JP4441855B2 - Polyamide resin composition - Google Patents
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本発明は複数のポリアミド系樹脂とポリプロピレン樹脂および／または変性ポリプロピレン樹脂、および無機強化材からなる無機強化ポリアミド樹脂組成物に関する。詳しくは、本発明の組成物は強度、合成、成形品外観（鏡面光沢、シボ面均一性）に優れ、かつ振動減衰性の良好な無機強化ポリアミド樹脂に関する。とくに自動車外装備品やドアミラー部品、ギアなど機構部を収めるケース部品などに適するものである。 The present invention relates to an inorganic reinforced polyamide resin composition comprising a plurality of polyamide resins, a polypropylene resin and / or a modified polypropylene resin, and an inorganic reinforcing material. Specifically, the composition of the present invention relates to an inorganic reinforced polyamide resin having excellent strength, synthesis, appearance of a molded product (mirror gloss, textured surface uniformity) and good vibration damping properties. It is particularly suitable for equipment outside the automobile, door mirror parts, case parts that contain mechanical parts such as gears.
一般的にポリアミド樹脂は、機械的特性、耐熱性、耐衝撃性、耐薬品性に優れ、自動車部品、電機部品、電子部品、家庭雑貨等に広く使用されている。なかでもガラス繊維を代表とする無機強化材を添加したポリアミド樹脂は、剛性、強度、耐熱性が大幅に向上し、特に、剛性に関しては添加剤の量に比例して向上することが知られている。
しかしながらポリアミド樹脂に剛性、強度向上を目的にガラス繊維等の強化材を５０〜７０質量％と大量に添加すれば、成形品外観（鏡面表面光沢、シボ面均一性等）が極度に低下し、商品価値が著しく損なわれる。そこで成形品外観を向上させる方法として、結晶性ポリアミドに非結晶樹脂を添加することが提案されている。
However, if a reinforcing material such as glass fiber is added in a large amount of 50 to 70% by mass for the purpose of improving rigidity and strength to the polyamide resin, the appearance of the molded product (mirror surface gloss, textured surface uniformity, etc.) is extremely reduced, The commercial value is significantly impaired. Therefore, as a method for improving the appearance of the molded product, it has been proposed to add an amorphous resin to the crystalline polyamide.
しかし、これらの方法では良好な鏡面の表面外観、あるいはシボが均一な表面光沢は得られない。また半芳香族ポリアミド樹脂（ナイロンＭＸＤ−６）にナイロン６６、ガラス繊維、マイカを高充填し、強度、剛性を上げる方法が知られているが、この場合、成形時に金型温度１３５℃もの高温に上げる必要があったり、高温に上げた場合でも良好な成形品外観が得られない場合もあった。
一方、一般的に無機強化材を高充填し剛性を上げると、外部振動に対して共振周波数はより高くなるが、共振点における減衰性を示す損失係数は共振周波数が高くなるにしたがって低下していく傾向がある。 On the other hand, generally, when the inorganic reinforcing material is highly filled and the rigidity is increased, the resonance frequency becomes higher with respect to external vibration, but the loss coefficient indicating the attenuation at the resonance point decreases as the resonance frequency increases. There is a tendency to go.
そこで、本発明はポリアミド樹脂に強度、剛性向上を目的にガラス繊維等の強化材を５０質量％以上と大量に添加した強度と剛性が高い成形品においても、成形品の外観が低下せずに、かつ高い共振周波数を発現すると同時に共振の減衰性を示す損失係数の大きい成形品の提供を課題とするものである。 Therefore, the present invention does not deteriorate the appearance of the molded product even in a molded product having a high strength and rigidity in which a reinforcing material such as glass fiber is added in a large amount of 50% by mass or more for the purpose of improving the strength and rigidity of the polyamide resin. An object of the present invention is to provide a molded article having a large loss factor that exhibits a high resonance frequency and at the same time exhibits a damping property of resonance.
本発明者等は、上記課題を解決する為に鋭意研究した結果、複数のポリアミド系樹脂とポリプロピレンおよび／または変性ポリプロピレン樹脂、および無機強化材を特定の比率で配合し、溶融混合後の無機強化ポリミド樹脂が、ある一定以上のメルトインデックス値を満足した時に、上記目的を達成し得ることを見出し、本発明を完成するに至った。 As a result of diligent research to solve the above problems, the present inventors blended a plurality of polyamide-based resins, polypropylene and / or modified polypropylene resin, and an inorganic reinforcing material at a specific ratio, and inorganic reinforcement after melt mixing. The inventors have found that the above object can be achieved when the polyimide resin satisfies a certain melt index value above a certain level, and has completed the present invention.
すなわち本発明は、（１）（Ａ）成分としてポリカプラミド樹脂である結晶性ポリアミド樹脂および／またはヘキサメチレンジアミンとアジピン酸を構成単位とする結晶性ポリアミド樹脂、（Ｂ）成分として（Ａ）以外のポリアミド樹脂が非結晶性の半芳香族ポリアミド、（Ｃ）成分としてポリプロピレン樹脂および／またはポリアミドとの反応性基を有するマレイン酸変性ポリプロピレン樹脂の各成分が以下の配合比を満足し、
０．２０＜（Ｂ）／（（Ａ）＋（Ｃ））≦１
（Ｄ）成分の無機強化材としてガラス繊維（Ｄ−１）、板状晶の無機強化材（Ｄ−２）、針状ワラストナイトおよび／またはミルドファイバー（Ｄ−３）を含有し、各成分の配合比、配合量が下記式を満足するポリアミド樹脂組成物であって、曲げ弾性率が１２〜２５ＧＰａであり、かつ２７５℃で２１６０ｇ荷重で測定されたメルトフローインデックスが４．０〜５０．０ｇ／１０分であることを特徴とするポリアミド樹脂組成物。
３０質量％≦（Ａ）＋（Ｂ）＋（Ｃ）≦５５質量％
５質量％≦（Ｂ）≦２０質量％
２質量％≦（Ｃ）≦１５質量％
４５質量％≦（Ｄ）≦７０質量％
２０質量％≦（Ｄ−１）≦４５質量％
１０質量％≦（Ｄ−２）≦３０質量％
０質量％≦（Ｄ−３）≦２５質量％
更に好ましい態様は、（２）振動特性として共振周波数が２００Ｈｚ以上であり、かつ損失係数ηが０．２２以上である請求項１に記載のポリアミド樹脂組成物である。
That is, the present invention comprises (1) a crystalline polyamide resin which is a polycapramide resin as component (A) and / or a crystalline polyamide resin having hexamethylenediamine and adipic acid as constituent units, and component (B) other than (A) The polyamide resin is a non-crystalline semi-aromatic polyamide, each component of the maleic acid-modified polypropylene resin having a reactive group with the polypropylene resin and / or polyamide as the component (C) satisfies the following blending ratio,
0.20 <(B) / ((A) + (C)) ≦ 1
As the inorganic reinforcing material of component (D), glass fiber (D-1), plate-like inorganic reinforcing material (D-2), acicular wollastonite and / or milled fiber (D-3) are contained, and The composition ratio and blending amount of the components satisfy the following formula , the flexural modulus is 12 to 25 GPa, and the melt flow index measured at 275 ° C. with a load of 2160 g is 4.0 to 50 Polyamide resin composition characterized by being 0.0 g / 10 min.
