JP2007063380A - Method for producing polyimide precursor powder for expansion molding use - Google Patents
Method for producing polyimide precursor powder for expansion molding use Download PDFInfo
- Publication number
- JP2007063380A JP2007063380A JP2005250280A JP2005250280A JP2007063380A JP 2007063380 A JP2007063380 A JP 2007063380A JP 2005250280 A JP2005250280 A JP 2005250280A JP 2005250280 A JP2005250280 A JP 2005250280A JP 2007063380 A JP2007063380 A JP 2007063380A
- Authority
- JP
- Japan
- Prior art keywords
- polyimide precursor
- foam molding
- precursor powder
- polyimide
- producing
- 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.)
- Pending
Links
Images
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
この発明は、発泡成形用ポリイミド前駆体粉末の製法に関し、さらに詳しくは大量生産が可能でしかも比較的均一な粒子径を有し界面活性剤を含有せず良好な発泡体を与え得る発泡成形用ポリイミド前駆体粉末の製法に関する。 The present invention relates to a process for producing a polyimide precursor powder for foam molding, and more particularly, for foam molding that can be mass-produced and that has a relatively uniform particle size and does not contain a surfactant and can provide a good foam. The present invention relates to a method for producing a polyimide precursor powder.
従来、合成樹脂発泡体としては、ポリウレタン系、ポリスチレン系、ポリオレフィン系の発泡体が広く使用されている。
しかし、これらの合成樹脂発泡体は耐熱性が低いため、耐熱性発泡体としてポリイミド系発泡体が種々検討されている（特許文献１、特許文献２）。
特に、ガラス転移温度が３００℃以上のポリイミドからなる発泡ポリイミドが提案された（特許文献３）。
また、前記の発泡ポリイミドの発泡倍率を制御した発泡ポリイミドおよびその製法が提案された（特許文献４）。
一方、溶液から乾燥法によって粉末を得る方法として、加熱空気中に溶液を噴霧し乾燥して粉末を得る噴霧乾燥法（特許文献５）が知られている。
Conventionally, polyurethane-based, polystyrene-based, and polyolefin-based foams have been widely used as synthetic resin foams.
However, since these synthetic resin foams have low heat resistance, various polyimide foams have been studied as heat-resistant foams (Patent Documents 1 and 2).
In particular, a foamed polyimide composed of polyimide having a glass transition temperature of 300 ° C. or higher has been proposed (Patent Document 3).
Moreover, the foaming polyimide which controlled the expansion ratio of the said foaming polyimide and its manufacturing method were proposed (patent document 4).
On the other hand, as a method for obtaining a powder from a solution by a drying method, a spray drying method (Patent Document 5) is known in which a solution is sprayed in heated air and dried to obtain a powder.
しかし、これら公知文献に記載の発泡ポリイミドに用いられる発泡成形用ポリイミド前駆体粉末は、界面活性剤を含有するものであるため得られる発泡ポリイミドの物性、特に限界酸素指数などのポリイミド発泡体が本来有する耐熱性が低下するとか、エバポレ−タ−を用いて少量で得られるものであるため粉末を大量生産によって製造する場合には不向きであることが指摘されている。
また、前記の噴霧乾燥法では、１００℃以上の温度での乾燥を必要とし、得られた粉末は発泡成形用には適さない。
However, the polyimide precursor powder for foam molding used in the foamed polyimide described in these known documents contains a surfactant, so that the properties of the resulting foamed polyimide, especially the polyimide foam such as the critical oxygen index, are inherently It has been pointed out that it is unsuitable for producing powders by mass production because the heat resistance of the powders is reduced or it is obtained in a small amount by using an evaporator.
Further, the spray drying method requires drying at a temperature of 100 ° C. or higher, and the obtained powder is not suitable for foam molding.
