JP2852973B2 - Method for producing polyimide resin powder - Google Patents
Method for producing polyimide resin powderInfo
- Publication number
- JP2852973B2 JP2852973B2 JP24734990A JP24734990A JP2852973B2 JP 2852973 B2 JP2852973 B2 JP 2852973B2 JP 24734990 A JP24734990 A JP 24734990A JP 24734990 A JP24734990 A JP 24734990A JP 2852973 B2 JP2852973 B2 JP 2852973B2
- Authority
- JP
- Japan
- Prior art keywords
- organic solvent
- polyimide resin
- resin powder
- tetracarboxylic acid
- aromatic tetracarboxylic
- 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
Links
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、工程の簡略化されたポリイミド樹脂粉末の
製造方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for producing a polyimide resin powder whose steps are simplified.
ポリイミド樹脂粉末は、特開昭61−95029号公報に記
載されているように、芳香族テトラカルボン酸成分と芳
香族ジアミン成分のいずれか一方を、Ｎ−メチル−２−
ピロリドン、N,N−ジメチルアセトアミド、N,N−ジメチ
ルホルムアミド、ジエチレングリコールジメチルエーテ
ル等の高沸点有機溶剤に溶解又は懸濁して置き、これに
他方を徐々に添加反応させることによってポリアミド酸
を生成せしめ、次いでこのポリアミド酸をイミド化して
生成したイミド化物を沈澱させた後このイミド化物を濾
別洗浄し、粉砕することにより製造している。このよう
なポリイミド樹脂粉末の製造方法は、大量の高価な高沸
点有機溶媒や触媒を必要とする他、前述の濾別洗浄のた
めの器具を必要とし、しかも高沸点有機溶剤が残存する
と成形時に気泡となって成形製品の品質を損なうため十
分に洗浄しなければならず、製造工程が繁雑で、コスト
が高いという欠点があった。As described in JP-A-61-95029, a polyimide resin powder is prepared by adding one of an aromatic tetracarboxylic acid component and an aromatic diamine component to N-methyl-2-amine.
Pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dissolved or suspended in a high-boiling organic solvent such as diethylene glycol dimethyl ether, and the other is gradually added and reacted to form a polyamic acid. The imidized product produced by imidizing the polyamic acid is precipitated, and then the imidized product is separated by filtration, washed, and pulverized. Such a method for producing a polyimide resin powder requires a large amount of an expensive high-boiling organic solvent and a catalyst, and also requires the above-mentioned equipment for filtration and washing. There is a drawback that bubbles must be sufficiently washed to form bubbles and impair the quality of the molded product, so that the manufacturing process is complicated and the cost is high.
また、得られたポリイミド樹脂粉末は、300〜10,000K
gf/cm2という高圧下で加熱圧縮成形しなければ成形が困
難であるため、成形器具や成形手段が著しく制約される
という問題があった。In addition, the obtained polyimide resin powder is 300 to 10,000K
Unless heat compression molding is performed under a high pressure of gf / cm 2, molding is difficult, and there has been a problem that molding tools and molding means are significantly restricted.
本発明の目的は、前述したイミド化物の濾別や溶媒除
去のための洗浄を必要としないで工程を簡略化し、コス
トの低減を可能にしたポリイミド樹脂粉末の製造方法を
提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyimide resin powder which simplifies the process without requiring the above-mentioned filtration of the imidized product and washing for removing the solvent, thereby enabling cost reduction.
