３mm）を用
いた。成形された小平板を平らな面に置き、ソ
リによつて生じる局部的なすき間を観察し、す
き間の程度を小さい順にＡ，Ｂ，及びＣで評価
した。実施例１ (1) ガラス繊維配合ポリアミド組成物粒状体の
調製。ナイロン66（レオナ 1300：旭化成工業KK
製）60Kgとガラス繊維（06MA416：旭フアイ
バーグラスKK製）40KgをＶ型ブレンダーでブ
レンド後、ガラス繊維で強化したポリアミド組
成物のペレツト（直径2.5mm長さ３mm）を得た。 (2) マイカ配合ポリアミド組成物粒状体の調
製。ナイロン66（レオナ 1300：旭化成工業KK
製）60Kgとマイカ（スゾライトマイカ200K1：
クラレ製）40KgをＶ型ブレンダーでブレンド後
70mmφの単軸押出機を用いて、290℃で溶融混
合し、マイカで強化したポリアミド組成物のペ
レツト（直径2.5mm長さ３mm）を得た。上記、のペレツトをそれぞれ17.5Kg、2.5
Kg秤取し、コーンブレンダーを用いてブレンド
後、射出成形機を用いて290℃の温度で物性測定
用試験片に成形した。次いで該試験片につき、機
械的性質、ソリ変形を評価した。その結果を第１
表に示した。実施例２〜４実施例１で調製したガラス繊維配合ポリアミド
組成物のペレツト、及びマイカ配合ポリアミド
組成物のペレツトをそれぞれ下記に示す割合で
秤取したほかは実施例１と全く同じ様に行つた。
その評価の結果を第１表に示した。 The present invention relates to a method for producing reinforced polyamide molded articles. Specifically, the present invention relates to a method for producing a reinforced polyamide molded article that provides a molded article that has particularly excellent mechanical properties and thermal properties among the excellent properties inherently possessed by polyamide resins, and has little warping deformation and good dimensional stability. Conventionally, polyamide resins have been used in many fields due to their mechanical properties, heat resistance, electrical properties, and sliding properties. Especially recently, the weight reduction of automobiles,
Due to process rationalization, it has come to be used instead of metal in automobile parts that are exposed to high temperature environments around engines. In such applications, compositions reinforced with glass fibers are preferred in order to improve the above-mentioned mechanical properties and thermal properties as much as possible. However, as is well known, with this composition, there is a problem due to the orientation of the glass fibers, that is, due to the anisotropy of molding shrinkage, there is a problem that warping deformation occurs in the molded product. As a solution to this problem, it has been proposed to incorporate an inorganic filler such as ore powder into polyamide in addition to glass fiber. In accordance with this proposal, a reinforcing composition was obtained by mixing and melt-kneading inorganic fillers such as polyamide granules, chopped strands of glass fiber, and mineral powder using a conventional method. However, the reinforced composition thus obtained cannot fully exhibit the effects of using glass fibers. In other words, although the reinforced composition obtained in this way does indeed improve the warping deformation of molded products, it has low mechanical strengths such as tensile breaking strength, bending strength, and impact strength, and these properties are strongly required. I can't stand the field. As a result of intensive research to improve the above-mentioned drawbacks, the present inventors have discovered a method for manufacturing molded products that can improve the problem of warpage without reducing the mechanical strength of glass fiber reinforced polyamide, and have achieved the present invention. It's ivy. That is, in order to obtain a polyamide molded product reinforced with glass fiber and an inorganic filler such as ore powder, the present inventors mixed and melt-kneaded the glass fiber, an inorganic filler such as ore powder, and polyamide granules. Instead of the conventional method, we have found that the above-mentioned problem can be improved by a method in which glass fiber-containing polyamide composition granules and ore powder-containing polyamide composition granules are prepared in advance and mixed in a predetermined ratio. Furthermore, in this invention, the present inventors
It has been found that the effects of the present invention are significantly exhibited when the inorganic filler such as ore powder is mica. That is, in the present invention, the glass fiber content is 10 to 60% by weight.
The present invention relates to a method for producing a reinforced polyamide molded article by mixing a glass fiber-containing polyamide composition granule containing the present invention with a mica-containing polyamide composition granule containing 10 to 60% by weight of mica. The present invention will be explained in more detail below. The polyamide according to the present invention includes nylon 66, nylon 69, nylon 610, and nylon 612 obtained by condensation polymerization of diamine and dicarboxylic acid, nylon 6, nylon 12, and nylon 612 obtained by ring-opening polymerization of lactam.
