JP2000154316A - Polyamide resin composition - Google Patents
Polyamide resin compositionInfo
- Publication number
- JP2000154316A JP2000154316A JP11260540A JP26054099A JP2000154316A JP 2000154316 A JP2000154316 A JP 2000154316A JP 11260540 A JP11260540 A JP 11260540A JP 26054099 A JP26054099 A JP 26054099A JP 2000154316 A JP2000154316 A JP 2000154316A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- polyamide resin
- resin composition
- reinforcing material
- component
- 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.)
- Granted
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリカプラミド樹
脂、ポリカプラミド樹脂以外のポリアミド樹脂および無
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、剛性・強度に優れ、
かつ成形品外観（鏡面表面光沢、シボ面均一表面性）に
優れる無機強化ポリアミド樹脂組成物に関する。特に自
動車外装部品やドアミラー部品に適するものである。The present invention relates to an inorganic reinforced polyamide resin composition comprising a polycapramide resin, a polyamide resin other than the polycapramide resin, and an inorganic reinforcing material. Specifically, the composition of the present invention has excellent rigidity and strength,
The present invention also relates to an inorganic reinforced polyamide resin composition having excellent appearance of a molded article (mirror surface gloss, textured surface uniformity). In particular, it is suitable for automobile exterior parts and door mirror parts.
【０００２】[0002]
【従来の技術】一般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重
量％と大量に添加すれば、成形品外観（鏡面表面光沢、
シボ面均一表面性等）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、結晶性ポリアミド樹脂に非晶性樹脂を添加すること
が提案されている。（例えば、特開平２―１４０２６５
号公報、特開平３−９９５２号公報、特開平３−２６９
０５６号公報、特開平４−２０２３５８号公報）2. Description of the Related Art Generally, polyamide resins have mechanical properties,
It has excellent heat resistance, impact resistance, and chemical resistance, and is widely used in automobile parts, electric parts, electronic parts, household goods, and the like. Above all, polyamide resin to which inorganic reinforcement represented by glass fiber is added, rigidity, strength and heat resistance are greatly improved,
In particular, it is known that rigidity increases in proportion to the amount of addition. However, rigidity,
If a reinforcing material such as glass fiber is added in a large amount of 50 to 70% by weight for the purpose of improving the strength, the appearance of the molded product (mirror surface gloss,
The surface uniformity of the grain surface is extremely reduced, and the commercial value is significantly impaired. Therefore, as a method for improving the appearance of a molded article, it has been proposed to add an amorphous resin to a crystalline polyamide resin. (For example, Japanese Patent Application Laid-Open No. 2-140265)
JP, JP-A-3-9952, JP-A-3-269
056, JP-A-4-202358)
【０００３】しかし、これらの方法では良好な鏡面表面
光沢、シボ面均一表面光沢は得られない。また、半芳香
族ポリアミド樹脂（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
（例えば、特開平１−２６３１５１号公報）が知られて
いるが、この場合、成形時の金型温度を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。However, these methods do not provide good mirror surface gloss and uniform surface gloss. Also, a method is known in which a semi-aromatic polyamide resin (MXD-6) is highly filled with nylon 66, glass fiber, and mica to increase strength and rigidity (for example, JP-A-1-263151). In such a case, it was necessary to increase the mold temperature during molding to as high as 135 ° C., or even when the temperature was increased, a good appearance of a molded product could not be obtained.
【０００４】[0004]
【発明が解決しようとする課題】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重量％以上と大量に添加しても、成形品外観
が低下せずに強度・剛性を同時に満足させ、かつ成形時
の金型温度が１００℃以下で良好な成形品の提供を可能
にならしめることを課題とするものである。Accordingly, the present invention does not deteriorate the appearance of a molded product even when a reinforcing material such as glass fiber is added in a large amount of 50% by weight or more for the purpose of improving strength and rigidity to a polyamide resin. Another object of the present invention is to make it possible to simultaneously provide strength and rigidity and to provide a good molded product at a mold temperature of 100 ° C. or less during molding.
【０００５】[0005]
【課題を解決するための手段】本発明者等は、上記の課
題を解決するために鋭意研究した結果、ポリカプラミド
樹脂、ポリカプラミド樹脂以外のポリアミド樹脂および
無機強化材を特定の比率で配合し、溶融混合後の無機強
化ポリアミド樹脂が、ある一定値以上のメルトインデッ
クス値を満足し、かつ熱的性質がある基準値を満足した
時に、上記目的を達成し得ることを見出し、本発明を完
成するに到った。Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a polycapramide resin, a polyamide resin other than the polycapramide resin, and an inorganic reinforcing material are blended at a specific ratio and melted. When the inorganic reinforced polyamide resin after mixing satisfies a melt index value of a certain value or more, and when a thermal property satisfies a certain reference value, it has been found that the above object can be achieved, and to complete the present invention. It has arrived.
