JPH04126721A - Production of polyimide resin powder and compression molding thereof - Google Patents
Production of polyimide resin powder and compression molding thereofInfo
- Publication number
- JPH04126721A JPH04126721A JP24734990A JP24734990A JPH04126721A JP H04126721 A JPH04126721 A JP H04126721A JP 24734990 A JP24734990 A JP 24734990A JP 24734990 A JP24734990 A JP 24734990A JP H04126721 A JPH04126721 A JP H04126721A
- Authority
- JP
- Japan
- Prior art keywords
- boiling point
- organic solvent
- tetracarboxylic acid
- resin powder
- 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.)
- Granted
Links
- 239000000843 powder Substances 0.000 title claims abstract description 25
- 229920001721 polyimide Polymers 0.000 title claims description 13
- 239000009719 polyimide resin Substances 0.000 title claims description 13
- 238000000748 compression moulding Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000009835 boiling Methods 0.000 claims abstract description 29
- -1 aromatic tetracarboxylic acid Chemical class 0.000 claims abstract description 23
- 239000003960 organic solvent Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 16
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 abstract description 4
- FHBXQJDYHHJCIF-UHFFFAOYSA-N (2,3-diaminophenyl)-phenylmethanone Chemical compound NC1=CC=CC(C(=O)C=2C=CC=CC=2)=C1N FHBXQJDYHHJCIF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 238000001914 filtration Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- DDCJHFYXAPQYLA-UHFFFAOYSA-N (3-chlorophenyl)-phenylmethanol Chemical compound C=1C=CC(Cl)=CC=1C(O)C1=CC=CC=C1 DDCJHFYXAPQYLA-UHFFFAOYSA-N 0.000 description 1
- KNDQHSIWLOJIGP-UMRXKNAASA-N (3ar,4s,7r,7as)-rel-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione Chemical compound O=C1OC(=O)[C@@H]2[C@H]1[C@]1([H])C=C[C@@]2([H])C1 KNDQHSIWLOJIGP-UMRXKNAASA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- YGOFNNAZFZYNIX-UHFFFAOYSA-N 3-N-phenylbenzene-1,2,3-triamine Chemical compound NC=1C(=C(C=CC1)NC1=CC=CC=C1)N YGOFNNAZFZYNIX-UHFFFAOYSA-N 0.000 description 1
- AIVVXPSKEVWKMY-UHFFFAOYSA-N 4-(3,4-dicarboxyphenoxy)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1OC1=CC=C(C(O)=O)C(C(O)=O)=C1 AIVVXPSKEVWKMY-UHFFFAOYSA-N 0.000 description 1
- AVCOFPOLGHKJQB-UHFFFAOYSA-N 4-(3,4-dicarboxyphenyl)sulfonylphthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1S(=O)(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 AVCOFPOLGHKJQB-UHFFFAOYSA-N 0.000 description 1
- IWXCYYWDGDDPAC-UHFFFAOYSA-N 4-[(3,4-dicarboxyphenyl)methyl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1CC1=CC=C(C(O)=O)C(C(O)=O)=C1 IWXCYYWDGDDPAC-UHFFFAOYSA-N 0.000 description 1
- OHMDZMAJDUVGHO-UHFFFAOYSA-N 5-ethenyl-2-benzofuran-1,3-dione Chemical compound C=CC1=CC=C2C(=O)OC(=O)C2=C1 OHMDZMAJDUVGHO-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
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)
Abstract
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
造方法及びその圧縮成形方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for producing polyimide resin powder with simplified steps and a method for compression molding the same.
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ｍ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 No. 61-95029, polyimide resin powder is prepared by replacing either the aromatic tetracarboxylic acid component or the aromatic diamine component with N-methyl-
2-pyrrolidone, N,N-dimethylacetamide, N,
A polyamic acid is produced by dissolving or suspending it in a high boiling point organic solvent such as N-dimethylformamide or diethylene glycol dimethyl ether, and then gradually adding the other to the solution, and then imidizing this polyamic acid to produce an imidized product. After precipitating, the imidized product is filtered, washed, and pulverized. This method of producing polyimide resin powder requires a large amount of expensive high-boiling point solvents and catalysts, as well as equipment for the above-mentioned filtration and washing, and if high-boiling point organic solvents remain, molding may occur. The disadvantages are that the molded product sometimes becomes bubbles and impairs the quality of the molded product, so it must be thoroughly cleaned, 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．
０００Ｋｇｆ／ｃｍ”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。Moreover, the obtained polyimide resin powder was 300 to 10.