- Nylon 7, nylon 11 obtained by self-polycondensation of aminocarboxylic acids, and copolymers and blends thereof. Especially nylon 66, nylon
610, nylon 612 and nylon 6 are preferred,
Nylon 66 is most preferred. The glass fiber used in the present invention may be one that can be used as a reinforcing material for polyamide, and there is no particular restriction on the shape of the glass fiber. In other words, it can be of any shape, from long fiber types (glass rovings) to short fiber types (chopped strands and milled fibers). Among these, chopped strands are most preferred. Mica referred to in the present invention is usually called mica, and is muscovite [KAl ₂ (AlSi ₃ O ₁₀ ). (OH) ₂ ], soda mica, rhodotite, biotite [K(MgFe) ₃ (AlSi ₃ O ₁₀ )
(OH) ₂ ], Phlogopite [KMg ₃ (AlSiO ₃ O ₁₀ ) (OH) ₂ ],
It includes various types of iron mica. It is preferable that the mica has its surface treated with an organic silane coupling agent. The glass fiber content of the glass fiber-containing holamide composition granules used in the present invention is 10 to 60% by weight. If the blended amount of glass fiber exceeds 60% by weight,
Melt mixing and granulation are difficult, and the effect of the amount of glass fiber blending is small. Further, if the amount is less than 10% by weight, the effect of adding glass fiber will not be sufficient. The mica content of the mica-containing polyamide composition granules used in the present invention is 10 to 60% by weight. If the amount of mica added exceeds 60% by weight, melt mixing and granulation will be difficult, and the effect of the amount of mica added will be small. Furthermore, if the amount is less than 10% by weight, the effect of mica blending is not sufficient. The method for producing the polyamide composition granules of the present invention will be described. A method for producing glass fiber-containing polyamide composition granules will be exemplified. In other words, polyamide and glass fiber are mixed in a blender, then melt-mixed in a conventional single-screw extruder to form a rope, cooled, and granulated. Alternatively, for melt mixing, there is also a method of melting the polyamide in advance and adding glass fiber thereto. A method for manufacturing a polyamide composition granule containing mica will be exemplified. In this method, polyamide and mica are mixed in a blender, melt-mixed in a conventional single-screw extruder, formed into a rope shape, cooled, and granulated. Another method of melt-mixing is to melt the polyamide in advance and add mica thereto. Note that the term "granules" as used herein refers to the general shape of raw materials used in injection molding and extrusion molding, and is not intended to limit the shape. In other words, this granular material may be cylindrical with a diameter of 3 mm and a length of 3 mm, or may be a powder with an average particle size of 300 μm. The glass fiber-containing polyamide composition granules and the mica-containing polyamide composition granules obtained in separate processes are blended at a desired mixing ratio, and a reinforced polyamide molded product is produced by mixing and molding the two. can get. As the mixing method, an ordinary well-known method is employed. Examples include a corn blender, a V-type tumbler blender, and a Hensel mixer. The mixing ratio of the glass fiber-containing polyamide composition granules and the mica-containing polyamide composition granules is determined depending on the purpose of the reinforced polyamide molded article.
The glass fiber concentration in the reinforced polyamide composition obtained by mixing both of the present invention is (A) weight %, and the mica concentration is
(B) When expressed as % by weight, the relationship between (A) and (B) is preferably the following two equations. 10% by weight<(A)+(B)<60% by weight and 1/20<(A)/(A)+(B)<19/20 Preferably 6/10<(A)/(A)+(B) )<9/10 The method for producing a molded article of the present invention consists in supplying a mixture of glass fiber-containing polyamide composition granules and mica-containing polyamide composition granules to a molding machine and molding the mixture. Molding includes melt molding such as injection molding and extrusion molding, but the manufacturing method is not particularly limited. The reinforced polyamide molded product obtained by the production method of the present invention has a glass fiber/mica/polyamide composition obtained by the conventional method of simultaneously melt-mixing polyamide, glass fiber, and mica and molding. Mechanical strength is significantly improved compared to that of conventional materials. The molded product obtained by the manufacturing method of the present invention includes:
Examples include automobile underhood parts such as radiator tanks, cylinder head covers, oil pans, water inlets, timing belt covers, water pump housings, and impellers. The molded product of the present invention may contain various additives, such as heat stabilizers, ultraviolet absorbers,
Oxidative deterioration inhibitors, plasticizers, lubricants, antistatic agents, dyes, pigments, etc., and other resin polymers can be added within a range that does not impair the purpose of the present invention. Hereinafter, the present invention will be explained in more detail with reference to specific examples. Mechanical properties and warp deformation in each example were measured as follows. [1] Mechanical properties The test pieces used for measurement were immediately placed in a desiccator containing silica gel placed in a constant temperature room after molding.
