JP2761563B2 - Polyetherimide resin composition - Google Patents
Polyetherimide resin compositionInfo
- Publication number
- JP2761563B2 JP2761563B2 JP63143873A JP14387388A JP2761563B2 JP 2761563 B2 JP2761563 B2 JP 2761563B2 JP 63143873 A JP63143873 A JP 63143873A JP 14387388 A JP14387388 A JP 14387388A JP 2761563 B2 JP2761563 B2 JP 2761563B2
- Authority
- JP
- Japan
- Prior art keywords
- polyetherimide resin
- resin composition
- potassium
- ptw
- fiber
- 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.)
- Expired - Lifetime
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は射出成形法を主体に、押出成形法、場合によ
つては圧縮成形法によつても、優れた機械的性質、熱的
性質、成形加工性、寸法精度を有する各種成形品を製造
することが可能なポリエーテルイミド樹脂組成物に関す
る。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is mainly based on injection molding, and is also excellent in mechanical properties and thermal properties by extrusion molding and sometimes compression molding. The present invention relates to a polyetherimide resin composition capable of producing various molded articles having molding processability and dimensional accuracy.
（従来の技術） ポリエーテルイミド樹脂は非晶性ながら、機械的、熱
的及び化学的性質に優れたエンジニアリングプラスチツ
クの１つであり、射出成形材料として各種の分野に、
又、押出フイルムとして電気的用途を主体に使用されて
いる。(Prior art) Polyetherimide resin is one of engineering plastics having excellent mechanical, thermal and chemical properties while being amorphous, and is used as an injection molding material in various fields.
In addition, it is mainly used as an extruded film for electrical applications.
射出成形材料としては非強化（ナチュラル）のままで
使用されたり、ガラス繊維、炭素繊維で強化されたもの
が一般的であり、押出用に外観が悪くなること及び押出
機、ダイスの損傷の面から、ガラス繊維、炭素繊維強化
品は使用されず、せいぜい微粒子状充填剤（タルク、炭
酸カルシウム等）が、10重量％以下で使用されるに過ぎ
ない。Injection molding materials are generally used as unreinforced (natural) or reinforced with glass fiber or carbon fiber, resulting in poor appearance for extrusion and damage to extruders and dies. Therefore, glass fiber and carbon fiber reinforced products are not used, and at most a particulate filler (such as talc and calcium carbonate) is used at 10% by weight or less.
そこでミクロフアイバーでありウイスカーとして経済
的なチタン酸カリウム繊維が注目され、ポリエーテルイ
ミド樹脂の強化剤としての応用も種々検討されている
が、今迄一般的に市販されていたチタン酸カリウム繊維
では、溶融状態（加工機械中での溶融滞留時）に、増粘
現象が大で、ひどい場合にはゲル化によつて加工機械が
運転不能となつたり、又、ウイスカー強化材料の特徴で
ある精密成形においては、肝心の溶融粘度管理ができな
いため、応用分野が非常に制約をうけているのが実状で
あつた。Therefore, potassium titanate fiber, which is a microfiber and economical as a whisker, has attracted attention, and various applications of polyetherimide resin as a reinforcing agent have been studied. In the molten state (during melt retention in the processing machine), the phenomenon of thickening is large, and in severe cases, the processing machine becomes inoperable due to gelation, and precision is a characteristic of whisker reinforced materials. In molding, since the melt viscosity cannot be controlled crucially, the actual field of application is very limited.
（発明が解決しようとする課題） 本発明の目的はポリエーテルイミド樹脂の強度、剛
性、耐熱性を更に向上させると共に、溶融時の粘度変化
が少なく、成形加工管理ひいては量産性に非常に優れ
た、殊に小型、薄肉製品の成形加工に適したポリエーテ
ルイミド樹脂組成物を提供することにある。(Problems to be Solved by the Invention) An object of the present invention is to further improve the strength, rigidity, and heat resistance of a polyetherimide resin, to reduce a change in viscosity at the time of melting, and to be excellent in molding process management and, consequently, mass productivity. In particular, it is an object of the present invention to provide a polyetherimide resin composition suitable for molding small and thin products.