30% by mass ≦ (A) + (B) + (C) ≦ 55% by mass
5% by mass ≦ (B) ≦ 20% by mass
2% by mass ≦ (C) ≦ 15% by mass
45% by mass ≦ (D) ≦ 70% by mass
20% by mass ≦ (D-1) ≦ 45% by mass
10% by mass ≦ (D-2) ≦ 30% by mass
0% by mass ≦ (D-3) ≦ 25% by mass
The polyamide resin composition according to claim 1, wherein (2) the resonance frequency is 200 Hz or more and the loss coefficient η is 0.22 or more as vibration characteristics .
本発明はポリアミド樹脂に強度、剛性向上を目的にガラス繊維等の強化材を５０質量％以上と大量に添加して強度、剛性を充分に満足させても、成形品外観が低下せずに、かつ高い共振周波数を発現すると同時に損失係数の大きい成形品の提供し、自動車外装備品やドアミラー部品、ギアなど機構部を収めるケース部品等の部品において幅広い分野で使用することが出来、産業界に寄与すること大である。 In the present invention, the appearance of the molded product does not deteriorate even if the strength and rigidity are sufficiently satisfied by adding a large amount of reinforcing material such as glass fiber to the polyamide resin in an amount of 50% by mass or more for the purpose of improving the strength and rigidity. In addition, it provides molded products with a high loss frequency and a high loss factor, and can be used in a wide range of fields such as external parts for automobiles, door mirror parts, and case parts that contain mechanical parts such as gears, contributing to the industry. It is great to do.
以下に本発明を具体的に説明する。
本発明における（Ａ）成分のうちポリカプラミド樹脂を主成分とする結晶性ポリアミド樹脂とは、通常ナイロン６とよばれるε―カプロラクタムから得られる重合体を主成分とする結晶性ポリアミド樹脂のことである。
ポリカプラミド樹脂を主成分とする結晶性ポリアミド樹脂は、成形材料として使用する場合９６質量％硫酸溶液測定による相対粘度が２．３以上であるものが使用されている。しかし、本発明に使用する場合超低粘度のものが好ましく、９６質量％硫酸溶液（ポリアミド樹脂濃度１ｇ／ｄｌ）測定による相対粘度は１．７〜２．２の範囲が好ましい。特に好ましくは１．９〜２．１の範囲である。１．７未満ではタフネス性が低下するため好ましくなく、２．２を超えると流動性が低下し、成形品外観が悪くなる傾向があるので好ましくない。
The present invention will be specifically described below.
Of the component (A) in the present invention, the crystalline polyamide resin mainly composed of polycapramide resin is a crystalline polyamide resin mainly composed of a polymer obtained from ε-caprolactam called nylon 6. .
As the crystalline polyamide resin mainly composed of polycapramide resin, one having a relative viscosity of 2.3 or more as measured by a 96% by mass sulfuric acid solution is used as a molding material. However, when used in the present invention, those having an extremely low viscosity are preferred, and the relative viscosity measured by 96% by mass sulfuric acid solution (polyamide resin concentration 1 g / dl) is preferably in the range of 1.7 to 2.2. Especially preferably, it is the range of 1.9-2.1. If it is less than 1.7, it is not preferable because the toughness is lowered, and if it exceeds 2.2, the fluidity is lowered and the appearance of the molded product tends to be unfavorable.
本発明における（Ａ）成分のうちヘキサメチレンジアミンとアジピン酸を主成分とする結晶性のポリアミド樹脂とは通常ナイロン６６と呼ばれるヘキサメチレンジアミンとアジピン酸から得られる重合体を主成分とする結晶性ポリアミド樹脂である。ナイロン６６を主成分とする結晶性ポリアミド樹脂を成形材料として使用する場合９６質量％硫酸溶液（ポリアミド樹脂濃度１ｇ／ｄｌ）測定による相対粘度は２．４以上であるものが使用されている。本発明に使用する場合超低粘度のものが好ましく、相対粘度は１．７〜２．３の範囲が好ましい。なお、１．７未満ではタフネス性が低下するため好ましくなく、２．３を超えると流動性が低下し、成形品外観が悪くなる傾向があるので好ましくない。 Of the component (A) in the present invention, the crystalline polyamide resin mainly composed of hexamethylene diamine and adipic acid is a crystallinity mainly composed of a polymer obtained from hexamethylene diamine and adipic acid, usually called nylon 66. Polyamide resin. When a crystalline polyamide resin mainly composed of nylon 66 is used as a molding material, a material having a relative viscosity of 2.4 or more as measured by a 96 mass% sulfuric acid solution (polyamide resin concentration 1 g / dl) is used. When used in the present invention, those having an extremely low viscosity are preferred, and the relative viscosity is preferably in the range of 1.7 to 2.3. In addition, when less than 1.7, since toughness falls, it is unpreferable, and when it exceeds 2.3, fluidity | liquidity falls and there exists a tendency for a molded article external appearance to worsen, and is not preferable.