【０００６】即ち本発明は、（Ａ）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、（Ｂ）（Ａ）
以外のポリアミド樹脂および（Ｃ）無機強化材を含有す
る組成物であって、組成物の水分率０．０５％以下での
メルトフローインデックス（ＭＦＩ）が４．０ｇ／１０
分以上であり、かつ示差走査熱量計（ＤＳＣ）で測定し
降温結晶化温度（ＴＣ２）が、（ＴＣ２）≦１８５℃で
あることを特徴とするポリアミド樹脂組成物、（Ｃ）
無機強化材が、（Ｃ−１）ガラス繊維、（Ｃ−２）ミル
ドファイバーおよび／または針状ワラストナイト、およ
び（Ｃ−３）板状晶を含有している前記記載のポリア
ミド樹脂組成物、（Ｂ）（Ａ）以外のポリアミド樹脂
が半芳香族非晶性ポリアミド樹脂である前記記載のポ
リアミド樹脂組成物、（Ａ）成分と（Ｂ）成分との配
合比が０．２５＜（Ｂ）／（Ａ）≦１を満足する前記
記載のポリアミド樹脂組成物、各成分の配合比、配合
量が下記式を満足する前記記載のポリアミド樹脂組成
物である。 ３０重量％≦（Ａ）＋（Ｂ）≦５５重量％ ８重量％≦（Ｂ）≦１８重量％ ２０重量％≦（Ｃ−１）≦４０重量％ ８重量％≦（Ｃ−２）≦２５重量％ ８重量％≦（Ｃ−３）≦２５重量％ ４５重量％≦（Ｃ−１）＋（Ｃ−２）＋（Ｃ−３）≦７
０重量％である。That is, the present invention relates to (A) a crystalline polyamide resin containing a polycapramide resin as a main component, (B) (A)
A polyamide resin other than the above and a (C) inorganic reinforcing material, wherein the composition has a water content of 0.05% or less and a melt flow index (MFI) of 4.0 g / 10.
(C2) or more, and (C2) a temperature-reducing crystallization temperature (TC2) measured by a differential scanning calorimeter (DSC), wherein (TC2) ≦ 185 ° C.
The polyamide resin composition as described above, wherein the inorganic reinforcing material contains (C-1) glass fiber, (C-2) milled fiber and / or acicular wollastonite, and (C-3) platelet. , (B) The polyamide resin composition as described above, wherein the polyamide resin other than (A) is a semi-aromatic amorphous polyamide resin, wherein the compounding ratio of component (A) to component (B) is 0.25 <(B ) / (A) ≦ the above-mentioned polyamide resin composition satisfying ≦ 1, and the above-mentioned polyamide resin composition wherein the compounding ratio and the amount of each component satisfy the following formula. 30% by weight ≦ (A) + (B) ≦ 55% by weight 8% by weight ≦ (B) ≦ 18% by weight 20% by weight ≦ (C-1) ≦ 40% by weight 8% by weight ≦ (C-2) ≦ 25 % By weight 8% by weight ≦ (C-3) ≦ 25% by weight 45% by weight ≦ (C-1) + (C-2) + (C-3) ≦ 7
0% by weight.
【０００７】[0007]
【発明の実施の形態】以下、本発明を具体的に説明す
る。本発明における（Ａ）成分は、通常ナイロン６と呼
ばれるε―カプロラクタムの重縮合によって得られるポ
リカプラミド樹脂であり、通常よく用いられている成形
材料の９６％−Ｈ2ＳＯ4測定による相対粘度は２．３以
上であるが、本発明に使用する場合の相対粘度は、１．
７〜２．２の範囲が好ましい。特に好ましいのは１．９
〜２．１の範囲である。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、２．２を越えると流動
性が低下し、目的とする成形品外観が得られないので好
ましくない。しかし、ナイロン６の相対粘度を規制する
より無機強化ポリアミド樹脂のメルトフローインデック
スを規制する方が現実的である。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. The component (A) in the present invention is a polycapramide resin usually obtained by polycondensation of ε-caprolactam called nylon 6, and the relative viscosity of a commonly used molding material measured by 96% -H 2 SO 4 is 2%. , But the relative viscosity when used in the present invention is 1.
The range of 7 to 2.2 is preferred. Particularly preferred is 1.9.
~ 2.1. If it is less than 1.7, the toughness decreases, and if it exceeds 2.2, the fluidity decreases, and the desired appearance of the molded product cannot be obtained. However, it is more realistic to regulate the melt flow index of the inorganic reinforced polyamide resin than to regulate the relative viscosity of nylon 6.