（課題を解決するための手段） 本発明はpH6.0〜8.5、Ｘ線回析チヤートにおける２θ
＝13.8゜の特性ピークにおける半値幅が0.10以下の６−
チタン酸カリウム繊維を、５〜60重量％含有させたこと
を特徴とするポリエーテルイミド樹脂組成物に係る。(Means for Solving the Problems) The present invention relates to a method for preparing a 2θ in an X-ray diffraction chart at pH 6.0 to 8.5.
6-1. The half width at the characteristic peak of 13.8 ° is 0.10 or less.
The present invention relates to a polyetherimide resin composition containing 5 to 60% by weight of potassium titanate fiber.
本発明においてポリエーテルイミド樹脂として一般式 （R1はＣ６〜30の２価の芳香族有機基、R2はＣ６〜30の
２価の芳香族有機基又はＣ２〜20のアルキレン基、シク
ロアルキレン基、アルキレン末端ポリジオルガノシロキ
サン基の中から選択される２価の有機基を示す。ｎ＝５
〜500）で表わされ、固有粘度がジメチルホルムアミド
中、25℃で0.2〜1.5dl/gのものを例示でき、その製法は
例えば米国特許第3,803,085号に開示されている。In the present invention, a polyetherimide resin represented by the general formula (R 1 is a C 6-30 divalent aromatic organic group, R 2 is a C 6-30 divalent aromatic organic group or a C 2-20 alkylene group, cycloalkylene group, alkylene-terminated polydiorganosiloxane A divalent organic group selected from the groups: n = 5
500500) and an intrinsic viscosity in dimethylformamide of 0.2 to 1.5 dl / g at 25 ° C., and its production method is disclosed, for example, in US Pat. No. 3,803,085.
上記一般式のなかでも、2,2−ビス〔４−（3,4−ジカ
ルボキシフエノキシ）フエニル〕プロパン二無水物を、
芳香族ビス（エーテル無水物）成分とし、有機ジアミン
成分として、ｍ−フエニレンジアミンを縮重合してな
る、下記構造式のポリエーテルイミド樹脂（商品名ウル
テム、ゼネラル・エレクトリツク社製）が好適であり、
ジメチルホルムアミド中、25℃での固有粘度が0.3〜1.0
dl/gのものが一般的である。Among the above general formulas, 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride is
As the aromatic bis (ether anhydride) component and the organic diamine component, a polyetherimide resin (trade name: Ultem, manufactured by General Electric Co., Ltd.) having the following structural formula obtained by condensation polymerization of m-phenylenediamine is preferable. And
In dimethylformamide, the intrinsic viscosity at 25 ° C is 0.3 to 1.0
dl / g is common.
尚、前述のポリエーテルイミド樹脂の構成成分である
芳香族ビス（エーテル無水物）として好適なものは前述
の2,2−ビス〔４−（3,4−ジカルボキシフエノキシ）フ
エニル〕プロパン二無水物の他に、2,2−ビス〔４−
（2,3−ジカルボキシフエノキシ）フエニル〕プロパン
二無水物、４−（2,3−ジカルボキシフエノキシ）−
４′−（3,4−ジカルボキシフエノキシ）ジフエニル−
2,2−プロパン二無水物及びこれらの混合物が挙げら
れ、又、一方の有機ジアミン成分の好適なものとして、
前述のｍ−フエニレンジアミンの他に、4,4′−ジアミ
ノジフエニルメタン、4,4′−ジオキシジアニリン及び
これらの混合物が具体例として挙げられるが、これらに
限定されるものではない。 The aromatic bis (ether anhydride) which is a constituent component of the above-mentioned polyetherimide resin is preferably 2,2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane. In addition to dianhydride, 2,2-bis [4-
(2,3-Dicarboxyphenoxy) phenyl] propane dianhydride, 4- (2,3-dicarboxyphenoxy)-
4 '-(3,4-dicarboxyphenoxy) diphenyl-
2,2-propane dianhydride and mixtures thereof, and as a suitable one of the organic diamine component,
In addition to the aforementioned m-phenylenediamine, specific examples include, but are not limited to, 4,4'-diaminodiphenylmethane, 4,4'-dioxydianiline and mixtures thereof. .