しかし成形品の外観は、ナイロン６やナイロン６６の相対粘度を反映したポリアミド樹脂組成物の流動性に依存しているので、ポリアミド樹脂組成物のメルトフローインデックスが重要である。ナイロン６やナイロン６６の相対粘度が前記範囲より大きくても、分子切断剤（減粘剤ともいう）を使用してポリアミド樹脂組成物のメルトフローインデックスを大きくすることができる。
なお、結晶性ポリアミド樹脂とは、例えば、ポリアミド樹脂をＪＩＳ Ｋ７１２１に準じて昇温速度２０℃／分でＤＳＣ測定した場合に、明確な融点（融解ピーク温度Ｔｐｍ）を示すものである。
本発明における（Ａ）成分の添加量として、好ましくは３０質量％以上、５５質量％以下が好ましく、３０質量％未満では十分な機会的強度が得られない。なお、他の成分の必要な添加量から（Ａ）成分の添加量は５５質量％を超えることはない。
However, since the appearance of the molded product depends on the flowability of the polyamide resin composition reflecting the relative viscosity of nylon 6 or nylon 66, the melt flow index of the polyamide resin composition is important. Even if the relative viscosity of nylon 6 or nylon 66 is larger than the above range, the melt flow index of the polyamide resin composition can be increased by using a molecular cutting agent (also referred to as a viscosity reducing agent).
The crystalline polyamide resin indicates, for example, a clear melting point (melting peak temperature Tpm) when the polyamide resin is subjected to DSC measurement at a temperature rising rate of 20 ° C./min according to JIS K7121.
The addition amount of the component (A) in the present invention is preferably 30% by mass or more and 55% by mass or less, and if it is less than 30% by mass, sufficient opportunity strength cannot be obtained. In addition, the addition amount of (A) component does not exceed 55 mass% from the required addition amount of another component.
本発明における（Ｂ）成分の（Ａ）以外のポリアミド樹脂とは、アジピン酸、テレフタル酸、イソフタル酸、トリメチルヘキサメチレンジアミン、ヘキサメチレンジアミン、メタキシリレンジアミン、ε−カプロラクタム等により得られる重合体を主成分とするポリアミド樹脂である。具体例としてはヘキサメチレンジアミンとテレフタル酸の重合体、ヘキサメチレンジアミンとイソフタル酸の重合体、ヘキサメチレンジアミンとテレフタル酸およびイソフタル酸の重合体、ヘキサメチレンジアミンとアジピン酸およびテレフタル酸の重合体、ヘキサメチレンジアミンとテレフタル酸およびε−カプロラクタムの重合体、メタキシリレンジアミンとアジピン酸の重合体、トリメチルヘキサメチレンジアミンとテレフタル酸の重合体、トリメチルヘキサメチレンジアミンとテレフタル酸とε−カプロラクタムの重合体、トリメチルヘキサメチレンジアミンとテレフタル酸とイソフタル酸の重合体、テレフタル酸およびイソフタル酸とヘキサメチレンジアミンおよびε−カプロラクタム重合体、メタキシリレンジアミンとテレフタル酸およびイソフタル酸とε−カプロラクタムの共重合体等のポリアミド樹脂が挙げられる。 The polyamide resin other than (A) of the component (B) in the present invention is a polymer obtained from adipic acid, terephthalic acid, isophthalic acid, trimethylhexamethylenediamine, hexamethylenediamine, metaxylylenediamine, ε-caprolactam, etc. Is a polyamide resin containing as a main component. Specific examples include a polymer of hexamethylene diamine and terephthalic acid, a polymer of hexamethylene diamine and isophthalic acid, a polymer of hexamethylene diamine and terephthalic acid and isophthalic acid, a polymer of hexamethylene diamine and adipic acid and terephthalic acid, Hexamethylenediamine and terephthalic acid and ε-caprolactam polymer, metaxylylenediamine and adipic acid polymer, trimethylhexamethylenediamine and terephthalic acid polymer, trimethylhexamethylenediamine, terephthalic acid and ε-caprolactam polymer , Trimethylhexamethylenediamine and terephthalic acid and isophthalic acid polymer, terephthalic acid and isophthalic acid and hexamethylenediamine and ε-caprolactam polymer, metaxylylenediamine and terephthalic acid And polyamides resins such as a copolymer of isophthalic acid and ε- caprolactam.
本発明において（Ｂ）成分は主に樹脂組成物の結晶性を落として金型転写製を向上させ、成型品外観を良好にする目的で添加される。この目的において、（Ｂ）成分はジアミン成分又はカルボン酸成分のいずれか一方が芳香族である結晶性または非結晶性の半芳香族ポリアミド樹脂、特に非結晶性の半芳香族ポリアミド樹脂が好ましい。（Ｂ）成分の添加量は、５質量％以上、２０質量％以下が好ましく、５質量％未満では成形品の外観の改良効果は充分でなく、２０質量％を超えるとポリアミド樹脂組成物の結晶性が低下しすぎて成型時に離型不良等の不具合を生じる場合がある。なお、非結晶性のポリアミド樹脂とは、例えば、ポリアミド樹脂をＪＩＳ Ｋ７１２１に準じて昇温速度２０℃／分でＤＳＣ測定した場合に、明確な融点（融解ピーク温度Ｔｐｍ）を示さないものである。
これらのポリアミド樹脂の相対粘度は特に限定されるものではないが、９６質量％硫酸溶液（ポリアミド樹脂濃度１ｇ／ｄｌ）測定による相対粘度の好ましい範囲は１．８〜２．４である。
In the present invention, the component (B) is added mainly for the purpose of improving the mold transfer by reducing the crystallinity of the resin composition and improving the appearance of the molded product. For this purpose, the component (B) is preferably a crystalline or noncrystalline semiaromatic polyamide resin, particularly an amorphous semiaromatic polyamide resin, in which either the diamine component or the carboxylic acid component is aromatic. The amount of component (B) added is preferably 5% by mass or more and 20% by mass or less, and if it is less than 5% by mass, the effect of improving the appearance of the molded product is not sufficient. In some cases, the properties are too low to cause defects such as mold release defects during molding. The non-crystalline polyamide resin, for example, does not show a clear melting point (melting peak temperature Tpm) when the polyamide resin is subjected to DSC measurement at a heating rate of 20 ° C./min according to JIS K7121. .
The relative viscosity of these polyamide resins is not particularly limited, but a preferable range of the relative viscosity by measuring a 96% by mass sulfuric acid solution (polyamide resin concentration 1 g / dl) is 1.8 to 2.4.