【０００８】本発明における（Ｂ）成分のポリカプラミ
ド樹脂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―カプロラクタム等より得られる重合体である。
具体例としては、ヘキサメチレンジアミンとアジピン酸
重合体、ヘキサメチレンジアミンとテレフタル酸重合
体、ヘキサメチレンジアミンとイソフタル酸重合体、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
酸重合体、ヘキサメチレンジアミンとテレフタル酸およ
びアジピン酸重合体、ヘキサメチレンジアミンとテレフ
タル酸およびε―カプロラクタム重合体、メタキシリレ
ンジアミンとアジピン酸重合体、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
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、イソフタル酸重合体、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
タムの共重合体、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、本発明においては、ジ
アミン成分又はジカルボン酸成分のいずれかが芳香族で
ある半芳香族非晶性ポリアミド樹脂が好ましいが特に限
定されるものではない。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、好ましい範囲
は１．８〜２．４である。The polyamide resin other than the polycapramide resin as the component (B) in the present invention is obtained from adipic acid, terephthalic acid, isophthalic acid, trimethylhexamethylenediamine, hexamethylenediamine, metaxylylenediamine, ε-caprolactam and the like. It is a polymer.
Specific examples include hexamethylene diamine and adipic acid polymer, hexamethylene diamine and terephthalic acid polymer, hexamethylene diamine and isophthalic acid polymer, hexamethylene diamine and terephthalic acid and isophthalic acid polymer, and hexamethylene diamine and terephthalic acid. And adipic acid polymer, hexamethylenediamine and terephthalic acid and ε-caprolactam polymer, metaxylylenediamine and adipic acid polymer, trimethylhexamethylenediamine and terephthalic acid polymer, trimethylhexamethylenediamine and terephthalic acid and ε-caprolactam Polymer, trimethylhexamethylenediamine and terephthalic acid, isophthalic acid polymer, copolymer of terephthalic acid and isophthalic acid with hexamethylenediamine and ε-caprolactam, meta Examples include polyamide resins such as copolymers of silylene diamine and terephthalic acid and isophthalic acid and ε-caprolactam, and in the present invention, a semi-aromatic amorphous polyamide in which either the diamine component or the dicarboxylic acid component is aromatic A resin is preferable, but not particularly limited. The relative viscosity of these polyamide resins is not particularly limited, but the preferred range is 1.8 to 2.4.
【０００９】（Ａ）成分と（Ｂ）成分の合計添加量は、
３０〜５５重量％であり、好ましくは３５〜５０重量％
である。また、（Ａ）成分と（Ｂ）成分の配合割合は特
に限定はないが、（Ａ）成分と（Ｂ）成分の合計添加量
に対する（Ｂ）成分の添加量は８〜１８重量％が好まし
い。（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
結晶固化が悪くなり、成形時に離型不良が生じたり熱間
剛性が低下したりする。また、本発明においては（Ａ）
成分と（Ｂ）成分との配合比は下記式を満足することが
好ましい。 ０．２５＜（Ｂ）／（Ａ）≦１The total amount of the components (A) and (B) is
30 to 55% by weight, preferably 35 to 50% by weight
It is. Further, the mixing ratio of the component (A) and the component (B) is not particularly limited, but the addition amount of the component (B) is preferably 8 to 18% by weight based on the total addition amount of the component (A) and the component (B). . If the added amount of the component (B) is too small, a good appearance of the molded article cannot be obtained. Conversely, if the added amount of the component (B) is too large, the solidification of the molded article will be poor, resulting in mold release failure or heat during molding. Or the rigidity between them decreases. In the present invention, (A)
The compounding ratio of the component and the component (B) preferably satisfies the following formula. 0.25 <(B) / (A) ≦ 1
【００１０】本発明における（Ｃ）成分としては無機強
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
の無機強化材やが挙げられる。好ましい無機強化材とし
ては、ガラス繊維（Ｃ−１）、粉末状ガラス（ミルドフ
ァイバー）および／または針状ワラストナイト（Ｃ−
２）、マイカ、タルク、カオリン（Ｃ−３）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種以
上を併用使用することもできる。また、これらの無機強
化材は、ポリアミド樹脂の強化材に使用する場合、表面
処理剤として一般的にアミノシラン処理されているもの
を使用してもよい。The component (C) in the present invention is an inorganic reinforcing material. Specific examples thereof include a fibrous inorganic reinforcing material such as glass fiber, acicular wollast, whisker, carbon fiber and ceramic fiber, silica, alumina and talc. , Kaolin, quartz, glass, mica, graphite, and other powdery inorganic reinforcing materials. Preferred inorganic reinforcing materials include glass fiber (C-1), powdered glass (milled fiber) and / or acicular wollastonite (C-
2), mica, talc, kaolin (C-3) and the like. These inorganic reinforcing materials can be used alone or in combination of two or more. In addition, when these inorganic reinforcing materials are used as a reinforcing material of a polyamide resin, those generally treated with aminosilane as a surface treating agent may be used.