一方、６−チタン酸カリウム繊維（以下PTWと略記す
る）とは、K2O・6TiO2で示される単結晶繊維（ウイスカ
ー）であり、K2Oの出発原料としてはK2O、K2CO3など、T
iO2の出発原料としてはTiO2或いはTiO2含有化合物（ル
チルサンド等の天然鉱物を含む）を挙げることができ、
これらの混合比、反応温度及び反応系の塩基度等を調整
することにより、水熱法、フラツクス法、焼成法、溶融
法、融体法等により製造され、各種の平均繊維径、平均
繊維長、pH値、結晶化度のPTWが得られる。On the other hand, 6-A potassium titanate fiber (hereinafter abbreviated as PTW), a single crystal fibers (whiskers) represented by K 2 O · 6TiO 2, as the starting material K 2 O K 2 O, K 2 CO 3 etc., T
TiO 2 or TiO 2 -containing compounds (including natural minerals such as rutile sand) can be mentioned as starting materials for iO 2 ;
By adjusting the mixing ratio, the reaction temperature and the basicity of the reaction system, etc., it is produced by a hydrothermal method, a flux method, a firing method, a melting method, a melt method, etc., and various average fiber diameters and average fiber lengths. , PH value and crystallinity PTW are obtained.
本発明においては該PTWの平均繊維径及び平均繊維長
については特に制限はなく、平均繊維径0.05〜2.0μ
ｍ、平均繊維長１〜500μｍのものが全て使用可能であ
り、補強効果の点からアスペクト比（平均繊維長／平均
繊維径）が10以上のものが望ましい。In the present invention, the average fiber diameter and the average fiber length of the PTW are not particularly limited, and the average fiber diameter is 0.05 to 2.0 μm.
m, an average fiber length of 1 to 500 μm can all be used, and an aspect ratio (average fiber length / average fiber diameter) of 10 or more is desirable from the viewpoint of the reinforcing effect.
しかし使用するPTWのpH値と結晶化度については、PTW
配合のポリエーテルイミド樹脂組成物の溶融粘度の粘度
安定性の面から、PTWのpHが6.0〜8.5、好ましくは6.5〜
8.0、Ｘ線回析チヤートにおける２θ＝13.8゜の特性ピ
ークの半値幅が0.10以下、好ましくは、0.05以下である
ことが必須要件となることが判明した。However, regarding the pH value and crystallinity of the PTW used,
From the viewpoint of the viscosity stability of the melt viscosity of the blended polyetherimide resin composition, the pH of the PTW is 6.0 to 8.5, preferably 6.5 to 8.5.
8.0, it has been found that the half-width of the characteristic peak at 2θ = 13.8 ° in the X-ray diffraction chart is 0.10 or less, preferably 0.05 or less.
ここでPTWのpHとは、PTWの1.0重量％懸濁水溶液（脱
イオン水を使用）を、10分間撹拌後、20℃でpHを測定し
た値をいい、従来市販されているPTWの殆どのものはpH
8.0を越え、9.0〜10.5のアルカリ性のものが多かつた。Here, the pH of PTW refers to a value obtained by measuring the pH at 20 ° C. after stirring a 1.0% by weight aqueous suspension of PTW (using deionized water) for 10 minutes. Things are pH
Most of them exceeded 8.0 and were alkaline in the range of 9.0 to 10.5.