本発明における（Ｃ）成分のポリプロピレン樹脂および／または変性ポリプロピレン樹脂としては、特に粘度、密度等に制限はされず広範囲のポリプロピレン樹脂を選択することが出来る。またこのポリプロピレン樹脂は（Ａ）、（Ｂ）成分のポリアミド樹脂と相溶性を向上させるためにポリアミドと反応性を有する官能基を付与した変性ポリプロピレン樹脂が好ましい。ポリアミドと反応性を有する官能基とは、具体的にはカルボン酸、酸無水物、エポキシ基、オキサゾリン基、アミノ基、イソシアネート基等が例示されるがこの中でも酸無水基がもっとも反応性が高く、特に好ましい。 The polypropylene resin and / or modified polypropylene resin of component (C) in the present invention is not particularly limited in viscosity, density, etc., and a wide range of polypropylene resins can be selected. The polypropylene resin is preferably a modified polypropylene resin to which a functional group having reactivity with the polyamide is added in order to improve compatibility with the polyamide resins of the components (A) and (B). Specific examples of functional groups having reactivity with polyamide include carboxylic acids, acid anhydrides, epoxy groups, oxazoline groups, amino groups, isocyanate groups, etc. Among them, acid anhydride groups have the highest reactivity. Is particularly preferred.
本発明において（Ｃ）成分は減衰特性を向上させる目的で添加される。添加量として、好ましくは２〜１５質量％であるが強化材の種類と量によって発現する弾性率に大きく影響するため任意の強化材に対して、最適な添加量で設計する必要がある。添加量が充分でなければ減衰性の改良効果は小さく、添加量が多すぎると強度、剛性を低下させ実用的でない。（Ｃ）成分にポリアミド樹脂と反応性を有する官能基が付与されていれば添加量に対して機械特性の低下が低減され良好な機械特性と減衰特性を同時に発現させることが出来るので好ましい。 In the present invention, the component (C) is added for the purpose of improving the attenuation characteristics. The addition amount is preferably 2 to 15% by mass, but since it greatly affects the elastic modulus expressed by the type and amount of the reinforcing material, it is necessary to design with an optimal addition amount for any reinforcing material. If the addition amount is not sufficient, the effect of improving the damping property is small, and if the addition amount is too large, the strength and rigidity are lowered, which is not practical. It is preferable that a functional group having reactivity with the polyamide resin is imparted to the component (C), since a decrease in mechanical properties is reduced with respect to the amount added, and good mechanical properties and damping properties can be exhibited at the same time.
（Ａ）成分と（Ｂ）成分、（Ｃ）成分の合計添加量は、３３〜５５質量％であり、好ましくは３５〜５０質量％である。また（Ａ）成分と（Ｂ）成分、（Ｃ）成分の配合割合は特に限定はないが、（Ａ）成分と（Ｂ）成分、（Ｃ）成分の合計添加量に対する（Ｂ）成分の添加量は５〜２０質量％で、（Ａ）成分と（Ｂ）成分、（Ｃ）成分の配合比は下記式を満足することが好ましい。
０．２０＜（Ｂ）／（（Ａ）＋（Ｃ））≦１
（Ａ）＋（Ｃ）に対する（Ｂ）成分の添加量が少ないと良好な成形品外観が得られず、反対に（Ｂ）成分の添加量が多いと成形品の結晶化が悪くなり離型不良が生じたり、熱間剛性が低下したりする。
The total addition amount of the component (A), the component (B), and the component (C) is 33 to 55% by mass, preferably 35 to 50% by mass. The blending ratio of the (A) component, the (B) component, and the (C) component is not particularly limited, but the addition of the (B) component with respect to the total addition amount of the (A) component, the (B) component, and the (C) component. The amount is 5 to 20% by mass, and the blending ratio of the component (A) to the component (B) and the component (C) preferably satisfies the following formula.
0.20 <(B) / ((A) + (C)) ≦ 1
If the addition amount of the component (B) relative to (A) + (C) is small, a good appearance of the molded product cannot be obtained. Conversely, if the addition amount of the component (B) is large, the crystallization of the molded product becomes worse and the mold release is performed. Defects occur or hot stiffness decreases.
本発明における（Ｄ）成分は無機強化材であり、具体例としては、ガラス繊維、針状ワラスト、ウィスカー、カーボン繊維、セラミック繊維などの繊維状無機強化材、シリカ、アルミナ、タルク、カオリン、石英、ガラス、マイカ、グラファイトなどの粉末状無機強化材が挙げられる。好ましい無機強化材としては、ガラス繊維（Ｄ−１）、マイカ、タルク、カオリンなどの板状晶無機強化材（Ｄ−３）、ミルドファイバーおよび／または針状ワラストナイトなどの針状の無機強化材（Ｄ−２）、等が挙げられる。これらの無機強化材は、単独で使用または２種類以上の併用使用することもできる。また、これらの無機強化材は、表面処理としてシラン処理されているものを使用してもよい。 The component (D) in the present invention is an inorganic reinforcing material, and specific examples thereof include fibrous inorganic reinforcing materials such as glass fiber, acicular wallast, whisker, carbon fiber, and ceramic fiber, silica, alumina, talc, kaolin, and quartz. , Powdered inorganic reinforcing materials such as glass, mica and graphite. Preferred inorganic reinforcing materials include glass fibers (D-1), plate-like inorganic reinforcing materials (D-3) such as mica, talc and kaolin, and needle-shaped inorganic materials such as milled fiber and / or acicular wollastonite. A reinforcing material (D-2), etc. are mentioned. These inorganic reinforcing materials can be used alone or in combination of two or more. Further, these inorganic reinforcing materials may be silane-treated as a surface treatment.
前記（Ｄ−１）ガラス繊維としては、平均粒径は４〜２０μｍ程度、カット長は３〜６ｍｍ程度であり、ごく一般的なものを採用することができる。成形品中のガラス繊維平均繊維長は加工工程（押し出し工程・成型工程）で短くなり１５０〜３００μｍ程度になる。表面処理としてアミノシラン処理されているものを使用してもよい。ガラス繊維の強化材量としては２０〜４５質量％であり、好ましくは２５〜４０質量％である、２０質量％未満であれば強度剛性が低く反対に４５質量％を超えると、良好な成形品外観が得られ難いので好ましくない。 As said (D-1) glass fiber, an average particle diameter is about 4-20 micrometers, cut length is about 3-6 mm, and a very general thing can be employ | adopted. The average fiber length of the glass fiber in the molded product is shortened in the processing step (extrusion step / molding step) and is about 150 to 300 μm. As the surface treatment, those treated with aminosilane may be used. The amount of glass fiber reinforcing material is 20 to 45% by mass, preferably 25 to 40% by mass. If it is less than 20% by mass, the strength rigidity is low, and conversely, if it exceeds 45% by mass, a good molded product is obtained. Since the appearance is difficult to obtain, it is not preferable.