この発明の目的は、界面活性剤を含有せず良好な物性を有する発泡ポリイミドを与えることができ、しかも大量生産が可能である発泡成形用ポリイミド前駆体粉末の製法を提供することである。 An object of the present invention is to provide a process for producing a polyimide precursor powder for foam molding which can provide a foamed polyimide having no physical properties and having good physical properties and which can be mass-produced.
この発明は、界面活性剤を含有しない発泡成形用ポリイミド前駆体溶液を液体の粒子として噴霧し、溶液中の希釈剤の沸点未満の乾燥温度で噴霧乾燥することを特徴とする発泡成形用ポリイミド前駆体粉末の製法に関する。
また、この発明は、界面活性剤を含有しないテトラカルボン酸ジエステル、ジアミンおよびメチルアルコ−ルから得られる混合溶液からなる発泡成形用ポリイミド前駆体溶液を液体の粒子として噴霧し、４０℃以下の乾燥温度で噴霧乾燥することを特徴とする発泡成形用ポリイミド前駆体粉末の製法に関する。
The present invention relates to a polyimide precursor for foam molding characterized by spraying a polyimide precursor solution for foam molding not containing a surfactant as liquid particles and spray drying at a drying temperature lower than the boiling point of the diluent in the solution. The present invention relates to a method for producing body powder.
The present invention also sprays a polyimide precursor solution for foam molding comprising a mixed solution obtained from a tetracarboxylic acid diester not containing a surfactant, a diamine and methyl alcohol as liquid particles, and is dried at 40 ° C. or lower. The present invention relates to a method for producing a polyimide precursor powder for foam molding characterized by spray drying at a temperature.
この発明の発泡成形用ポリイミド前駆体粉末の製法は、大量生産が可能でしかも比較的均一な粒子径を有し界面活性剤を含有せず良好な発泡ポリイミドを与え得る発泡成形用ポリイミド前駆体粉末の製造を可能とする。 The production method of the polyimide precursor powder for foam molding of the present invention is a polyimide precursor powder for foam molding that can be mass-produced and has a relatively uniform particle size and does not contain a surfactant and can provide a good foamed polyimide. It is possible to manufacture.
この発明の実施の形態を次に示す。
１）発泡成形用ポリイミド前駆体粉末が、１０μｍ以下の一次粒子径である上記の発泡成形用ポリイミド前駆体粉末の製法。
２）ポリイミド前駆体溶液が、テトラカルボン酸ジエステル、ジアミンおよび希釈剤から得られる混合溶液からなる上記の発泡成形用ポリイミド前駆体粉末の製法。
３）ジアミンが、芳香族ジアミンとジアミン成分中０．１〜１０モル％のジアミノシロキサンからなる上記の発泡成形用ポリイミド前駆体粉末の製法。
４）希釈剤が、アルコ−ルである上記の発泡成形用ポリイミド前駆体粉末の製法。
５）テトラカルボン酸ジエステルが、２，３，３’，４’−ビフェニルテトラカルボン酸二無水物を５０モル％以上含むテトラカルボン酸二無水物から導かれるものである上記の発泡成形用ポリイミド前駆体粉末の製法。
Embodiments of the present invention will be described below.
1) A process for producing the above-mentioned polyimide precursor powder for foam molding, wherein the polyimide precursor powder for foam molding has a primary particle size of 10 μm or less.
2) A process for producing the above polyimide precursor powder for foam molding, wherein the polyimide precursor solution is a mixed solution obtained from a tetracarboxylic acid diester, a diamine and a diluent.
3) A process for producing the above-mentioned polyimide precursor powder for foam molding, wherein the diamine comprises an aromatic diamine and 0.1 to 10 mol% of diaminosiloxane in the diamine component.
4) A process for producing the above-mentioned polyimide precursor powder for foam molding, wherein the diluent is alcohol.
5) The above-mentioned polyimide precursor for foam molding, wherein the tetracarboxylic acid diester is derived from a tetracarboxylic dianhydride containing 50 mol% or more of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride. Body powder manufacturing method.