PTWのpHが8.5を越えると、ポリエーテルイミド樹脂の
加工温度である380℃近辺での溶融粘度が、徐々に増大
してくると共にPTWの配合量の多いポリエーテルイミド
樹脂組成物では、ゲル化を起こし、例えば射出成形機が
こわれてしまうという現象が生じる恐れがある。一方pH
が6.0を下回ると、得られるポリエーテルイミド樹脂組
成物の強度の向上効果が小さいのみならず、加工機械、
金型を腐食する原因にもなるので望ましくない。When the pH of PTW exceeds 8.5, the melt viscosity near 380 ° C, which is the processing temperature of the polyetherimide resin, gradually increases and gelation occurs in the polyetherimide resin composition with a high PTW content. This may cause a phenomenon that the injection molding machine is broken, for example. PH
Is less than 6.0, the effect of improving the strength of the resulting polyetherimide resin composition is not only small, but also
It is not desirable because it causes corrosion of the mold.
一方Ｘ線回析チヤートにおける２θ＝13.8゜の特性ピ
ークにおける半値幅とは13.8゜におけるピーク高さ
（Ｈ）、1/2Hでのピーク幅（Ｗ）とすると、W/Hで表わ
される値であり、従来市販されているPTWの殆どのもの
は、半値幅が0.1を越えるものが多かつた。On the other hand, the half-width at the characteristic peak of 2θ = 13.8 ° in the X-ray diffraction chart is a value represented by W / H, where the peak height (H) at 13.8 ° and the peak width (W) at 1 / 2H are shown. In fact, most of the conventional commercially available PTWs have a half width exceeding 0.1 in many cases.
PTWの半値幅が0.1を越えると、PTW自体の結晶化度が
充分でなく、強度の向上効果、溶融粘度の安定化、耐薬
品性に悪影響を及ぼす傾向にあり本発明の目的には望ま
しくない。本発明の目的には、0.10以下、好ましくは0.
05以下であることが望ましい。When the half width of PTW exceeds 0.1, the crystallinity of PTW itself is not sufficient, the effect of improving strength, stabilization of melt viscosity, and a tendency to adversely affect chemical resistance, which is not desirable for the purpose of the present invention. . For the purpose of the present invention, 0.10 or less, preferably 0.
It is desirable to be 05 or less.
本発明のPTWのポリエーテルイミド樹脂に配合される
量は、ポリエーテルイミド樹脂と該PTWの合計量に対し
て、PTW5〜60重量％が適当であり、５重量％未満の場合
には耐熱性・剛性・強度の改良効果が不充分であり、
又、60重量％を越える場合には、溶融混練機へのPTWの
供給が、PTW自体が非常に嵩高い為、シランカツプリン
グ剤、チタネート系カツプリング剤等の表面処理剤で表
面処理をしてPTWの供給性を改良しても、尚困難である
し、得られた樹脂組成物の成形時の溶融流動性が著しく
低下するので、実用性に乏しい。The amount of the PTW of the present invention to be blended with the polyetherimide resin is suitably 5 to 60% by weight of the PTW based on the total amount of the polyetherimide resin and the PTW.・ The effect of improving rigidity and strength is insufficient.
If the content exceeds 60% by weight, the supply of PTW to the melt kneader is very bulky, so the surface is treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. Even if the supply of PTW is improved, it is still difficult and the melt fluidity of the obtained resin composition at the time of molding is significantly reduced, so that the practicality is poor.
表面処理剤としては、ポリエーテルイミド樹脂の溶融
温度が300℃を越える為、加工温度に耐えるカツプリン
グ剤は殆どないが、γ−メルカプトプロピルトリメトキ
シシラン、β−（3,4−エポキシシクロヘキシル）エチ
ルトリメトキシシラン、Ｎ−フエニル−γ−アミノプロ
ピルトリメトキシシランが比較的加工温度に耐え、PTW
の補強効果発現に効果がみられることを見出した。As the surface treatment agent, there is almost no coupling agent that can withstand the processing temperature because the melting temperature of the polyetherimide resin exceeds 300 ° C., but γ-mercaptopropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane are relatively resistant to processing temperatures,
It was found that the effect of the reinforcement effect was exhibited.