前記（Ｄ−３）の板状晶無機強化材としては、タルク、マイカ、未焼成クレー等が挙げられる。添加量は８〜３０質量％、好ましくは１０〜２５質量％である。８質量％未満では強度、剛性が低く、反対に２５質量％を超えると良好な成形品外観が得られ難いので好ましくない。 Examples of the plate-like inorganic reinforcing material (D-3) include talc, mica, and unfired clay. The addition amount is 8 to 30% by mass, preferably 10 to 25% by mass. If the amount is less than 8% by mass, the strength and rigidity are low. On the other hand, if it exceeds 25% by mass, it is difficult to obtain a good appearance of the molded product.
前記（Ｄ−２）のミルドファイバーとは、（Ｄ−１）のガラス繊維長の長さを短くしたものであり、平均径は４〜２０μｍ程度、カット長は３５〜８０μｍ程度であり、加工工程（押し出し・成型工程）でほとんど短くならないため成形品中の繊維長は３０〜７０μｍ程度である。また針状ワラストナイトは、平均径が３〜４０μｍ程度で平均繊維長は２０〜８０μｍ程度のワラストナイトである。
これら（Ｄ−２）の添加量は、０〜２５質量％好ましくは５〜２０質量％である。（Ｄ−２）成分は強度、剛性を発現する目的としては（Ｄ−１）のガラス繊維より効果が少ないので目的の強度、剛性が（Ｄ−１）、（Ｄ−３）の強化材の組み合わせで得られて、かつ良好な成形品外観が得られる場合は添加する必要はない場合がある。添加する場合は目的の成形品形状、大きさに対して（Ｄ−１）と（Ｄ−３）の組み合わせで目的の強度、剛性を満足するが、良好な外観特性が得られない場合（Ｄ−１）、（Ｄ−３）に対して適当量置換していけば強度、剛性の低下を最小限に抑えながら外観特性を向上させる効果がある。添加量として２５質量％を超えると無機強化材総量に対する（Ｄ−２）成分の比率が高くなり、十分な強度、剛性が発現しない。
The milled fiber of (D-2) is obtained by shortening the length of the glass fiber length of (D-1), the average diameter is about 4 to 20 μm, the cut length is about 35 to 80 μm, The fiber length in the molded product is about 30 to 70 μm because it is hardly shortened in the process (extrusion / molding process). Acicular wollastonite is wollastonite having an average diameter of about 3 to 40 μm and an average fiber length of about 20 to 80 μm.
The addition amount of these (D-2) is 0-25 mass%, preferably 5-20 mass%. The component (D-2) is less effective than the glass fiber of (D-1) for the purpose of developing strength and rigidity, so that the target strength and rigidity of the reinforcing material of (D-1) and (D-3) When it is obtained in combination and a good molded article appearance is obtained, it may not be necessary to add. When added, the combination of (D-1) and (D-3) satisfies the target strength and rigidity with respect to the target molded product shape and size, but good appearance characteristics cannot be obtained (D -1) and (D-3) are effective in improving the appearance characteristics while minimizing the decrease in strength and rigidity by substituting an appropriate amount. When the added amount exceeds 25% by mass, the ratio of the component (D-2) to the total amount of the inorganic reinforcing material increases, and sufficient strength and rigidity are not exhibited.
本発明（Ｄ）成分の無機強化材の配合量は４５〜７０質量％であり、好ましくは５０〜６５質量％である。４５質量％未満の場合は強度、剛性が低くなり反対に７０質量％より上になれば良好な成形品外観が得られず、また強度に関しても低下する、本発明の（Ｄ）成分として、（Ｄ−１）が２０〜４０質量％、（Ｄ−２）が１０〜３０質量％、（Ｄ−３）が０〜２５質量％、の範囲内で添加することにより強度と剛性が高く、しかも成形品の表面外観（鏡面表面光沢、シボ面均一性）が良好な成形品を得ることができるので好適である。 The compounding quantity of the inorganic reinforcing material of this invention (D) component is 45-70 mass%, Preferably it is 50-65 mass%. In the case of less than 45% by mass, the strength and rigidity become low, and on the contrary, if it exceeds 70% by mass, a good molded article appearance cannot be obtained, and the strength also decreases as the component (D) of the present invention ( D-1) is added in the range of 20 to 40% by mass, (D-2) is 10 to 30% by mass, and (D-3) is added in the range of 0 to 25% by mass. It is preferable because a molded product having a good surface appearance (mirror surface gloss, textured surface uniformity) can be obtained.
さらに、本発明のポリアミド樹脂組成物は、ＩＳＯ−１７８に準じて測定した曲げ弾性率が１３〜２５ＧＰａであり、かつＪＩＳ Ｋ７２１０に準じて２７５℃で２１６０ｇ荷重で測定されたメルトフローインデックスが４．０〜５０．０ｇ／１０分であることが必要である。
ポリアミド樹脂組成物の曲げ弾性率の値が１３ＧＰａより小さい時は、良好な耐振動特性を発現するための十分に高い共振周波数を得ることができない。曲げ弾性率を高くするには限界があるので本発明のポリアミド樹脂組成物の場合は２５ＧＰａ以下である。
メルトフローインデックスは、ポリアミド樹脂組成物の水分率を予め０．０５質量％に調整してＪＩＳ Ｋ７２１０に準じて２７５℃で２１６０ｇ荷重で測定された値である。メルトフローインデックスが４．０ｇ／１０分未満の場合、良好な成形品外観が得られない。良好な成形品外観が得るためにはメルトフローインデックスが大きい方が好ましいが、機械的強度が不十分になる場合があるので５０．０ｇ／１０分以下が好ましい。
Furthermore, the polyamide resin composition of the present invention has a flexural modulus measured according to ISO-178 of 13 to 25 GPa and a melt flow index measured at 275 ° C. under a load of 2160 g according to JIS K7210. It must be 0-50.0 g / 10 min.