このような目的を達成する本発明のポリイミド樹脂粉
末の製造方法は、芳香族テトラカルボン酸成分を沸点12
0℃以下の低沸点有機溶剤に溶解し、得られた該芳香族
テトラカルボン酸成分の溶液に芳香族ジアミン成分を添
加して固形分80重量％前後の混合溶液となし、この混合
溶液を前記低沸点有機溶剤の沸点以上の温度に減圧下で
加熱して芳香族テトラカルボン酸成分と芳香族ジアミン
成分とを反応させると共に該低沸点有機溶剤を蒸発させ
てポリアミド酸の乾固物を生成せしめ、この乾固物を破
砕し、ついで得られる破砕物を減圧下に加熱してポリア
ミド酸をイミド化した後、得られるポリイミド樹脂を粉
末化してなることを特徴とする。The method for producing a polyimide resin powder of the present invention that achieves the above object has a feature that the aromatic tetracarboxylic acid component has a boiling point
Dissolved in a low boiling organic solvent at 0 ° C. or lower, and added an aromatic diamine component to the obtained solution of the aromatic tetracarboxylic acid component to form a mixed solution having a solid content of about 80% by weight. The aromatic tetracarboxylic acid component and the aromatic diamine component are reacted by heating under reduced pressure to a temperature equal to or higher than the boiling point of the low boiling organic solvent, and the low boiling organic solvent is evaporated to produce a dried polyamic acid. Then, the dried product is crushed, the obtained crushed product is heated under reduced pressure to imidize the polyamic acid, and the obtained polyimide resin is powdered.
このように芳香族テトラカルボン酸成分と芳香族ジア
ミン成分とを低沸点有機溶剤中で、その沸点以上の温度
に加熱し、溶剤を蒸発させながら反応させることによっ
て、実質的に溶剤を含有せず、濾別や洗浄を行う必要の
ないポリアミド酸を得ることができる。また、得られた
ポリアミド酸を粉末化して加熱プリイミド化したポリイ
ミド樹脂粉末は10〜30Kgf/cm2の低い圧力下で成形する
ことができるため、その成形が容易で、成形用の器具や
手段の制約を著しく少なくすることができる。Thus, by heating the aromatic tetracarboxylic acid component and the aromatic diamine component in a low-boiling organic solvent to a temperature equal to or higher than the boiling point and causing the reaction to proceed while evaporating the solvent, substantially no solvent is contained. A polyamic acid which does not need to be filtered or washed can be obtained. Also, polyimide resin powder polyamic acid was heated Puriimido by being powdered to obtain since it can be molded under low pressure of 10~30Kgf / cm 2, the molding is easy, the equipment and means for molding Restrictions can be significantly reduced.
以下、本発明のポリイミド樹脂粉末の製造方法を順序
をおって説明する。Hereinafter, the method for producing the polyimide resin powder of the present invention will be described in order.
まず、適当な容器に低沸点有機溶剤を入れた後芳香族
テトラカルボン酸成分を添加して溶解し、これに芳香族
ジアミン成分を混合する。First, a low boiling organic solvent is placed in a suitable container, and then an aromatic tetracarboxylic acid component is added and dissolved, and an aromatic diamine component is mixed therein.
本発明に使用する芳香族テトラカルボン酸成分として
は、たとえばベンゾフェノンテトラカルボン酸又はその
酸二無水物、ピロメリット酸又はその酸二無水物、ビス
（3,4−ジカルボキシフェニル）エーテル又はその酸無
水物、ビス（3,4−ジカルボキシフェニル）スルホン又
はその酸無水物、ビス（3,4−ジカルボキシフェニル）
メタン又はその酸無水物等がある。好ましくはベンゾフ
ェノンテトラカルボン酸又はその酸二無水物を単独又は
他の芳香族テトラカルボン酸と併用するのがよい。The aromatic tetracarboxylic acid component used in the present invention includes, for example, benzophenonetetracarboxylic acid or its acid dianhydride, pyromellitic acid or its acid dianhydride, bis (3,4-dicarboxyphenyl) ether or its acid Anhydride, bis (3,4-dicarboxyphenyl) sulfone or its anhydride, bis (3,4-dicarboxyphenyl)
There are methane and its acid anhydride. Preferably, benzophenone tetracarboxylic acid or its dianhydride is used alone or in combination with another aromatic tetracarboxylic acid.