【００１１】前記（Ｃ−１）ガラス繊維としては、平均
粒径は４〜２０μ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（押出工程・成形
工程）で短くなり１５０〜３００μ程度になる。ポリア
ミド樹脂の強化材に使用する場合の表面処理剤としては
一般的にアミノシラン処理されている。ガラス繊維の強
化材量としては２０〜４０重量％であり、好ましくは２
５〜３５重量％である。２０重量％未満であれば強度、
剛性が低く反対に４０重量％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。The (C-1) glass fiber has an average particle size of about 4 to 20 μm and a cut length of about 3 to 6 mm, and a very common fiber can be used. The average fiber length of the glass fibers in the molded product is reduced in the processing step (extrusion step / forming step) to about 150 to 300 μm. When used as a reinforcing material for a polyamide resin, an aminosilane treatment is generally used as a surface treatment agent. The amount of glass fiber reinforcement is 20 to 40% by weight, preferably 2 to 40% by weight.
5 to 35% by weight. If less than 20% by weight, strength,
On the other hand, if the rigidity is low and exceeds 40% by weight, it is difficult to obtain a good appearance of the molded product, which is not preferable.
【００１２】前記（Ｃ−２）のミルドファイバーとは
（Ｃ−１）のガラス繊維の長さを短くしたものであり、
平均粒径は４〜２０μ程度、カット長は３５〜８０μ程
度であり、加工工程（押出工程・成形工程）でほとんど
短くならないため成形品中の繊維長は３０〜７５μ程度
である。又（Ｃ−２）の針状ワラストナイトとは平均粒
径は３〜４０μ程度であり平均繊維長は２０〜８０μ程
度のワラストナイトである。これら（Ｃ−２）の添加量
は８〜２５重量％好ましくは１０〜２０重量％である。
８重量％未満であれば強度、剛性が低く反対に２５重量
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。The milled fiber (C-2) is obtained by shortening the length of the glass fiber (C-1).
The average particle size is about 4 to 20 μm, the cut length is about 35 to 80 μm, and the fiber length in the molded product is about 30 to 75 μm because it hardly becomes short in the processing step (extrusion step / forming step). The acicular wollastonite (C-2) is a wollastonite having an average particle size of about 3 to 40 μm and an average fiber length of about 20 to 80 μm. The addition amount of these (C-2) is 8 to 25% by weight, preferably 10 to 20% by weight.
If it is less than 8% by weight, the strength and rigidity are low, and if it exceeds 25% by weight, it is difficult to obtain a good appearance of the molded product, which is not preferable.
【００１３】前記（Ｃ−３）の板状晶とはタルク、マイ
カ、未焼成クレー等が挙げられ、その形状は魚のウロコ
のような形態を示す。添加量は８〜２５重量％、好まし
くは１０〜２０重量％である。８重量％未満であれば強
度、剛性が低く、反対に２５重量％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。なお（Ｃ−
３）の板状晶のなかでも強度、剛性の面より特にマイカ
が優れている。The plate-like crystal of the above (C-3) includes talc, mica, unfired clay and the like, and its shape shows a form like fish scale. The addition amount is 8 to 25% by weight, preferably 10 to 20% by weight. If it is less than 8% by weight, strength and rigidity are low, and if it is more than 25% by weight, it is difficult to obtain a good appearance of a molded product, which is not preferable. (C-
Among the plate crystals of 3), mica is particularly excellent in terms of strength and rigidity.
【００１４】本発明（Ｃ）成分の強化材の配合量は４５
〜７０重量％であり好ましくは５５〜６５重量％であ
る。４５重量％未満の場合は強度、剛性が低くなり反対
に７０重量％より上になれば良好な成形品外観は得られ
ず、又強度に関しても低下する。本発明の（Ｃ）成分中
（Ｃ−１）が２０〜４０重量％、（Ｃ−２）が８〜２５
重量％（Ｃ−３）が８〜２５重量％の範囲内で添加する
ことにより強度剛性が優れており、しかも成形品表面外
観（鏡面表面光沢シボ面均一表面性）が優れる。The compounding amount of the reinforcing material of the present invention (C) is 45.
７０70% by weight, preferably 55-65% by weight. If the content is less than 45% by weight, the strength and rigidity are reduced. On the other hand, if the content is more than 70% by weight, a good appearance of the molded article is not obtained, and the strength is also reduced. In the component (C) of the present invention, (C-1) is 20 to 40% by weight, and (C-2) is 8 to 25%.