When the value of the flexural modulus of the polyamide resin composition is smaller than 13 GPa, it is not possible to obtain a sufficiently high resonance frequency for expressing good vibration resistance characteristics. In the case of the polyamide resin composition of the present invention, it is 25 GPa or less because there is a limit to increasing the flexural modulus.
The melt flow index is a value measured by adjusting the moisture content of the polyamide resin composition to 0.05% by mass in advance at 275 ° C. under a load of 2160 g according to JIS K7210. When the melt flow index is less than 4.0 g / 10 minutes, a good molded product appearance cannot be obtained. In order to obtain a good appearance of a molded product, a larger melt flow index is preferable, but 50.0 g / 10 min or less is preferable because mechanical strength may be insufficient.
メルトフローインデックスが４．０ｇ／１０分以上のポリアミド樹脂組成物は、前記のとおり例えば、超低粘度の結晶性ポリアミド樹脂（Ａ）を使用するか、コンパウンド加工時にポリアミド樹脂の分子切断剤を添加する等の特別で処方を採用する必要がある。
前記ポリアミド樹脂の分子切断剤（減粘剤ともいう）としては、カルボン酸基やアミノ基や水酸基を持った低分子化合物が挙げられるが、特に脂肪族ジカルボン酸、芳香族ジカルボン酸等が有効であり、具体的にはシュウ酸、マロン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸、フタル酸、テレフタル酸等が挙げられる。また、その添加量は本発明の（Ａ）＋（Ｂ）成分の合計１００質量部に対して０．１〜１０質量部で、本発明組成物のメルトフローインデックスが４．０ｇ／１０分以上になる。ただしコンパウンド加工条件により分子切断の効果は変化し、当然のことながら加工温度が高いほど、またコンパウンド時のポリマー滞留時間が長いほど効果は優れる。通常、コンパウンド加工温度は２４０℃〜３００℃の範囲内およびコンパウンド時のポリマー滞留時間は１５〜６０秒が一般的である。
As described above, the polyamide resin composition having a melt flow index of 4.0 g / 10 min or more uses, for example, an ultra-low viscosity crystalline polyamide resin (A) or adds a polyamide resin molecular cutting agent during compound processing. It is necessary to adopt a special prescription such as to do.
Examples of the molecular cutting agent (also referred to as a thinning agent) of the polyamide resin include low molecular compounds having a carboxylic acid group, an amino group, or a hydroxyl group. Particularly, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and the like are effective. Specific examples include oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid and the like. Moreover, the addition amount is 0.1-10 mass parts with respect to a total of 100 mass parts of (A) + (B) component of this invention, and the melt flow index of this invention composition is 4.0 g / 10min or more. become. However, the effect of molecular cutting varies depending on the compound processing conditions. Naturally, the higher the processing temperature and the longer the polymer residence time during compounding, the better the effect. Usually, the compound processing temperature is in the range of 240 ° C to 300 ° C, and the polymer residence time during compounding is generally 15 to 60 seconds.
また、本発明の無機強化ポリアミド樹脂組成物には、必要に応じて耐熱安定剤、酸化防止剤、紫外線吸収剤、光安定剤、可塑剤、滑剤、結晶核剤、離型剤、帯電防止剤、難燃剤、顔料、染料あるいは多種ポリマーなどの添加することができる。 In addition, the inorganic reinforced polyamide resin composition of the present invention includes a heat resistance stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a lubricant, a crystal nucleating agent, a release agent, and an antistatic agent as necessary. Further, flame retardants, pigments, dyes or various polymers can be added.
本発明の組成物を得る方法としては、上述した（Ａ）、（Ｂ）、（Ｃ）、（Ｄ）成分、とその他配合物は上記配合組成にて任意の配合順序で配合した後、溶融混合される。溶融混合方法は当業者に周知のいづれかの方法でも可能であり、単軸押し出し機、２軸押し出し機を使用することが好ましい。また、押し出し加工時破損しやすいガラス繊維、針状ワラスト等は、２軸押し出し機のサイド口より投入することが好ましいが特に限定されるものではい。 As a method for obtaining the composition of the present invention, the components (A), (B), (C) and (D) described above and other blends are blended in the blending composition in an arbitrary blending order and then melted. Mixed. The melt mixing method can be any method known to those skilled in the art, and it is preferable to use a single screw extruder or a twin screw extruder. Further, glass fiber, needle-shaped wallast and the like which are easily damaged during extrusion are preferably introduced from the side port of the biaxial extruder, but are not particularly limited.
以下に実施例により本発明を更に詳細に説明するが、本発明はこれらの実施例により何ら制限されるものではない。また実施例、比較例において示した各特性、物性値は、下記の試験方法で測定した。
（１）相対粘度（硫酸溶液法） ：ウベローデ粘度管を用い、２０℃において９６質量％硫酸溶液（ポリアミド樹脂濃度１ｇ／ｄｌ）で測定した。
（２）メルトフローインデックス ：ＪＩＳ Ｋ７２１０に準じて２７５℃、２１６０ｇｆ荷重で測定した。
EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. Moreover, each characteristic and physical-property value shown in the Example and the comparative example were measured with the following test method.
(1) Relative viscosity (sulfuric acid solution method): Measured with a 96 mass% sulfuric acid solution (polyamide resin concentration 1 g / dl) at 20 ° C. using an Ubbelohde viscosity tube.
(2) Melt flow index: measured at 275 ° C. and 2160 gf load according to JIS K7210.
（３）曲げ強度 ：ＩＳＯ−１７８に準じて測定した。
（４）曲げ弾性率 ：ＩＳＯ−１７８に準じて測定した。
（５）鏡面光沢度 ：鏡面仕上げの１００×１００×２ｍｍｔの金型を使用し、樹脂温度２８５℃、金型温度１００℃で成形品を作製した後、ＪＩＳ Ｚ−８７１４に準じて入射角６０度の光沢度を測定した。数値が高いほど、光沢度が良い。
判定は、光沢度９０以上：○、光沢度８９〜７５：△、光沢度７４以下：×で行った。
(3) Bending strength: Measured according to ISO-178.
(4) Flexural modulus: measured in accordance with ISO-178.
(5) Mirror gloss: A mirror-finished 100 × 100 × 2 mmt mold was used, and after forming a molded product at a resin temperature of 285 ° C. and a mold temperature of 100 ° C., an incident angle of 60 according to JIS Z-8714 The degree of gloss was measured. The higher the value, the better the gloss.