また、芳香族ジアミン成分としては、たとえばメチレ
ンジアニリン、ジアミノベンゾフェノン、ジアミノジフ
ェニルスルホン、ジアミノジフェニルアミン等がある。
好ましくはメチレンジアニリンを単独又は他の芳香族ジ
アミン成分と併用するのがよい。これらの芳香族テトラ
カルボン酸成分と芳香族ジアミン成分とは低沸点有機溶
剤に対し固形分重量で80重量％前後となるように混合す
る。80重量％前後としたのは、有機溶剤は芳香族テトラ
カルボン酸成分と芳香族ジアミン成分とを溶解するに足
る量であれば、蒸発除去のためにはなるべく少ない量で
あるのがよいからである。Examples of the aromatic diamine component include methylene dianiline, diaminobenzophenone, diaminodiphenylsulfone, diaminodiphenylamine and the like.
Preferably, methylene dianiline is used alone or in combination with another aromatic diamine component. The aromatic tetracarboxylic acid component and the aromatic diamine component are mixed so that the solid content is about 80% by weight based on the low boiling point organic solvent. The reason why the amount is set to about 80% by weight is that the organic solvent should be as small as possible for evaporation and removal as long as it is sufficient to dissolve the aromatic tetracarboxylic acid component and the aromatic diamine component. is there.
さらに末端基形成成分として、ナジック酸無水物、４
−ビニルフタル酸無水物、４−エチニルフタル酸無水物
又はこれらのアルキルエステルを混合することもでき
る。Further, as a terminal group forming component, nadic anhydride, 4
-Vinylphthalic anhydride, 4-ethynylphthalic anhydride or their alkyl esters can also be mixed.
これらの芳香族テトラカルボン酸成分と芳香族ジアミ
ン成分の反応媒体の低沸点有機溶剤としては、沸点120
℃以下のものである。たとえば、メチルアルコール、エ
チルアルコールメチルセロソルブ等を挙げることがで
き、より好ましくはメチルアルコールを単独で使用する
のがよい。The low-boiling organic solvent of the reaction medium of the aromatic tetracarboxylic acid component and the aromatic diamine component has a boiling point of 120.
It is below ° C. For example, methyl alcohol, ethyl alcohol methyl cellosolve and the like can be mentioned, and it is more preferable to use methyl alcohol alone.
本発明に使用する反応容器は200℃程度の耐熱性を有
するものであればよい。たとえば金属製容器やアルミ箔
や弗素樹脂コーテッドガラス布を用いて作製した簡単な
容器を使用することができる。The reaction vessel used in the present invention may have a heat resistance of about 200 ° C. For example, a metal container or a simple container manufactured using aluminum foil or a fluororesin coated glass cloth can be used.
前述した低沸点有機溶剤中に芳香族テトラカルボン酸
成分を溶解させ（低沸点有機溶剤がアルコールである場
合、芳香族テトラカルボン酸成分はこのアルコールと反
応してエステルの形態となって溶解している）、次いで
芳香族ジアミン成分を投入溶解させる。これを前記の容
器に投入し、低沸点有機溶剤の沸点以上の温度に減圧下
で加熱する。この加熱により芳香族テトラカルボン酸成
分と芳香族ジアミン成分とが反応（アミド化反応）する
と共に、低沸点有機溶媒や揮発性の反応副生成物が除去
され、スラリー状のポリアミド酸が生成される。さらに
加熱を続けてポリアミド酸を乾燥状態の固形物にし、反
応容器から取り出し、粗く破砕する。破砕物を再度オー
ブン中で減圧下で加熱（たとえば200℃）し、イミド化
すると共に溶剤、揮発性の副生成物等を完全に除去す
る。このイミド化樹脂を破砕して微粉末状にすることに
よりポリイミド樹脂粉末とする。The aromatic tetracarboxylic acid component is dissolved in the low-boiling organic solvent described above (when the low-boiling organic solvent is an alcohol, the aromatic tetracarboxylic acid component reacts with the alcohol to form an ester and dissolve. ), And then the aromatic diamine component is introduced and dissolved. This is charged into the container and heated under reduced pressure to a temperature equal to or higher than the boiling point of the low boiling organic solvent. The heating causes the aromatic tetracarboxylic acid component and the aromatic diamine component to react (amidation reaction), and at the same time, removes the low-boiling organic solvent and volatile reaction by-products, thereby producing a slurry-like polyamic acid. . The heating is further continued to turn the polyamic acid into a dry solid, removed from the reaction vessel, and coarsely crushed. The crushed material is heated again in an oven under reduced pressure (for example, at 200 ° C.) to imidize it and completely remove the solvent, volatile by-products and the like. The imidized resin is pulverized into fine powder to obtain a polyimide resin powder.