この発明におけるポリイミドを与えるポリイミド前駆体は、テトラカルボン酸成分、好適には芳香族テトラカルボン酸とその炭素数４以下の低級一級アルコ−ルのモノおよび／またはジエステルとの混合体であり、炭素数４以下の低級一級アルコ−ルによって一部モノエステル化および／またはジエステル化された芳香族テトラカルボン酸ジエステル、好適には芳香族テトラカルボン酸ジエステルとジアミン、好適には芳香族ジアミンとを、テトラカルボン酸成分に対してアミノ基総量が略２：１となる割合で反応させることによって得られる。 The polyimide precursor that gives the polyimide in this invention is a mixture of a tetracarboxylic acid component, preferably an aromatic tetracarboxylic acid and its mono- and / or diester of a lower primary alcohol having 4 or less carbon atoms. An aromatic tetracarboxylic acid diester partially monoesterified and / or diesterified with a lower primary alcohol having a number of 4 or less, preferably an aromatic tetracarboxylic acid diester and a diamine, preferably an aromatic diamine, It can be obtained by reacting the total amount of amino groups with the tetracarboxylic acid component at a ratio of about 2: 1.
前記のテトラカルボン酸成分として、２，３，３’、４’−ビフェニルテトラカルボン酸誘導体（以下、ａ−ＢＰＤＡ誘導体と略記することもある。）あるいは２，２’，３，３’−ビフェニルテトラカルボン酸誘導体（以下、ｉ−ＢＰＤＡ誘導体と略記することもある。）が５０％以上であることが好ましい。テトラカルボン酸成分として、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（以下、ｓ−ＢＰＤＡと略記することもある）あるいは、ピロメリット酸二無水物（以下、ＰＭＤＡと略記することもある）、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物（以下、ＢＴＤＡと略記することもある）、ビス（３，４−ジカルボキシフェニル）エ−テル二無水物、２，３，６，７−ナフタレンテトラカルボン酸二無水物、１，２，５，６−ナフタレンテトラカルボン酸二無水物、１，２，４，５−ナフタレンテトラカルボン酸二無水物、１，４，５，８−ナフタレンテトラカルボン酸二無水物、２，２−ビス（２，５−ジカルボキシフェニル）プロパン二無水物、１，１−ビス（２，３−ジカルボキシフェニル）エタン二無水物、１，１−ビス（３，４−ジカルボキシフェニル）スルホン二無水物、１，３−ビス（３，４−ジカルボキシフェニル）−１，１，３，３−テトラメチルジシロキサン二無水物などの芳香族テトラカルボン酸二無水物をテトラカルボン酸成分１００モル％中の０〜５０モル％程度の量で、得られるポリイミドのＴｇの調整、発泡倍率（使用量が増大すると低下する）の調整などを目的として使用してもよい。Ｔｇが大幅に変化しない限り一般的に使用されているテトラカルボン酸成分はすべて使用可能である。
As the tetracarboxylic acid component, 2,3,3 ′, 4′-biphenyltetracarboxylic acid derivative (hereinafter sometimes abbreviated as a-BPDA derivative) or 2,2 ′, 3,3′-biphenyl The tetracarboxylic acid derivative (hereinafter sometimes abbreviated as i-BPDA derivative) is preferably 50% or more. As the tetracarboxylic acid component, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (hereinafter sometimes abbreviated as s-BPDA) or pyromellitic dianhydride (hereinafter abbreviated as PMDA). 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride (hereinafter sometimes abbreviated as BTDA), bis (3,4-dicarboxyphenyl)