The determination was made with a glossiness of 90 or more: ◯, a glossiness of 89 to 75: Δ, and a glossiness of 74 or less: x.
（６）振動特性 ：振動減衰試験はＩＳＯ６７２１−１を参考にＩＳＯ引張りダンベル試験片を使用して、中央加振法で行なった。（図１参照） 試験片中央を加振機に固定し、２３℃、５０％ＲＨの雰囲気で加振機より振動を与え、加速度応答をＩＳＯ６７２１−１に準じてフーリエ変換を行なう事により周波数応答関数を算出し共振周波数と損失係数を求めた。損失係数ηは共振周波数ｆ0を中心として、その前後において振幅が、共振振幅の１／√２になる２点の振動周波数差Δｆとして、以下の式より算出した。
η＝Δｆ／ｆ0
共振周波数が２００Ｈｚ以上であり、かつ損失係数ηが０．２２以上である場合、振動特性が良好と評価した。
(6) Vibration characteristics: The vibration damping test was performed by the central vibration method using an ISO tensile dumbbell test piece with reference to ISO 6721-1. (See Fig. 1) Fix the center of the test piece to the shaker, apply vibration from the shaker in an atmosphere of 23 ° C and 50% RH, and perform the Fourier response according to ISO 6721-1 to perform frequency response. The function was calculated and the resonance frequency and loss factor were obtained. The loss coefficient η was calculated from the following equation as a vibration frequency difference Δf at two points where the amplitude is 1 / √2 of the resonance amplitude around the resonance frequency f 0 .
η = Δf / f 0
When the resonance frequency was 200 Hz or more and the loss factor η was 0.22 or more, the vibration characteristics were evaluated as good.
（実施例１〜３、比較例１〜４）
（Ａ）成分として相対粘度の異なる２種のナイロン６（東洋紡績株式会社製）と相対粘度２．１のナイロン６６（東洋紡績株式会社製）を用い、（Ｂ）成分としてはヘキサメチレンテレフタレート／ヘキサメチレンイソフタレート共重合樹脂（ナイロン６Ｔ／６Ｉ樹脂：東洋紡績株式会社製、Ｔ−７１４Ｅ）、ポリメタキシリレンアジパミド（ナイロンＭＸＤ６樹脂：東洋紡績株式会社製、Ｔ−６００）を用いた。また（Ｃ）成分であるポリプロピレンはマレイン酸変性ポリプロピレン（株式会社グランドポリマー製、ＭＭＰ００６）を使用した。（Ｄ）成分としては、ガラス繊維（日本板硝子株式会社製、ＲＥＳ０３Ｔ−ＴＰ５７Ｅ）、針状ワラストナイト（株式会社ＮＹＣＯ製、ＮＹＧＬＯＳ８）、板状晶無機強化材としてマイカ（株式会社レプコ製、Ｍ３２５Ｓ）、タルク（林化成株式会社、ＦＵ５１）、ポリアミド樹脂の分子切断剤としてセバシン酸（ナカライテスク株式会社製、試薬ＧＲ）を使用した。その他、黒顔料としてカーボンブラックマスター（住化カラー株式会社製、ＰＡＢ８Ｋ４７０）を１．０質量％、離型剤としてモンタン酸カルシウム（クラリアントジャパン株式会社製 リコモントＣａＶ１０２）を０．５質量％添加した。
(Examples 1-3, Comparative Examples 1-4)
(A) Two types of nylon 6 (manufactured by Toyobo Co., Ltd.) having different relative viscosities and nylon 66 (manufactured by Toyobo Co., Ltd.) having a relative viscosity of 2.1 are used as component (A), and hexamethylene terephthalate / Hexamethylene isophthalate copolymer resin (nylon 6T / 6I resin: manufactured by Toyobo Co., Ltd., T-714E) and polymetaxylylene adipamide (nylon MXD6 resin: manufactured by Toyobo Co., Ltd., T-600) were used. The polypropylene as component (C) was maleic acid-modified polypropylene (MMP006, manufactured by Grand Polymer Co., Ltd.). As the component (D), glass fiber (manufactured by Nippon Sheet Glass Co., Ltd., RES03T-TP57E), acicular wollastonite (manufactured by NYCO, NYGLOS8), mica (made by Repco, M325S) as a plate-like inorganic reinforcing material ), Talc (Hayashi Kasei Co., Ltd., FU51), and sebacic acid (manufactured by Nacalai Tesque, Inc., reagent GR) was used as a molecular cutting agent for polyamide resin. In addition, 1.0% by mass of carbon black master (manufactured by Sumika Color Co., Ltd., PAB8K470) was added as a black pigment, and 0.5% by mass of calcium montanate (re-common CaV102 manufactured by Clariant Japan Co., Ltd.) was added as a release agent.
予備乾燥した原料を表１に示した配合比（質量比）に従い計量して、二軸押出機（池貝鉄工株式会社製、ＰＣＭ３０）でシリンダー温度２８０℃、スクリュー回転数７０ｒｐｍにて溶融混練し、水浴にストランド状に押出して冷却後、樹脂組成物のペレットを得た。得られた樹脂組成物ペレットを熱風乾燥機にて水分率０．０５質量％以下になるまで乾燥後、射出成形機（東芝機械株式会社製、ＩＳ８０）でシリンダー温度２８５℃、金型温度１００℃にて各種試験用テストピースを成形して評価に供した。評価結果を表１に示した。 The pre-dried raw material was weighed according to the blending ratio (mass ratio) shown in Table 1, and melt-kneaded at a cylinder temperature of 280 ° C. and a screw rotation speed of 70 rpm with a twin-screw extruder (Ikekai Tekko Co., Ltd., PCM30). After extruding into a water bath in a strand shape and cooling, pellets of the resin composition were obtained. The obtained resin composition pellets are dried with a hot air drier until the water content becomes 0.05% by mass or less, and then the cylinder temperature is 285 ° C. and the mold temperature is 100 ° C. with an injection molding machine (Toshiba Machine Co., Ltd., IS80). Test pieces for various tests were molded and used for evaluation. The evaluation results are shown in Table 1.