Since molding is difficult without heat compression molding under a high pressure of 0.000 Kgf/cm'', there is a problem in that molding equipment and molding means are severely 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。An object of the present invention is to provide a method for producing polyimide resin powder that simplifies the process without requiring the above-mentioned filtration of the imidide or washing to remove the solvent, thereby making it possible to reduce costs.
本発明の他の目的は成形時の圧力を著しく低減すること
ができ、成形が容易で、かつ成形用の器具や手段の制約
を受けないポリイミド樹脂粉末の成形方法を提供するこ
とにある。Another object of the present invention is to provide a method for molding polyimide resin powder that can significantly reduce the pressure during molding, is easy to mold, and is not limited by molding equipment or means.
〔課題を解決するための手段〕
このような目的を達成する本発明は、芳香族テトラカル
ボン酸成分を低沸点有機溶剤に溶解して該芳香族テトラ
カルボン酸成分の溶液を作製し、これに芳香族ジアミン
成分を添加した上、前記低沸点有機溶剤の沸点以上の温
度に加熱反応せしめてポリアミド酸を生成せしめ、次い
で減圧下で加熱してポリアミド酸をプリイミド化するこ
とを特徴とする。[Means for Solving the Problems] The present invention achieves the above object by dissolving an aromatic tetracarboxylic acid component in a low boiling point organic solvent to prepare a solution of the aromatic tetracarboxylic acid component, and adding a solution to the aromatic tetracarboxylic acid component. The method is characterized in that an aromatic diamine component is added and then heated to a temperature higher than the boiling point of the low boiling point organic solvent to produce a polyamic acid, and then heated under reduced pressure to preimide the polyamic acid.
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／ｃｍ”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。In this way, by heating the aromatic tetracarboxylic acid component and the aromatic diamine component in a low-boiling point organic solvent to a temperature higher than the boiling point of the component, and causing the reaction to occur while evaporating the solvent, it is possible to create a product that does not contain substantially any solvent. , it is possible to obtain polyamic acid that does not require filtration or washing. In addition, the polyimide resin powder obtained by pulverizing the obtained polyamic acid and heating preimide can be molded under a low pressure of 10 to 30 Kgf/cm, making it easy to mold and requiring no molding equipment or means. 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 polyimide resin powder of the present invention will be explained 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 point organic solvent is placed in a suitable container, 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。Examples of the aromatic tetracarboxylic acid component used in the present invention include 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 acid anhydride, bis(3,4-dicarboxyphenyl)methane or its acid anhydride, etc. be. Preferably, benzophenone tetracarboxylic acid or its acid dianhydride is used alone or in combination with other aromatic tetracarboxylic acids.
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
るのがよい。Examples of aromatic diamine components include methylene dianiline, diaminobenzophenone, diaminodiphenylsulfone, and diaminodiphenylamine. Preferably, methylene dianiline is used alone or in combination with other aromatic diamine components. These aromatic tetracarboxylic acid components and aromatic diamine components are preferably mixed in a solid content of about 80% by weight based on the low boiling point organic solvent.