前記のジアミン成分としては、ベンゼン環が２つ（２核）のジアミンまでを主成分としジアミノポリシロキサンと併用することが好ましく、これによって発泡ポリイミドのＴｇ３００℃以上を達成することが容易になる。多置換アミン成分は高温での発泡の収縮防止、発泡強度（発泡中に割れにくい）増大のために、必須なものではないが一部含まれている方が好ましい。ジアミノジシロキサンは界面活性剤的に作用し、発泡均一化のために０．１〜１０モル％の範囲、特に０．２〜５モル％使用することが好ましい。少量では発泡が均一化しづらく、多量ではＴｇ低下および熱安定性の低下をまねく。ジアミノポリシロキサンでも発泡の均一性は達成されるが海島構造をとり、高温下では分解しやすく耐熱性が低下し好ましくない。 As the diamine component, it is preferable to use a diaminopolysiloxane having a benzene ring having up to two (binuclear) diamine as a main component, and this makes it easy to achieve Tg of 300 ° C. or higher of the foamed polyimide. The multi-substituted amine component is not essential, but it is preferable that it is partially contained in order to prevent foam shrinkage at high temperatures and increase foam strength (hard to break during foaming). Diaminodisiloxane acts as a surfactant and is preferably used in the range of 0.1 to 10 mol%, particularly 0.2 to 5 mol% for uniform foaming. A small amount makes it difficult to make the foam uniform, and a large amount leads to a decrease in Tg and thermal stability. Even with diaminopolysiloxane, evenness of foaming is achieved, but it is not preferable because it has a sea-island structure and easily decomposes at high temperatures, resulting in a decrease in heat resistance.
前記のポリイミド前駆体は、好適には次の工程によって得ることができる。
すなわち、先ずテトラカルボン酸二無水物のハ−フエステルであるテトラカルボン酸ジエステルとジアミン、例えば、ｐ−フェニレンジアミン（以下、ＰＰＤと略記することもある。）、４，４’−ジアミノジフェニルエ−テル（以下、ＯＤＡと略記することもある。）などの芳香族ジアミンを主とし、発泡均一化のための成分としてのジアミノジシロキサンおよびさらに必要ならばテトラアミノビフェニルのような分子内に３個以上のアミノ基を有するアミン化合物、例えば芳香族トリアミン化合物または芳香族テトラアミン化合物を高分子量のポリイミドとなるような組成比でエステル化溶媒、例えばメタノ−ル、エタノ−ル、ｎ−プロパノ−ル、ｎ−ブタノ−ルなどの低級一級アルコ−ル、好適にはメタノ−ルあるいはエタノ−ルと均一混合し、溶解する第一の工程からなる。この際に、各成分の濃度はジアミン類等の溶解度限界までは可能であるが、全量中の溶媒を除く固形分量は１０％〜５０％程度までである。前記の組成を有するポリイミドは、耐熱性および耐放射線性が良好である。
The polyimide precursor can be preferably obtained by the following steps.
That is, first, a tetracarboxylic acid diester which is a half ester of tetracarboxylic dianhydride and a diamine, for example, p-phenylenediamine (hereinafter sometimes abbreviated as PPD), 4,4′-diaminodiphenyl ether. It is mainly composed of aromatic diamines such as ter (hereinafter sometimes abbreviated as ODA), and 3 in the molecule such as diaminodisiloxane as a component for uniform foaming and, if necessary, tetraaminobiphenyl. An amine compound having an amino group as described above, for example, an aromatic triamine compound or an aromatic tetraamine compound in a composition ratio so as to become a high molecular weight polyimide, such as methanol, ethanol, n-propanol, Uniform with lower primary alcohols such as n-butanol, preferably methanol or ethanol It consists of the first step of mixing and dissolving. At this time, the concentration of each component is possible up to the solubility limit of diamines and the like, but the solid content excluding the solvent in the total amount is about 10% to 50%. The polyimide having the above composition has good heat resistance and radiation resistance.