When the weight% (C-3) is in the range of 8 to 25% by weight, the strength and rigidity are excellent, and the surface appearance of the molded product (specular surface gloss / texture uniform surface property) is excellent.
【００１５】さらに、本発明の無機強化ポリアミド樹脂
の水分率が０．０５％以下でのメルトフローインデック
スが４．０ｇ／１０分以上で、かつ示差走査熱量計（Ｄ
ＳＣ）で測定した降温結晶化温度（ＴＣ２）が、（ＴＣ
２）≦１８５℃であることが必要である。メルトフロー
インデックスは、ＪＩＳ Ｋ−７２１０に準じて２７５
℃×２１６０ｇ荷重で測定した値である。また、降温結
晶化温度（ＴＣ２）の測定は示差走査熱量計（ＤＳＣ）
を用い、窒素気流下で２０℃／分の昇温速度にて３００
℃まで昇温し、その温度で５分間保持した後、１０℃／
分の速度にて１００℃まで降温させることにより測定し
た。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。メルトフロー
インデックスが４．０ｇ／１０分以上の無機強化ポリア
ミド樹脂組成物を得るには、通常よく用いられている相
対粘度２．３以上の結晶性ポリアミド樹脂を用いると、
前記メルトフローインデックスの範囲に達せず（４．０
ｇ／１０分未満）、超低粘度（相対粘度１．７〜２．
２）の結晶性ポリアミド樹脂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鎖切断剤を添加する等の
処方を採用しても良い。前記ポリアミド樹脂の分子鎖切
断剤（減粘剤ともいう）としては、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
れるが、特に限定されるものではない。また、その添加
量は本発明の（Ａ）＋（Ｂ）＋（Ｃ）成分の合計１００
重量部に対し０．１〜３重量部前後で、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鎖切断剤
の効果は変化し、当然のことながら加工温度が高い程、
またコンパウンド時のポリマー滞留時間が長い程効果は
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秒以内が一般的である。さらに、降温結晶化
温度（ＴＣ２）が、（ＴＣ２）≦１８５℃を満足しない
場合は、組成物の結晶化速度に起因して良好な成形品外
観が得られない。Further, when the water content of the inorganic reinforced polyamide resin of the present invention is 0.05% or less, the melt flow index is 4.0 g / 10 minutes or more, and the differential scanning calorimeter (D) is used.
SC), the cooling crystallization temperature (TC2)
2) It is necessary that ≦ 185 ° C. The melt flow index is 275 according to JIS K-7210.
It is a value measured under a load of 2 ° C. × 2160 g. In addition, the measurement of the cooling crystallization temperature (TC2) is performed by a differential scanning calorimeter (DSC).
At a heating rate of 20 ° C./min.
Temperature, and kept at that temperature for 5 minutes.
The measurement was performed by lowering the temperature to 100 ° C. at a rate of minutes. 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 an inorganic reinforced polyamide resin composition having a melt flow index of 4.0 g / 10 minutes or more, a crystalline polyamide resin having a relative viscosity of 2.3 or more, which is commonly used, is used.
The melt flow index range was not reached (4.0
g / 10 minutes), very low viscosity (relative viscosity 1.7 to 2.
A prescription such as using a crystalline polyamide resin of 2) or adding a molecular chain scission agent for the polyamide resin during compounding may be employed. Aliphatic dicarboxylic acids, aromatic dicarboxylic acids and the like are effective as the molecular chain scission agent (also referred to as a viscosity reducing agent) of the polyamide resin, and specifically,
Oxalic acid, malonic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, terephthalic acid, and the like are included, but are not particularly limited. Further, the amount of addition is 100% in total of (A) + (B) + (C) components of the present invention.
The melt flow index of the composition of the present invention becomes 4.0 g / 10 min or more when the content is about 0.1 to 3 parts by weight based on the weight part. However, the effect of the molecular chain cutting agent changes depending on the compound processing conditions.
The longer the residence time of the polymer during compounding, the better the effect. Usually, the compounding temperature is 240-300
The polymer residence time in the range of ° C. and during compounding is generally within 15 to 60 seconds. Further, when the cooling crystallization temperature (TC2) does not satisfy (TC2) ≦ 185 ° C., a good molded article appearance cannot be obtained due to the crystallization speed of the composition.
【００１６】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、染料あるいは他種ポリ
マーなども添加することができる。The inorganic reinforced polyamide resin composition of the present invention may further comprise a heat stabilizer, an antioxidant, an ultraviolet absorber, a light stabilizer, a plasticizer, a lubricant, a crystal nucleating agent, a release agent, if necessary. Antistatic agents, flame retardants, pigments, dyes or other polymers can also be added.