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。Furthermore, as terminal group forming components, nadic acid anhydride, 4-
Vinyl phthalic anhydride, 4-ethynyl phthalic anhydride, or alkyl esters thereof 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
℃以下のものが好ましい。たとエバ、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 point organic solvent used as the reaction medium for these aromatic tetracarboxylic acid components and aromatic diamine components has a boiling point of 120
℃ or less is preferable. Examples include methyl alcohol, ethyl alcohol, methyl cellosolve, etc., 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
や弗素樹脂コーテン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 be one having heat resistance of about 200°C. For example, a metal container or a simple container made of aluminum foil or 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
分を溶解又はエステル化し、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。The aromatic tetracarboxylic acid component is dissolved or esterified in the above-mentioned low boiling point organic solvent, and then the aromatic diamine component is added and dissolved. This is placed in the container and heated under reduced pressure to a temperature higher than the boiling point of the low boiling point organic solvent. Through this heating, the aromatic tetracarboxylic acid component and the aromatic diamine component react (amidation reaction), and the low-boiling organic solvent and volatile reaction by-products are removed, producing a slurry of polyamic acid. .
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、
ブリ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。Further heating is continued to turn the polyamic acid into a dry solid, which is taken out from the reaction vessel and coarsely crushed. The crushed material is heated again under reduced pressure in an oven (for example, 200 ° C.),
While briimidizing, solvents, volatile by-products, etc. are completely removed.
このプリ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。This preimidized resin is crushed to form a fine powder to obtain 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, this polyamic acid can be imidized using an imidizing agent such as acetic anhydride, propionic anhydride, butyric anhydride, or an imidizing catalyst such as trimethylamine, triethylamine, pyridine, picoline, etc. Since it is easier to obtain an excellent molded product when the reaction proceeds slowly, it is preferable to proceed with the reaction only by heating without a catalyst.
か（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／ｃ
ｍ”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 obtained by
By compression molding under the conditions of ``m'', it is possible to produce various products that are completely crosslinked and cured.
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 specifically explained 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２５０
ｍｍ＋ 、長さ２７０１）ｍ１、高さ１５０ｍ５の箱型
容器を使用した。The reaction vessel was made of fluororesin-coated glass cloth (the fluororesin used was polyethylene tetrafluoride) with a width of 250 mm.
A box-shaped container of mm+, length 2701) m1, and height 150 m5 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６０．８ ｇを添加して溶解させた後
、メチレンジアニリン６８．９ｇ、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
), 60.8 g of 3.3', 4.4°-benzophenone tetracarboxylic dianhydride was added and dissolved, and then 68.9 g of methylene dianiline and 58.4 g of nadic acid methyl ester were added. (Solid content weight 82% by weight)
.
この混合樹脂を反応容器に入れ、１２０℃に加熱された
オープン中に投入し、減圧（２００ｍ＋ｗＨｇ）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 resin was placed in a reaction vessel, placed in an open tank heated to 120°C, and heated under reduced pressure (200m+wHg) for 1 hour.
．． After heating for 5 hours, a solid reaction product was taken out from the container.
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 material was crushed into 3 to 5 cm square pieces 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（１００＋＋＋ｓ＋Ｈｇ）下で３時間
加熱した。The crushed material was placed in the container, placed in an oven heated to 200° C., and heated under reduced pressure (100+++s+Hg) 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の樹脂粉末を得た。The crushed material was taken out from the container, transferred to a mortar, and ground until it became a fine powder to obtain 200 g of resin powder.
上述の工程を繰り返してさらに２００ｇのの樹脂粉末を
得た。The above process was repeated to obtain an additional 200 g of resin powder.
サイズが幅２０ＩＩＩＩ１）、長さ３２０ＩＩＩＩＩ＋
、高さ６１）ＩＩＩ＋のパイトンゴムシートを使用し、
サイズが輻５００＋ｍｓ。Size: width 20III1), length 320III+
, using a Paiton rubber sheet with a height of 61) III+,
The size is convergence 500+ms.
長さ５００＋ｗａ＋、高さ５ＩＩＩＩ１）のアルミ板上
に３００１）ＩＩ＋×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の樹脂粉末を充
填し、プレス成形機により圧力２５Ｋｇｆ／ｃｍ”、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３００＋＋ｍ、長さ３２０＋ｕ＋、高さ３
ＩＩＩＩ＋の樹脂成形品を得た。A frame of 3001) II + × 300 mm was assembled on an aluminum plate with a length of 500 + wa + and a height of 5III1), and 400 g of the resin powder prepared as described above was filled therein, and a pressure of 25 Kgf/cm was applied using a press molding machine. Press molding was carried out for 2 hours at a temperature of 316°C. After cooling, the size was 300++ m in width, 320 + u+ in length, and 3 in height.