この混合物には、１，２−ジメチルイミダゾ−ル、ベンズイミダゾ−ル、イソキノリン、置換ピリジンなどのイミド化触媒を加えてもよい。
また、他の公知の添加剤、例えば、無機フィラ−、無機あるいは有機顔料などを加えてもよい。
この発明においては、上記のようにして得られる発泡成形用ポリイミド前駆体溶液に界面活性剤を含有させないことが必要である。有機あるいは無機のいずれであっても界面活性剤を含有させることは発泡ポリイミドの特性が低下するため適当ではない。
To this mixture, an imidation catalyst such as 1,2-dimethylimidazole, benzimidazole, isoquinoline, substituted pyridine or the like may be added.
Further, other known additives such as inorganic fillers, inorganic or organic pigments may be added.
In the present invention, it is necessary that the foam precursor for polyimide molding obtained as described above does not contain a surfactant. Whether it is organic or inorganic, it is not appropriate to contain a surfactant because the properties of the foamed polyimide are deteriorated.
この発明においては、前記の発泡成形用ポリイミド前駆体溶液を液体の粒子として噴霧し、４０℃以下の温度で噴霧乾燥して、発泡成形用ポリイミド前駆体粉末を製造する。
前記の噴霧乾燥に好適な装置として、例えば特開平８−２９９７０１号公報に記載された噴霧乾燥装置を挙げることができる。前記の発泡成形用ポリイミド前駆体溶液はポリイミド前駆体（固形分）の溶液中の割合が２０〜６０質量％であることが好ましく、特に発泡成形用ポリイミド前駆体溶液は、粘度（２５℃）が１〜１００ｃｐ、特に１〜６０ｃｐであることが好ましい。
前記の噴霧乾燥装置は、好適にはミストドライヤ−として藤崎電機株式会社から製造販売されている装置（例えばＭＤＰ−０５０）を使用することができる。
この発明においては、噴霧乾燥温度を溶液中の希釈剤の沸点未満とすることが必要であり、この温度より高い温度で噴霧乾燥すると、良好な発泡体が得られない。
In this invention, the polyimide precursor solution for foam molding is sprayed as liquid particles and spray-dried at a temperature of 40 ° C. or less to produce a polyimide precursor powder for foam molding.
As an apparatus suitable for the spray drying, for example, a spray drying apparatus described in JP-A-8-299701 can be exemplified. The ratio of the polyimide precursor solution for foam molding in the solution of the polyimide precursor (solid content) is preferably 20 to 60% by mass. In particular, the polyimide precursor solution for foam molding has a viscosity (25 ° C.). It is preferably 1 to 100 cp, particularly 1 to 60 cp.
As the spray drying apparatus, an apparatus (for example, MDP-050) manufactured and sold by Fujisaki Electric Co., Ltd. as a mist dryer can be used.
In the present invention, the spray drying temperature needs to be lower than the boiling point of the diluent in the solution, and if the spray drying is performed at a temperature higher than this temperature, a good foam cannot be obtained.
この発明の方法によって得られる発泡成形用ポリイミド前駆体粉末は、好適には平均粒子径が１０μｍ以下で粒子径が揃っており、好適には２０μｍ以上の粒径のものが５％以下、特に１％未満である。
この発明によれば、前記の発泡成形用ポリイミド前駆体粉末を連続的に製造することができる。
なお、前記の発泡成形用ポリイミド前駆体は、ジエステルとジアミンとが結合した塩である。従って、発泡成形用ポリイミド前駆体粉末中にはイミド化によって生成する（脱離する）約１０〜２０質量％のアルコ−ルと約５〜１０質量％の水が含まれていることになる。
The polyimide precursor powder for foam molding obtained by the method of the present invention preferably has an average particle size of 10 μm or less and a uniform particle size, preferably 5 μm or less, particularly 1 %.
According to this invention, the said polyimide precursor powder for foam molding can be manufactured continuously.
The polyimide precursor for foam molding is a salt in which a diester and a diamine are bonded. Accordingly, the polyimide precursor powder for foam molding contains about 10 to 20% by mass of alcohol and about 5 to 10% by mass of water generated (desorbed) by imidization.