【００１７】本発明の組成物を得る方法としては、上述
した（Ａ）（Ｂ）（Ｃ）成分その他は、上記配合比率に
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、当業者に周知のいずれかの方法も可能であ
り、単軸押出機、２軸押出機、ニーダー、バンバリーミ
キサー、ロール等が使用できる。なかでも２軸押出機を
使用することが好ましい。また、押出加工時破損し易い
ガラス繊維、針状ワラスト等は、２軸押出機のサイド口
より投入することが好ましいが、特に限定されるもので
はない。As a method for obtaining the composition of the present invention, the above-mentioned components (A), (B), (C) and others are blended in an arbitrary blending order at the above blending ratio and then melt-mixed. As the melt mixing method, any method known to those skilled in the art can be used, and a single screw extruder, a twin screw extruder, a kneader, a Banbury mixer, a roll, and the like can be used. Among them, it is preferable to use a twin-screw extruder. In addition, glass fibers, needle-like wollasts, and the like, which are easily broken during extrusion processing, are preferably introduced through the side opening of the twin-screw extruder, but are not particularly limited.
【００１８】[0018]
【実施例】以下、実施例により本発明を更に詳細に説明
するが、本発明はこれら実施例により何ら制限されるも
のではない。また、以下の実施例、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。EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. The properties and physical properties shown in the following examples and comparative examples were measured by the following test methods.
【００１９】１）相対粘度（硫酸溶液法）：ＪＩＳ Ｋ
−６８１０に準じて、９６％−Ｈ2ＳＯ4溶液中で測定し
た。 ２）引張強度：ＡＳＴＭ Ｄ−６３８に準じて測定し
た。 ３）引張弾性率：ＡＳＴＭ Ｄ−６３８に準じて測定し
た。 ４）鏡面光沢度：鏡面仕上げの１００×１００×３mmt
の金型を使用し、樹脂温度２８０℃、金型温度８０℃で
成形品を作成し、ＪＩＳ Ｚ−８７１４に準じて入射角
６０度の光沢度を測定した。（数値が高い程、光沢度が
良い） 判定は、光沢度９２以上：○、光沢度９１〜７５：△、
光沢度７４以下：×で行なった。 ５）シボ面均一表面性：シボ加工された板状の金型（図
１にその平面図を示すが、図１において斜線部は樹脂が
挿入されない部分である）を使用し、樹脂温度８５℃、
金型温度８０℃で成形し、厚み２．５mmtの成形品を作
成後、シボ面の表面性を肉眼で判定した。 判定基準；○印：シボ転写性が全面にわたり良好で光沢斑がない。 △印：部分的にシボ転写性が異なり、光沢斑が少しある。 ×印：部分的にシボ転写性が大きく異なり、著しく光沢斑があ り外装部品として使用できない。1) Relative viscosity (sulfuric acid solution method): JIS K
According to -6810, it was measured at 96% -H 2 SO 4 solution. 2) Tensile strength: Measured according to ASTM D-638. 3) Tensile modulus: Measured according to ASTM D-638. 4) Specular gloss: 100 × 100 × 3 mmt with mirror finish
A molded product was prepared at a resin temperature of 280 ° C. and a mold temperature of 80 ° C., and the glossiness at an incident angle of 60 ° was measured according to JIS Z-8714. (The higher the numerical value, the better the glossiness.) The judgment was as follows: glossiness 92 or more: 、, glossiness 91 to 75: Δ,
Gloss 74 or less: x 5) Textured surface uniformity: Using a plate-shaped mold that has been textured (a plan view is shown in FIG. 1, the hatched portion in FIG. 1 is a portion where the resin is not inserted), and the resin temperature is 85 ° C. ,
After molding at a mold temperature of 80 ° C. to form a molded product having a thickness of 2.5 mmt, the surface properties of the grained surface were visually judged. Judgment criterion: 印: The transferability of the grain was good over the entire surface and there was no gloss unevenness. Δ: Partially different grain transferability, with slight gloss unevenness. X: Partially significantly different grain transferability, marked gloss spots, and cannot be used as exterior parts.