また、このポリアミド酸のイミド化には、無水酢酸、
無水プロピオン酸、無水酪酸等のイミド化剤やトリメチ
ルアミン、トリエチルアミン、ピリジン、ピコリン等の
イミド化触媒を使用してイミド化することができるが、
反応を穏やかに進める方が優良な成形物を得られ易いこ
とから、無触媒で加熱のみにより反応を進行させること
が好ましい。In addition, acetic anhydride,
Although it can be imidated using an imidizing agent such as propionic anhydride or butyric anhydride or an imidization catalyst such as trimethylamine, triethylamine, pyridine or picoline,
Since it is easy to obtain a good molded product when the reaction is gently advanced, it is preferable to proceed the reaction only by heating without a catalyst.
かくして得られたポリイミド樹脂粉末は、任意の各種
金型を用いて、250〜320℃、10〜30Kgf/cm2の条件下で
圧縮成形することにより、完全に架橋硬化した各種製品
を作製することができる。The polyimide resin powder thus obtained is compression molded under the conditions of 250 to 320 ° C. and 10 to 30 Kgf / cm 2 by using various molds to produce various products which are completely cross-linked and cured. Can be.
以下、実施例により本発明を具体的に説明する。 Hereinafter, the present invention will be described specifically with reference to examples.
反応容器として、弗素樹脂コーテッドガラス布（弗素
樹脂は四弗化ポリエチレンを使用した）からなる幅250m
m、長さ270mm、高さ150mmの箱型容器を使用した。The reaction vessel is made of fluororesin coated glass cloth (fluororesin used is tetrafluoroethylene), 250m wide
A box-shaped container having a length of 270 mm, a length of 270 mm and a height of 150 mm was used.
メチルアルコール（沸点63℃）70cc（55g）に、3,
3′,4,4′−ベンゾフェノンテトラカルボン酸二無水物6
0.8gを添加して溶解させた後、メチレンジアニリン68.9
g、ナジック酸メチルエステル58.4gを添加した（固形分
重量82重量％）。Methyl alcohol (boiling point 63 ℃) 70cc (55g), 3,
3 ', 4,4'-benzophenonetetracarboxylic dianhydride 6
After adding and dissolving 0.8 g, methylene dianiline 68.9
g and 58.4 g of nadic acid methyl ester (solids weight 82% by weight).
この混合溶液を前記箱形容器に入れ、この容器を120
℃に加熱されたオーブン中に投入し、減圧（200mmHg）
下で、1.5時間加熱した後容器内から固形の反応生成物
を取り出した。This mixed solution is placed in the box-shaped container, and the container is
Put into an oven heated to ℃, and decompress (200mmHg)
After heating for 1.5 hours, a solid reaction product was taken out of the vessel.
この固形物をスパチュラを用いて３〜5cm角の大きさ
に破砕した。This solid was crushed to a size of 3 to 5 cm square using a spatula.