尚、本発明のポリエーテルイミド樹脂組成物について
は、本発明の効果を損なわない範囲内で、熱安定剤、紫
外線吸収剤、滑剤、顔料などの着色剤、難燃剤、帯電防
止剤、ケツチエンブラツク等の導電性付与剤、CaCO3等
の粉末状或いはマイカ等の鱗片状充填剤、ガラス繊維、
炭素繊維等の強化剤などの各種添加剤を目的に応じて併
用してもよい。In addition, the polyetherimide resin composition of the present invention includes a heat stabilizer, an ultraviolet absorber, a lubricant, a coloring agent such as a pigment, a flame retardant, an antistatic agent, and a ketjene as long as the effects of the present invention are not impaired. Conductivity-imparting agents such as black, powder-like filler such as CaCO 3 or scaly filler such as mica, glass fiber,
Various additives such as a reinforcing agent such as carbon fiber may be used in combination depending on the purpose.
本発明の樹脂組成物はポリエーテルイミド樹脂とPTW
が均一に混合されていることが必要で、この添加混合方
法は特に制限されることはなく、種々の手段が採用でき
る。The resin composition of the present invention comprises a polyetherimide resin and PTW
Are required to be uniformly mixed, and this addition and mixing method is not particularly limited, and various means can be adopted.
例えば、各々別々に溶融押出機に供給して混合するこ
ともできるし、予めヘンシエルミキサー、リボンブレン
ダー、タンブラーなどの混合機を利用して予備混合した
上で、溶融混合機に供給して溶融混合することもでき
る。又、目的によつては、水性媒体や有機媒体に分散せ
しめて、湿式混合法により混合することも可能である。For example, they can be separately supplied to a melt extruder and mixed, or preliminarily mixed using a mixer such as a Hensiel mixer, a ribbon blender or a tumbler, and then supplied to a melt mixer to melt. They can also be mixed. Further, depending on the purpose, it is also possible to disperse in an aqueous medium or an organic medium and mix by a wet mixing method.
上記した本発明の樹脂組成物は、射出成形法、押出成
形法、圧縮成形法等の成形法により、所望の成形品（フ
ルム、シート等を含む）に成形することができる。The above-described resin composition of the present invention can be formed into a desired molded product (including a film, a sheet, and the like) by a molding method such as an injection molding method, an extrusion molding method, and a compression molding method.
（実 施 例） 以下、実施例により本発明を説明するが、これらは単
なる例示であり、本発明はこれらにより限定されるもの
ではない。(Examples) Hereinafter, the present invention will be described by way of examples, but these are merely examples, and the present invention is not limited thereto.
実施例１〜３ ポリエーテルイミド樹脂として、ウルテム1010〜1000
（ゼネラル・エレクトリツク社製）と、６−チタン酸カ
リウム繊維として、pH6.8、Ｘ線回析チヤート（第１図
参照）の２θ＝13.8゜の特性ピークにおける半値幅が0.
02、平均繊維径が0.3μｍ、平均繊維長15μｍのもの
を、供給性を良くする為に、Ｎ−フエニル−γ−アミノ
プロピルトリメトキシシランで６−チタン酸カリウム繊
維重量の１重量％添加により表面処理したもの（表面処
理後のpH7.3）を、第１表の割合となるように、二軸押
出機〔池貝鉄工（株）製、PCM45〕のメインホツパー及
びサイドフイーダーから別々に供給し、シリンダー温度
340℃にて、溶融混練した後、ストランドカツト方式に
よりペレツト化した。得られたペレツトを射出成形機
〔日精樹脂工業（株）製、FS−150N〕にて、シリンダー
温度370℃、金型温度120℃にて射出成形して各種試験片
を得た。Examples 1 to 3 Ultem 1010 to 1000 as a polyetherimide resin
As a 6-potassium titanate fiber (pH 6.8, X-ray diffraction chart (see FIG. 1)), the half-width at the characteristic peak of 2θ = 13.8 ° is 0.