【００２０】実施例１〜４，比較例１〜４ 結晶性ポリアミド樹脂として相対粘度の異なるナイロン
６を用い、結晶性ポリアミド樹脂以外のポリアミド樹脂
としてナイロン６６，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（６Ｔ／６Ｉ樹脂）、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―
カプロラクタム重合体（ＴＭＤ−Ｔ樹脂）を用いた。ま
た、無機強化材としては市販のガラス繊維（日本板硝子
（株）製ＲＥＳ０３Ｔ−ＴＰ６４Ｔ）を使用、ミルドフ
ァイバーとしては日本硝子繊維（株）製のＲＥＶ−８
（繊維径１３μ、平均繊維長７０μ、表面処理剤アミノ
シラン）を使用した。また針状ワラストとしてはＮＹＣ
Ｏ社のＮＹＧＬＯＳ−８（平均繊維径８μ、平均繊維長
１３０μ）を使用、板状晶のマイカとして（株）レプコ
社製のＭ−３２５Ｓ（平均粒子径１８μ、平均アスペク
ト比２０）を使用した。その他離型剤としてモンタン酸
カルシウムを各０．４部添加し、表１に示す組成で混合
後、３５φ２軸押出機を用いてシリンダー温度２７０
℃、スクリュー回転数７０ｒｐｍにてコンパウンドを実
施し、ペレットを作成した。得られたペレットは、熱風
乾燥機にて水分率０．０５％以下になるまで乾燥後、種
々特性を評価した。評価結果を表１に示す。Examples 1-4 and Comparative Examples 1-4 Nylon 6 having a different relative viscosity was used as a crystalline polyamide resin, and nylon 66, hexamethylene terephthalate / polyamide resin was used as a polyamide resin other than the crystalline polyamide resin.
Hexamethylene isophthalate (6T / 6I resin), trimethylhexamethylenediamine, terephthalic acid and ε-
A caprolactam polymer (TMD-T resin) was used. Also, commercially available glass fiber (RES03T-TP64T manufactured by Nippon Sheet Glass Co., Ltd.) was used as the inorganic reinforcing material, and REV-8 manufactured by Nippon Glass Fiber Co., Ltd. was used as the milled fiber.
(Fiber diameter 13 μ, average fiber length 70 μ, surface treating agent aminosilane). NYC as needle-shaped wollast
NYGLOS-8 (average fiber diameter 8μ, average fiber length 130μ) of Company O was used, and M-325S (average particle diameter 18μ, average aspect ratio 20) manufactured by Repco Co., Ltd. was used as mica of plate crystals. . In addition, 0.4 parts each of calcium montanate was added as a mold release agent, mixed with the composition shown in Table 1, and then heated to a cylinder temperature of 270 using a 35φ twin screw extruder.
Compounding was performed at 70 ° C. and a screw rotation speed of 70 rpm to produce pellets. The obtained pellets were dried with a hot air dryer until the water content became 0.05% or less, and then various characteristics were evaluated. Table 1 shows the evaluation results.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】本発明のポリアミド樹脂組成物は、ポリ
カプラミド樹脂とポリカプラミド樹脂以外のポリアミド
樹脂および無機強化材を含有する組成物からなり、組成
物のメルトフローインデックスおよび示差走査熱量計
（ＤＳＣ）で測定した降温結晶化温度（ＴＣ２）を限定
することにより、強度・剛性が優れかつ成形品外観（鏡
面表面光沢およびシボ面均一表面性）の優れる樹脂組成
物を供給することができる。このような優れた性能を有
する本発明のポリアミド樹脂組成物は、自動車用途、電
機・電子部品用途等エンジニアリングプラスチック用途
に好適に使用することができる。The polyamide resin composition of the present invention comprises a polycapramide resin, a composition containing a polyamide resin other than the polycapramide resin, and an inorganic reinforcing material. The composition is measured by a melt flow index and a differential scanning calorimeter (DSC). By limiting the measured cooling crystallization temperature (TC2), it is possible to supply a resin composition having excellent strength and rigidity and excellent molded article appearance (mirror surface gloss and textured surface uniformity). The polyamide resin composition of the present invention having such excellent performance can be suitably used for engineering plastic applications such as automotive applications, electric / electronic parts applications, and the like.
【図１】は、本発明組成物のシボ面均一表面性を評価す
る際に用いる金型の平面図である。BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a plan view of a mold used for evaluating the textured surface uniformity of the composition of the present invention.
Claims (5)
る結晶性ポリアミド樹脂、（Ｂ）（Ａ）以外のポリアミ
ド樹脂および（Ｃ）無機強化材を含有する組成物であっ
て、組成物の水分率０．０５％以下でのメルトフローイ
ンデックス（ＭＦＩ）が４．０ｇ／１０分以上であり、
かつ示差走査熱量計（ＤＳＣ）で測定し降温結晶化温度
（ＴＣ２）が、（ＴＣ２）≦１８５℃であることを特徴
とするポリアミド樹脂組成物。1. A composition containing (A) a crystalline polyamide resin containing a polycapramide resin as a main component, (B) a polyamide resin other than (A), and (C) an inorganic reinforcing material, wherein the composition contains water. The melt flow index (MFI) at a rate of 0.05% or less is 4.0 g / 10 minutes or more;
A polyamide resin composition characterized in that a temperature-reducing crystallization temperature (TC2) measured by a differential scanning calorimeter (DSC) is (TC2) ≦ 185 ° C.