破砕物を前記容器に入れて200℃に加熱されたオーブ
ン中に投入し減圧（100mmHg）下で３時間加熱した。The crushed material was put in the container, placed in an oven heated to 200 ° C., and heated under reduced pressure (100 mmHg) for 3 hours.
容器から破砕物を取り出し、擦り鉢に移して微粉末に
なるまで擦り潰し、200gのイミド樹脂粉末を得た。The crushed material was taken out of the container, transferred to a mortar and crushed until it became fine powder, to obtain 200 g of imide resin powder.
上述の工程を繰り返してさらに200gの樹脂粉末を得
た。The above steps were repeated to obtain another 200 g of resin powder.
サイズが幅20mm、長さ320mm、高さ6mmのバイトンゴム
シートを使用し、サイズが幅500mm,長さ500mm,高さ5mm
のアルミ板上に300mm×300mmのフレームを組み、そこに
前述のごとくして作製した400gのイミド樹脂粉末を充填
し、プレス成形機により圧力25Kgf/cm2,温度316℃の条
件で２時間プレス成形した。放冷した後サイズが幅300m
m,長さ320mm,高さ3mmの樹脂成形品を得た。Using a Viton rubber sheet with a width of 20 mm, a length of 320 mm, and a height of 6 mm, the size is 500 mm wide, 500 mm long, 5 mm high
A 300 mm x 300 mm frame was assembled on an aluminum plate, and 400 g of the imide resin powder prepared as described above was filled into the frame and pressed for 2 hours at a pressure of 25 kgf / cm 2 and a temperature of 316 ° C by a press molding machine. Molded. After cooling down, the size is 300m wide
m, a length of 320 mm and a height of 3 mm were obtained.
得られた樹脂成形品は、別々に作製した200gずつの樹
脂粉末を一緒にして成形したにもかかわらず、気泡等を
含くんでいない極めて均質なものであった。The obtained resin molded product was extremely homogeneous without containing bubbles and the like, despite the fact that 200 g of each separately prepared resin powder was molded together.
本発明によれば、芳香族テトラカルボン酸成分を沸点
120℃以下の低沸点有機溶剤に溶解し、得られた該芳香
族テトラカルボン酸成分の溶液に芳香族ジアミン成分を
添加して固形分80重量％前後の混合溶液となし、この混
合溶液を前記低沸点有機溶剤の沸点以上の温度に減圧下
で加熱して芳香族テトラカルボン酸成分と芳香族ジアミ
ン成分とを反応させると共に該低沸点有機溶剤を蒸発さ
せてポリアミド酸の乾固物を生成せしめ、この乾固物を
破砕し、ついで得られる破砕物を減圧下に加熱してポリ
アミド酸をイミド化した後、得られるポリイミド樹脂を
粉末化したため、簡単な反応容器を使用した減圧オーブ
ンによる加熱を主体とし、かつ濾別や洗浄の必要がない
単純化した方法により、実質的に溶剤を含有しない樹脂
粉末を低コストで製造することができる。According to the present invention, the aromatic tetracarboxylic acid component has a boiling point
Dissolved in a low boiling organic solvent of 120 ° C. or less, added an aromatic diamine component to the obtained solution of the aromatic tetracarboxylic acid component to form a mixed solution having a solid content of about 80% by weight, and prepared this mixed solution. The aromatic tetracarboxylic acid component and the aromatic diamine component are reacted by heating under reduced pressure to a temperature equal to or higher than the boiling point of the low boiling organic solvent, and the low boiling organic solvent is evaporated to produce a dried polyamic acid. After crushing the dried product, and then heating the obtained crushed product under reduced pressure to imidize the polyamic acid and then pulverizing the obtained polyimide resin, heating by a reduced-pressure oven using a simple reaction vessel was carried out. By a simplified method that is mainly used and does not require filtration or washing, resin powder substantially containing no solvent can be produced at low cost.