02. In order to improve the feedability, a fiber having an average fiber diameter of 0.3 μm and an average fiber length of 15 μm is added with N-phenyl-γ-aminopropyltrimethoxysilane by adding 1% by weight of 6-potassium titanate fiber weight. The surface-treated product (pH 7.3 after surface treatment) was supplied separately from the main hopper and side feeder of a twin-screw extruder [PCM45, manufactured by Ikegai Iron Works Co., Ltd.] so as to have the ratio shown in Table 1. , Cylinder temperature
After melt-kneading at 340 ° C., the mixture was pelletized by a strand cutting method. The obtained pellets were injection molded at 370 ° C. cylinder temperature and 120 ° C. mold temperature with an injection molding machine [FS-150N, manufactured by Nissei Plastics Industry Co., Ltd.] to obtain various test pieces.
引張特性、曲げ特性、熱変形温度は、それぞれ、ASTM
D−638、Ｄ−790、Ｄ−648に準拠して測定した。又、
溶融粘度安定性を評価するために、シリンダー温度390
℃、金型温度120℃、射出圧1000kg/cm2における、幅10m
m、深さ2mmの断面をスパイラル状に有する棒流動金型に
て、シリンダー中における滞留時間をかえて、流動長の
長さ変化を、５分おきに測定し、その代表値を記す。結
果を第１表に示す。Tensile properties, bending properties, and heat distortion temperatures
It measured according to D-638, D-790, and D-648. or,
Cylinder temperature 390 to evaluate melt viscosity stability
℃, mold temperature 120 ° C, injection pressure 1000kg / cm 2 , width 10m
The change in the length of the flow length was measured every 5 minutes using a rod flow mold having a section of 2 m in depth and a depth of 2 mm in a spiral shape, while changing the residence time in the cylinder, and the representative value was recorded. The results are shown in Table 1.
比較例１〜３ ウルテム1010−1000をそのまま射出成形した場合（比
較例１）と、６−チタン酸カリウム繊維として、pH9.
8、Ｘ線回析チヤート（第２図参照）の13.8゜の特性ピ
ークにおける半値幅が0.157のもの、或いは当該繊維を
更に550℃で１時間焼成した後、水洗後乾燥してpHが8.
6、半値幅が0.13で、平均繊維長、平均繊維径は実施例
と全く同じで、それぞれ0.3μｍ、15μｍのものを、同
様にシランカツプリング剤で表面処理した。Comparative Examples 1 to 3 When Ultem 1010-1000 was injection-molded as it was (Comparative Example 1), and when pH 6 was determined as 6-potassium titanate fiber.
8. X-ray diffraction chart (see FIG. 2) having a half-width at a characteristic peak of 13.8 ° of 0.157, or the fiber is further baked at 550 ° C. for 1 hour, washed with water, dried and adjusted to pH 8.
6. The half-width of 0.13, the average fiber length and the average fiber diameter were exactly the same as in the examples, and 0.3 μm and 15 μm, respectively, were similarly surface-treated with a silane coupling agent.
表面処理後のそれぞれの６−チタン酸カリウム繊維の
pHは、それぞれ10.2及び8.8であつた。Of each 6-potassium titanate fiber after surface treatment
The pH was 10.2 and 8.8, respectively.
これらのチタン酸カリウム繊維を、それぞれ実施例と
同様の方法で、ウルテム1010−1000 70重量％と、６−
チタン酸カリウム繊維30重量％となるように溶融混練
後、ペレツト化して後、同様の評価を行つた。結果をま
とめて第１表に示す。Each of these potassium titanate fibers was treated with Ultem 1010-1000 70% by weight and 6-
The same evaluation was performed after melt-kneading to 30% by weight of potassium titanate fiber and pelletizing. The results are summarized in Table 1.
第１表より、６−チタン酸カリウム繊維として、pH6.
0〜8.5の範囲内にあり、Ｘ線回析チヤートの２θ＝13.8
゜の特性ピークにおける半値幅が0.10以下の６−チタン
酸カリウム繊維を、５〜60重量％の範囲内で含有したポ
リエーテルイミド樹脂組成物は、本発明の特許請求の範
囲以外の６−チタン酸カリウム繊維を配合したものよ
り、射出成形機（加工機械）中での滞留時間が長くなつ
ても流動性が一定であり、pHの高い物では20分というか
なり短時間にもかかわらず、流動性が極端に悪くなり、
同じ成形条件では、シヨートショツトを起こしたり、更
に長時間滞留させた場合には、射出成形機中で固つてし
まい運転不能となる為、均質な成形品の長時間にわたる
量産を行う上で、根本的な問題となつていた。From Table 1, as a 6-potassium titanate fiber, pH 6.