It is left for 24 hours. (1) Tensile test According to ASTM-D638, crosshead speed
I went with 50mm/mm. (2) Bending test The bending test was conducted according to ASTM-D790 at a crosshead speed of 5 mm/mm. (3) Izod impact test The Izod impact test was conducted using a test piece with a V-notch (0.25 mmR) cut in accordance with ASTM-D256. [2] Warp deformation A small flat plate (130 x 110 x 3 mm) was used as a test piece. The formed small flat plate was placed on a flat surface, local gaps caused by warping were observed, and the degree of the gap was evaluated as A, B, and C in descending order. Example 1 (1) Preparation of glass fiber-containing polyamide composition granules. Nylon 66 (Leona 1300: Asahi Kasei KK
After blending 60 kg of glass fiber (06MA416: manufactured by Asahi Fiberglass KK) in a V-type blender, pellets (2.5 mm in diameter and 3 mm in length) of a polyamide composition reinforced with glass fiber were obtained. (2) Preparation of mica-containing polyamide composition granules. Nylon 66 (Leona 1300: Asahi Kasei KK
) 60Kg and mica (Suzorite Mica 200K1:
After blending 40kg (manufactured by Kuraray) using a V-type blender.
The mixture was melt-mixed at 290° C. using a 70 mmφ single-screw extruder to obtain pellets (2.5 mm in diameter and 3 mm in length) of a mica-reinforced polyamide composition. The above pellets are 17.5Kg and 2.5Kg respectively.
Kg was weighed out, blended using a cone blender, and then molded into a test piece for measuring physical properties using an injection molding machine at a temperature of 290°C. Next, the mechanical properties and warp deformation of the test pieces were evaluated. The result is the first
Shown in the table. Examples 2 to 4 The same procedure as in Example 1 was carried out except that the pellets of the glass fiber-containing polyamide composition prepared in Example 1 and the pellets of the mica-containing polyamide composition were weighed in the proportions shown below. .
The results of the evaluation are shown in Table 1.

【表】比較例１実施例１で用いた、ガラス繊維（06MA416：
旭フアイバーグラスKK製）35Kg、マイカ（スゾ
ライトマイカ200K1：クラレ製）５Kg、及びナイ
ロン66（レオナ 1300：旭化成工業KK製）60Kg
をＶ型ブレンダーに同時に投入しブレンド後、70
mmφの単軸押出機を用いて、290℃で同時に溶融
混合し、ガラス繊維／マイカで強化した組成物の
ペレツト（直径2.5mm長さ３mm）を得た。次いで
このペレツトを射出成形機を用いて290℃の温度
で物性測定用試験片に製形し、機械的性質とソリ
変形を評価した。評価の結果を第１表に示した。比較例２〜４ガラス繊維、マイカ及びナイロン66の配合割合
（重量比）ガラス繊維／マイカ／ナイロン66をそ
れぞれ30／10／60、25／15／60、20／20／60とし
た以外は比較例１と全く同様のことを行つた。そ
の評価の結果を第１表に示した。参考例１実施例１で用いたガラス繊維20Kgとナイロン66
30KgをＶ型ブレンダーに投入しブレンドした後、
70mmφの単軸押出機を用いて、290℃で溶融混合
しガラス繊維で強化した組成物のペレツト（直径
2.5mm長さ３mm）を得た。その評価結果を第１表
に示した。[Table] Comparative Example 1 Glass fiber (06MA416:
Asahi Fiberglass KK) 35kg, mica (Suzorite Mica 200K1: Kuraray) 5kg, and nylon 66 (Leona 1300: Asahi Kasei KK) 60kg
were added to a V-type blender at the same time, and after blending, 70
The mixtures were simultaneously melt-mixed at 290° C. using a mmφ single-screw extruder to obtain pellets (2.5 mm in diameter and 3 mm in length) of a glass fiber/mica reinforced composition. Next, this pellet was molded into a test piece for measuring physical properties using an injection molding machine at a temperature of 290°C, and mechanical properties and warp deformation were evaluated. The results of the evaluation are shown in Table 1. Comparative Examples 2 to 4 Comparison except that the blending ratio (weight ratio) of glass fiber, mica, and nylon 66 was 30/10/60, 25/15/60, and 20/20/60 for glass fiber/mica/nylon 66, respectively. Exactly the same thing as in Example 1 was carried out. The results of the evaluation are shown in Table 1. Reference example 1 Glass fiber 20Kg and nylon 66 used in Example 1
After putting 30kg into a V-type blender and blending,
Using a 70mmφ single-screw extruder, pellets (diameter
2.5mm long and 3mm long) was obtained. The evaluation results are shown in Table 1.

【table】

Claims

[Claims] 1 (a) 10 to 60% by weight of glass fiber and polyamide 40
90% by weight of mica, and then melt-mixing and extruding the mixture to form glass fiber-containing polyamide composition granules; (b) 10-60% by weight of mica and 40-90% by weight of polyamide; and then melt-mixing and extruding the mixture to form mica-containing polyamide composition granules; (c) the granules produced in step (a) above and the granules produced in step (b) above; (d) molding the mixture produced in step (c) above, a method for producing a reinforced polyamide molded article.