維、（Ｃ−２）ミルドファイバーおよび／または針状ワ
ラストナイト、および（Ｃ−３）板状晶を含有している
請求項１記載のポリアミド樹脂組成物。2. The (C) inorganic reinforcing material contains (C-1) glass fiber, (C-2) milled fiber and / or acicular wollastonite, and (C-3) platelet crystal. The polyamide resin composition according to claim 1.
香族非晶性ポリアミド樹脂である請求項１記載のポリア
ミド樹脂組成物。3. The polyamide resin composition according to claim 1, wherein the polyamide resin other than (B) and (A) is a semi-aromatic amorphous polyamide resin.
式を満足する請求項１記載のポリアミド樹脂組成物。 ０．２５＜（Ｂ）／（Ａ）≦１4. The polyamide resin composition according to claim 1, wherein the compounding ratio of the components (A) and (B) satisfies the following formula. 0.25 <(B) / (A) ≦ 1
る請求項２記載のポリアミド樹脂組成物。 ３０重量％≦（Ａ）＋（Ｂ）≦５５重量％ ８重量％≦（Ｂ）≦１８重量％ ２０重量％≦（Ｃ−１）≦４０重量％ ８重量％≦（Ｃ−２）≦２５重量％ ８重量％≦（Ｃ−３）≦２５重量％ ４５重量％≦（Ｃ−１）＋（Ｃ−２）＋（Ｃ−３）≦７
０重量％5. The polyamide resin composition according to claim 2, wherein the compounding ratio and amount of each component satisfy the following formula. 30% by weight ≦ (A) + (B) ≦ 55% by weight 8% by weight ≦ (B) ≦ 18% by weight 20% by weight ≦ (C-1) ≦ 40% by weight 8% by weight ≦ (C-2) ≦ 25 % By weight 8% by weight ≦ (C-3) ≦ 25% by weight 45% by weight ≦ (C-1) + (C-2) + (C-3) ≦ 7
0% by weight
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|---|---|---|---|
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26276398 | 1998-09-17 | ||
| JP10-262763 | 1998-09-17 | ||
| JP26054099A JP4487154B2 (en) | 1998-09-17 | 1999-09-14 | Polyamide resin composition |
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| Publication Number | Publication Date |
|---|---|
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ID=26544650
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| WO2001032781A1 (en) * | 1999-11-02 | 2001-05-10 | Daicel Chemical Industries, Ltd. | Thermoplastic resin composition |
| JP2005532435A (en) * | 2002-07-01 | 2005-10-27 | ランクセス・コーポレーション | Glass fiber filled thermoplastic composition with good surface performance |
| JP2007231076A (en) * | 2006-02-28 | 2007-09-13 | Unitika Ltd | Polyamide resin composition for light-reflective molded product |
| WO2008053911A1 (en) | 2006-11-01 | 2008-05-08 | Mitsubishi Engineering-Plastics Corporation | Pellet blend of polyamide resin composition, molded article, and process for producing pellet blend |
| JP2008189929A (en) * | 2007-02-07 | 2008-08-21 | Ems-Chemie Ag | Filling polyamide molding material showing reduction of water-absorbing property |
| JP2009051885A (en) * | 2007-08-24 | 2009-03-12 | Toyobo Co Ltd | Long fiber-reinforced polyamide resin composition |
| JP2009539659A (en) * | 2006-06-16 | 2009-11-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Semi-aromatic polyamide composite article and preparation method thereof |
| JP2011503306A (en) * | 2007-11-16 | 2011-01-27 | エムス−パテント・アクチェンゲゼルシャフト | Filled polyamide molding compound |
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| CN102341450A (en) * | 2009-03-04 | 2012-02-01 | 帝斯曼知识产权资产管理有限公司 | Process for preparing injection molded parts with decreased glass fiber read out |
| WO2017135338A1 (en) * | 2016-02-03 | 2017-08-10 | 宇部興産株式会社 | Polyamide resin composition |
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| WO2020110978A1 (en) | 2018-11-28 | 2020-06-04 | 東洋紡株式会社 | Polyamide resin composition and method for producing same |
| WO2020158498A1 (en) | 2019-01-30 | 2020-08-06 | 東洋紡株式会社 | Polyamide resin composition, and production method therefor |
| EP3725833B1 (en) | 2019-04-16 | 2021-03-17 | Ems-Chemie Ag | Reinforced thermpolastische moulding composition |
| WO2021149674A1 (en) | 2020-01-24 | 2021-07-29 | 東洋紡株式会社 | Method for producing polyamide resin composition |
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