In the range of 0 to 8.5, and 2θ = 13.8 of the X-ray diffraction chart.
The polyetherimide resin composition containing 6-potassium 6-titanate fiber having a half-value width of 0.10 or less in the characteristic peak of ゜ in the range of 5 to 60% by weight is a 6-titanium resin other than the claims of the present invention. The flowability is constant even when the residence time in the injection molding machine (processing machine) is longer than that containing potassium acid fiber. Sex becomes extremely bad,
Under the same molding conditions, if a short shot occurs or if it is kept for a longer period of time, it will become stiff in the injection molding machine and become inoperable. Problem.
又、半値幅の小さい（結晶化度が高い）本発明品の方
が得られる樹脂組成物の機械物性が優れる傾向にあるこ
とが明らかである。Also, it is clear that the resin composition of the present invention having a smaller half width (higher crystallinity) tends to have better mechanical properties of the obtained resin composition.
（発明の効果） 本発明はポリエーテルイミド樹脂に、pH6.0〜8.5、Ｘ
線回析チヤートの２θ＝13.8゜の特性ピークにおける半
値幅が0.10以下の６−チタン酸カリウム繊維を、５〜60
重量％配合することにより、機械的強度、剛性，耐熱性
の向上効果が顕著なことを認めると共に、従来の６−チ
タン酸カリウム繊維で大きな問題となり実用化を阻んで
いた。溶融時の粘度増加（加工機械に滞留時の流動性の
大幅な減少）、ひいてはゲル化により、加工機械の長時
間の稼動が不能となる点が解消し、広い応用分野、殊に
薄肉成形品（フイルム等の押出加工品、時計の歯車等の
超薄肉・小型射出成形品）において、ポリエーテルイミ
ド樹脂組成物の実用範囲を、飛躍的に拡大する効果が得
られた。 (Effect of the Invention) The present invention provides a polyetherimide resin having a pH of 6.0 to 8.5 and an X
A 6-potassium titanate fiber having a half value width of 0.10 or less at a characteristic peak of 2θ = 13.8 ° of a line diffraction chart was prepared by 5 to 60
It was recognized that the effect of improving the mechanical strength, rigidity, and heat resistance was remarkable by blending by weight%, and the conventional potassium 6-titanate fiber became a serious problem and prevented its practical use. Increased viscosity during melting (significant decrease in fluidity when staying in the processing machine) and, by extension, gelation eliminates the point where the processing machine cannot be operated for a long time. (Extruded products such as films, ultra-thin and small-sized injection-molded products such as timepiece gears), the effect of dramatically expanding the practical range of the polyetherimide resin composition was obtained.