この発明の発泡成形用ポリイミド前駆体粉末は、好適には予備成形体であるグリ−ン体を作製する工程、例えば、室温での圧縮成形に行い、次いで、好適にはマイクロ波加熱によって加熱し、最終的には（Ｔｇ＋α）℃の温度にて５〜６０分間、好適には１０分間程度加熱することによって、発泡ポリイミドを得ることができる。 The polyimide precursor powder for foam molding according to the present invention is preferably subjected to a step of producing a green body which is a preform, for example, compression molding at room temperature, and then preferably heated by microwave heating. Finally, the foamed polyimide can be obtained by heating at a temperature of (Tg + α) ° C. for 5 to 60 minutes, preferably about 10 minutes.
前記の予備成形体であるグリ−ン体の作製工程において、概略均一な状態のグリ−ン体であれば発泡時の均一化は達成できる。
また、前記のマイクロ波加熱による加熱においては、粉末重量当たりのマイクロ波出力を目安とし、例えば、１００ｇ／１ｋＷ程度で約１分で発泡を開始し、２〜３分で発泡は収束する。
上記発泡体はこの状態では非常に脆い発泡体であり、次いで熱風等の加熱により、２００℃程度から徐々に昇温し（一応の目安として、１００℃／１０分程度の昇温速度）、最終は（Ｔｇ＋α）℃の温度にて５〜６０分間、好適には１０分間程度加熱する。
In the production process of the green body as the preform, the green body can be made uniform during foaming if the green body is in a substantially uniform state.
Moreover, in the heating by the above microwave heating, the microwave output per weight of powder is used as a guide, for example, foaming starts at about 100 g / 1 kW in about 1 minute, and foaming converges in 2 to 3 minutes.
The foam is a very brittle foam in this state, and then gradually heated from about 200 ° C. by heating with hot air or the like (as a guideline, a rate of temperature increase of about 100 ° C./10 minutes). Is heated at a temperature of (Tg + α) ° C. for 5 to 60 minutes, preferably about 10 minutes.
前記の工程において、固体状態のポリイミド前駆体の加熱を、発泡のための加熱と熱固定（高分子量化）のための加熱の２段階である。
また、前記の発泡ポリイミドの製法において、マイクロ波加熱により加熱均一性向上が達成される。この発泡の際に、ガスが通過する遮蔽版を置いて圧縮力を加えることにより、機械的緻密化を併せて行い発泡倍率を制御することが好ましい。
次工程である熱固定（高分子量化）のための加熱を、発泡ポリイミドのガラス転移温度（Ｔｇ）以上の温度で行うことによってポリイミド発泡体のアウトガス量を低減させることができる。
In the above-described process, the heating of the solid state polyimide precursor is performed in two stages: heating for foaming and heating for heat setting (high molecular weight).
Moreover, in the manufacturing method of the said foaming polyimide, a heating uniformity improvement is achieved by microwave heating. In the foaming, it is preferable to control the foaming ratio by placing a shielding plate through which gas passes and applying a compressive force to perform mechanical densification.
The outgas amount of the polyimide foam can be reduced by performing heating for heat fixation (high molecular weight), which is the next step, at a temperature equal to or higher than the glass transition temperature (Tg) of the foamed polyimide.
前記の各工程によって加熱発泡することによって、均一な発泡状態の弾力性がありかつ復元力に優れた発泡体が得られる。この発泡体は連続孔を形成している。適当な形状に切断する事により各種用途向けの部材となり得る。
また、前記の方法によれば、ガラス転移温度が３００℃より高いポリイミドからなり、発泡倍率が１．５〜２００倍（密度９００〜７．５ｋｇ／ｍ３に相当する。）であり、任意の形状を有する発泡ポリイミド、好適には厚みが０．１〜５０ｍｍのシ−ト状の発泡ポリイミド成形体、特に引張強度が０．０５〜３ＭＰａである発泡ポリイミド成形体を得ることができる。
By foaming by heating in the above steps, a foam having a uniform foamed state elasticity and excellent restoring force can be obtained. This foam forms continuous pores. By cutting into an appropriate shape, it can be a member for various uses.