A resin molded product of III+ was 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 resulting resin molded product was extremely homogeneous and contained no air bubbles, even though 200 g of resin powder, which had been prepared separately, was molded together.
本発明によれば、芳香族テトラカルボン酸成分を低沸点
有機溶剤に溶解し、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ながら前記低沸点を線
溶剤の沸点以上の温度に加熱反応せしめ、溶剤を除去し
ながらポリアミド酸を生成せしめ、次いで減圧下で加熱
してブリイミド化したから、簡単な反応容器を使用した
減圧オープ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, an aromatic tetracarboxylic acid component is dissolved in a low boiling point organic solvent, and while an aromatic diamine component is added to the solution of the aromatic tetracarboxylic acid component, the low boiling point is reduced to a temperature equal to or higher than the boiling point of the linear solvent. A heating reaction was carried out to generate polyamic acid while removing the solvent, and then it was heated under reduced pressure to form a briimide.The main method was heating by opening under reduced pressure using a simple reaction vessel, and there was no need for filtration or washing. A substantially solvent-free resin powder can be produced at low cost by a simplified method that does not require any solvents.
しかも本発明により得られた樹脂粉末は、１０〜３０Ｋ
ｇ／ｃｍ”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 by the present invention has a temperature of 10 to 30K.
Compression molding can be performed under low pressure conditions of "g/cm", so general-purpose tools and methods can be used for molding.Also, since it does not substantially contain solvents that cause bubbles, molding with excellent homogeneity can be achieved. You can get the product.
代理人 弁理士 小 川 信 −Agent: Patent Attorney Nobuo Kogawa -
Claims (2)
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ながら前記低沸点有機溶
剤の沸点以上の温度に加熱反応せしめてポリアミド酸を
生成せしめ、次いで減圧下で加熱してポリアミド酸をプ
リイミド化するポリイミド樹脂粉末の製造方法。(1) An aromatic tetracarboxylic acid component is dissolved in a low boiling point organic solvent, and an aromatic diamine component is added to the resulting solution of the aromatic tetracarboxylic acid component while heating the solution to a temperature equal to or higher than the boiling point of the low boiling point organic solvent. A method for producing polyimide resin powder, which comprises causing a heating reaction to produce polyamic acid, and then heating under reduced pressure to preimide the polyamic acid.
溶解し、得られた該芳香族テトラカルボン酸成分の溶液
に芳香族ジアミンを添加しながら前記低沸点有機溶剤の
沸点以上の温度に加熱反応せしめてポリアミド酸を生成
せしめ、次いで減圧下で加熱し、プリイミド化すること
により得られた樹脂粉末を１０〜３０Ｋｇｆ／ｃｍ＾２
の加圧下で加熱するポリイミド樹脂粉末の圧縮成形方法
。(2) An aromatic tetracarboxylic acid component is dissolved in a low boiling point organic solvent, and an aromatic diamine is added to the resulting solution of the aromatic tetracarboxylic acid component while heating to a temperature equal to or higher than the boiling point of the low boiling point organic solvent. The resin powder obtained by reacting to produce polyamic acid and then heating under reduced pressure to preimide is heated at 10 to 30 Kgf/cm^2
A method for compression molding polyimide resin powder by heating under pressure.
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 true JPH04126721A (en) | 1992-04-27 |
| JP2852973B2 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) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0792903A1 (en) * | 1996-02-28 | 1997-09-03 | Research Institute Of Advanced Material Gas-Generator | Method of molding polyimide resin and apparatus therefor |
-
1990
- 1990-09-19 JP JP24734990A patent/JP2852973B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0792903A1 (en) * | 1996-02-28 | 1997-09-03 | Research Institute Of Advanced Material Gas-Generator | Method of molding polyimide resin and apparatus therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2852973B2 (en) | 1999-02-03 |
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