比較例１は流動性が高く成形品外観も良好であるが、剛性が低く曲げ弾性率の値が１３ＧＰａより小さく共振周波数が低いため、良好な耐振動特性が得られない。比較例２は共振周波数は高いが損失係数は低い。また充分な流動性が得られていないため外観も悪い。比較例３は共振周波数と損失係数については良好な振動特性が得られており、かつ充分な流動特性をもつが（Ｂ）成分の欠如によって良好な成形品外観が得られていない。比較例４は流動性、外観においては良好で、かつ高い共振周波数を発現しているが損失係数が低く良好な耐振動特性が得られない。これらの比較例に対して実施例１〜３では良好な外観と高い共振周波数を発現すると同時に、損失係数も大きい。実施例１〜３は良好な外観と耐振動特性を両立し、優れたポリアミド樹脂組成物を提供している。 In Comparative Example 1, the fluidity is high and the appearance of the molded product is good, but since the rigidity is low and the value of the flexural modulus is smaller than 13 GPa and the resonance frequency is low, good vibration resistance characteristics cannot be obtained. Comparative Example 2 has a high resonance frequency but a low loss factor. In addition, the appearance is poor because sufficient fluidity is not obtained. Comparative Example 3 has good vibration characteristics with respect to the resonance frequency and loss factor, and has sufficient flow characteristics, but a good molded article appearance is not obtained due to the lack of component (B). Comparative Example 4 is good in fluidity and appearance, and exhibits a high resonance frequency, but has a low loss coefficient and cannot provide good vibration resistance. In contrast to these comparative examples, Examples 1 to 3 exhibit a good appearance and a high resonance frequency, and at the same time have a large loss factor. Examples 1 to 3 provide both an excellent appearance and vibration resistance and provide an excellent polyamide resin composition.
本発明はポリアミド樹脂に強度、剛性向上を目的にガラス繊維等の強化材を５０質量％以上と大量に添加されており強度、剛性が充分高く、かつ成形品外観が良好である。それと同時に高い共振周波数と良好な減衰特性を兼ね備えており、良外観、高剛性、高強度、良耐震特性である成形品の提供し、自動車外装備品やドアミラー部品、ギアなど機構部を収めるケース部品等の部品において幅広い分野で使用することが出来、産業界に寄与すること大である。 In the present invention, a reinforcing material such as glass fiber is added to the polyamide resin in a large amount of 50% by mass or more for the purpose of improving the strength and rigidity, and the strength and rigidity are sufficiently high and the appearance of the molded product is good. At the same time, it has a high resonance frequency and good damping characteristics, and provides molded products with good appearance, high rigidity, high strength, and good earthquake resistance, and case parts that contain mechanical parts such as external equipment, door mirror parts, and gears. It can be used in a wide range of fields such as parts, and contributes to the industry.
１． 試験片
２． 振動出力（センサー）
３． 加振装置
４． 加振方向
1. Test piece Vibration output (sensor)
3.
Claims (2)
０．２０＜（Ｂ）／（（Ａ）＋（Ｃ））≦１
（Ｄ）成分の無機強化材としてガラス繊維（Ｄ−１）、板状晶の無機強化材（Ｄ−２）、針状ワラストナイトおよび／またはミルドファイバー（Ｄ−３）を含有し、各成分の配合比、配合量が下記式を満足するポリアミド樹脂組成物であって、曲げ弾性率が１２〜２５ＧＰａであり、かつ２７５℃で２１６０ｇ荷重で測定されたメルトフローインデックスが４．０〜５０．０ｇ／１０分であることを特徴とするポリアミド樹脂組成物。
３０質量％≦（Ａ）＋（Ｂ）＋（Ｃ）≦５５質量％
５質量％≦（Ｂ）≦２０質量％
２質量％≦（Ｃ）≦１５質量％
４５質量％≦（Ｄ）≦７０質量％
２０質量％≦（Ｄ−１）≦４５質量％
１０質量％≦（Ｄ−２）≦３０質量％
０質量％≦（Ｄ−３）≦２５質量％ A crystalline polyamide resin which is a polycapramide resin and / or a crystalline polyamide resin having hexamethylenediamine and adipic acid as structural units as component (A), and a polyamide resin other than (A) as a component Each component of the aromatic polyamide, maleic acid-modified polypropylene resin having a reactive group with a polypropylene resin and / or polyamide as the component (C) satisfies the following blending ratio:
0.20 <(B) / ((A) + (C)) ≦ 1
As the inorganic reinforcing material of component (D), glass fiber (D-1), plate-like inorganic reinforcing material (D-2), acicular wollastonite and / or milled fiber (D-3) are contained, and The composition ratio and blending amount of the components satisfy the following formula , the flexural modulus is 12 to 25 GPa, and the melt flow index measured at 275 ° C. with a load of 2160 g is 4.0 to 50 Polyamide resin composition characterized by being 0.0 g / 10 min.
30% by mass ≦ (A) + (B) + (C) ≦ 55% by mass
5% by mass ≦ (B) ≦ 20% by mass
2% by mass ≦ (C) ≦ 15% by mass
45% by mass ≦ (D) ≦ 70% by mass
20% by mass ≦ (D-1) ≦ 45% by mass
10% by mass ≦ (D-2) ≦ 30% by mass
0% by mass ≦ (D-3) ≦ 25% by mass
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| US8618209B2 (en) | 2010-12-21 | 2013-12-31 | Cheil Industries Inc. | Polyamide resin composition and molded product using the same |
| FR3103194A1 (en) | 2019-11-20 | 2021-05-21 | Hutchinson | Thermoplastic polymeric composition, its preparation process and vibration damping device incorporating it. |
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| EP2060607B2 (en) * | 2007-11-16 | 2019-11-27 | Ems-Patent Ag | Filled polyamide moulding materials |
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| JP5761632B2 (en) | 2013-04-16 | 2015-08-12 | 東洋紡株式会社 | Glass fiber reinforced polyamide resin composition |
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| US8618209B2 (en) | 2010-12-21 | 2013-12-31 | Cheil Industries Inc. | Polyamide resin composition and molded product using the same |
| FR3103194A1 (en) | 2019-11-20 | 2021-05-21 | Hutchinson | Thermoplastic polymeric composition, its preparation process and vibration damping device incorporating it. |
| EP3831885A1 (en) | 2019-11-20 | 2021-06-09 | Hutchinson | Thermoplastic polymer composition, method for preparing same and vibration-absorbing device including same |
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