第１〜２図はそれぞれ実施例及び比較例で用いた６−チ
タン酸カリウム繊維のＸ線回折チヤートである。1 and 2 are X-ray diffraction charts of potassium 6-titanate fiber used in Examples and Comparative Examples, respectively.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭59−207980（ＪＰ，Ａ) 特開 昭60−228557（ＪＰ，Ａ) 特開 昭61−42548（ＪＰ，Ａ) 特開 昭60−144363（ＪＰ，Ａ) 特開 昭61−37991（ＪＰ，Ａ) 特開 昭61−185566（ＪＰ，Ａ) 特開 昭62−207365（ＪＰ，Ａ) 特開 昭62−22549（ＪＰ，Ａ) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-59-207980 (JP, A) JP-A-60-228557 (JP, A) JP-A-61-42548 (JP, A) JP-A 60-228 144363 (JP, A) JP-A-61-37991 (JP, A) JP-A-61-185566 (JP, A) JP-A-62-207365 (JP, A) JP-A-62-22549 (JP, A)
Claims (3)
２価の芳香族有機基又はＣ２〜20のアルキレン基、シク
ロアルキレン基、アルキレン末端ポリジオルガノシロキ
サン基の中から選択される２価の有機基を示す。ｎ＝５
〜500）で表わされ、固有粘度がジメチルホルムアミド
中、25℃で0.2〜1.5dl/gであるポリエーテルイミド樹脂
にpH6.0〜8.5、Ｘ線回析チヤートにおける２θ＝13.8゜
の特性ピークにおける半値幅が0.10以下の６−チタン酸
カリウム繊維を、５〜60重量％含有させたことを特徴と
するポリエーテルイミド樹脂組成物。(1) General formula (R 1 is a C 6-30 divalent aromatic organic group, R 2 is a C 6-30 divalent aromatic organic group or a C 2-20 alkylene group, cycloalkylene group, alkylene-terminated polydiorganosiloxane A divalent organic group selected from the groups: n = 5
~ 500), polyetherimide resin having an intrinsic viscosity of 0.2-1.5 dl / g in dimethylformamide at 25 ° C, pH 6.0-8.5, characteristic peak of 2θ = 13.8 ° in X-ray diffraction chart. 5. A polyetherimide resin composition comprising 5 to 60% by weight of a potassium 6-titanate fiber having a half width of 0.10 or less in the above.
タン酸カリウム繊維の含有量が10〜40重量％である請求
項１記載のポリエーテルイミド樹脂組成物。2. The polyetherimide resin composition according to claim 1, wherein the content of potassium 6-titanate fiber having a pH of 6.5 to 8.0 and a half width of 0.05 or less is 10 to 40% by weight.
リング剤で表面処理されたものである請求項１又は２記
載のポリエーテルイミド樹脂組成物。3. The polyetherimide resin composition according to claim 1, wherein the potassium 6-titanate fiber is surface-treated with a silane coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63143873A JP2761563B2 (en) | 1988-06-10 | 1988-06-10 | Polyetherimide resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63143873A JP2761563B2 (en) | 1988-06-10 | 1988-06-10 | Polyetherimide resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01313558A JPH01313558A (en) | 1989-12-19 |
| JP2761563B2 true JP2761563B2 (en) | 1998-06-04 |
Family
ID=15348989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63143873A Expired - Lifetime JP2761563B2 (en) | 1988-06-10 | 1988-06-10 | Polyetherimide resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2761563B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1085707C (en) * | 1997-10-23 | 2002-05-29 | 上海市合成树脂研究所 | Potassium titanate crystal whisker reinforced polyimide composite material |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59207980A (en) * | 1983-05-11 | 1984-11-26 | Otsuka Chem Co Ltd | Friction material composition |
| JPS60144363A (en) * | 1983-12-30 | 1985-07-30 | Mitsubishi Chem Ind Ltd | Polyimide sliding material composition |
| JPS60228557A (en) * | 1984-04-27 | 1985-11-13 | Sumitomo Bakelite Co Ltd | Polyarylene polyether polyimide film |
| JPH0635675B2 (en) * | 1984-07-30 | 1994-05-11 | 大塚化学株式会社 | Resin composition for electric plating |
| JPS6142548A (en) * | 1984-08-06 | 1986-03-01 | Otsuka Chem Co Ltd | Electrically conductive expandable thermoplastic resin composition |
| JPS61185566A (en) * | 1985-02-12 | 1986-08-19 | Otsuka Chem Co Ltd | Resin composition for slidable parts |
| JP2540513B2 (en) * | 1986-03-07 | 1996-10-02 | 三井東圧化学株式会社 | Resin composition with excellent plating characteristics |
| JPS62220549A (en) * | 1986-03-24 | 1987-09-28 | Mitsui Toatsu Chem Inc | Plating resin composition having improved heat transfer characteristic |
| JPH0822954B2 (en) * | 1986-05-06 | 1996-03-06 | 三井東圧化学株式会社 | New polyimide resin composition |
-
1988
- 1988-06-10 JP JP63143873A patent/JP2761563B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01313558A (en) | 1989-12-19 |
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