しかも本発明により得られた樹脂粉末は、10〜30Kg/c
m2の低い加圧条件下で圧縮成形できるため、成形に際し
て汎用の器具や手段を使用できる。また、気泡の原因と
なる溶剤等を実質的に含有しないので、均質性に優れた
成形製品を得ることができる。Moreover, the resin powder obtained according to the present invention is 10 to 30 kg / c.
Since compression molding can be performed under a pressure of as low as m 2 , general-purpose instruments and means can be used for molding. In addition, since a solvent or the like that causes bubbles is not substantially contained, a molded product having excellent homogeneity can be obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平１−242622（ＪＰ，Ａ) 特開 昭61−241326（ＪＰ，Ａ) 特開 昭61−95028（ＪＰ，Ａ) 特開 昭62−212435（ＪＰ，Ａ) 特開 昭57−200453（ＪＰ，Ａ) 特開 昭56−163124（ＪＰ，Ａ) 特開 昭56−67338（ＪＰ，Ａ) 特開 昭49−134794（ＪＰ，Ａ) 特公 昭45−21957（ＪＰ，Ｂ１) 特公 昭49−13878（ＪＰ，Ｂ１) 特公 昭46−27821（ＪＰ，Ｂ１) ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-242622 (JP, A) JP-A-61-241326 (JP, A) JP-A-61-95028 (JP, A) JP-A-62 212435 (JP, A) JP-A-57-200453 (JP, A) JP-A-56-163124 (JP, A) JP-A-56-67338 (JP, A) JP-A-49-134794 (JP, A) JP-B-45-21957 (JP, B1) JP-B-49-13878 (JP, B1) JP-B-46-27821 (JP, B1)
Claims (1)
以下の低沸点有機溶剤に溶解し、得られた該芳香族テト
ラカルボン酸成分の溶液に芳香族ジアミン成分を添加し
て固形分80重量％前後の混合溶液となし、この混合溶液
を前記低沸点有機溶剤の沸点以上の温度に減圧下で加熱
して芳香族テトラカルボン酸成分と芳香族ジアミン成分
とを反応させると共に該低沸点有機溶剤を蒸発させてポ
リアミド酸の乾固物を生成せしめ、この乾固物を破砕
し、ついで得られる破砕物を減圧下に加熱してポリアミ
ド酸をイミド化した後、得られるポリイミド樹脂を粉末
化してなるポリイミド樹脂粉末の製造方法。1. An aromatic tetracarboxylic acid component having a boiling point of 120 ° C.
Dissolved in the following organic solvent having a low boiling point, and an aromatic diamine component was added to the obtained solution of the aromatic tetracarboxylic acid component to form a mixed solution having a solid content of about 80% by weight. The aromatic tetracarboxylic acid component is reacted with the aromatic diamine component by heating under reduced pressure to a temperature equal to or higher than the boiling point of the organic solvent, and the low boiling organic solvent is evaporated to produce a dried polyamic acid. A method for producing a polyimide resin powder, comprising crushing a dried product, heating the obtained crushed product under reduced pressure to imidize the polyamic acid, and then pulverizing the obtained polyimide resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24734990A JP2852973B2 (en) | 1990-09-19 | 1990-09-19 | Method for producing polyimide resin powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24734990A JP2852973B2 (en) | 1990-09-19 | 1990-09-19 | Method for producing polyimide resin powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04126721A JPH04126721A (en) | 1992-04-27 |
| JP2852973B2 true JP2852973B2 (en) | 1999-02-03 |
Family
ID=17162092
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24734990A Expired - Lifetime JP2852973B2 (en) | 1990-09-19 | 1990-09-19 | Method for producing polyimide resin powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2852973B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3018143B2 (en) * | 1996-02-28 | 2000-03-13 | 株式会社先進材料利用ガスジェネレータ研究所 | Method and apparatus for molding polyimide resin |
-
1990
- 1990-09-19 JP JP24734990A patent/JP2852973B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04126721A (en) | 1992-04-27 |
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