Moreover, according to the said method, it consists of a polyimide whose glass transition temperature is higher than 300 degreeC, and a foaming magnification is 1.5-200 times (it corresponds to a density of 900-7.5 kg / m < 3 >), Arbitrary A foamed polyimide having a shape, preferably a sheet-like foamed polyimide molded body having a thickness of 0.1 to 50 mm, particularly a foamed polyimide molded body having a tensile strength of 0.05 to 3 MPa can be obtained.
以下の記載において、各略号は次の化合物を意味する。
ａ−ＢＰＤＡ：２，３，３’，４’−ビフェニルテトラカルボン酸二無水物
ＢＴＤＡ：３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物
ＰＰＤ：ｐ−フェニレンジアミン
ＯＤＡ：４，４’−ジアミノジフェニルエ−テル
ＤＡＤＳｉ：１，３−ビス（３−アミノプロピル）テトラメチルジシロキサン
ＤＭＺ：１，２−ジメチルイミダゾ−ル
In the following description, each abbreviation means the following compound.
a-BPDA: 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride BTDA: 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride PPD: p-phenylenediamine ODA: 4, 4'-diaminodiphenyl ether DADSi: 1,3-bis (3-aminopropyl) tetramethyldisiloxane DMZ: 1,2-dimethylimidazole
参考例１
ポリイミド前駆体溶液の製造
２，３，３’，４’−ビフェニルテトラカルボン酸二無水物（以下ａ−ＢＰＤＡ）５５．３１ｋｇ（１８８モル）、３，３’，４，４’−ベンゾフェノンテトラカルボン酸二無水物（以下ＢＴＤＡ）１５．１４ｋｇ（４７モル）とメタノ−ル１００ｋｇを５００Ｌ反応釜に仕込み、攪拌しながら加熱昇温し、約６５℃で２時間還流下で攪拌を行って、２種類の芳香族テトラカルボン酸のジエステルを生成させた。反応終了後、溶液を冷却し、２０℃以下の温調下でｐ−フェニレンジアミン（以下ＰＰＤ）２５．１６ｋｇ（２３２．６５モル）を添加し完溶させた。ついで、１，３−ビス（３−アミノプロピル）テトラジメチルシロキサン０．６３ｋｇ（２．３５モル）を添加した。更に、１，２−ジメチルイミダゾ−ル２．９０ｋｇ（モル）を添加し、メタノ−ル４０ｋｇを加え４５質量％のポリイミド前駆体溶液（粘度：約５０ｃｐ、２５℃）を得た。
Reference example 1
Production of polyimide precursor solution 55,31 kg (188 mol) of 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride (hereinafter a-BPDA), 3,3 ′, 4,4′-benzophenonetetracarboxylic An acid dianhydride (hereinafter referred to as BTDA) 15.14 kg (47 mol) and methanol 100 kg were charged into a 500 L reaction kettle, heated to a temperature while stirring, and stirred at reflux at about 65 ° C. for 2 hours. Diesters of various aromatic tetracarboxylic acids were produced. After completion of the reaction, the solution was cooled, and 25.16 kg (232.65 mol) of p-phenylenediamine (hereinafter referred to as PPD) was added at a temperature of 20 ° C. or lower to complete dissolution. Then, 0.63 kg (2.35 mol) of 1,3-bis (3-aminopropyl) tetradimethylsiloxane was added. Furthermore, 2.90 kg (mol) of 1,2-dimethylimidazole was added, and 40 kg of methanol was added to obtain a 45% by mass polyimide precursor solution (viscosity: about 50 cp, 25 ° C.).
参考例１で得たポリイミド前駆体溶液を図１に示すミストドライヤ−（ＭＤＰ−０５０：藤崎電機株式会社製）（以下ＭＤＰ−０５０）を用いて、送液量０．４３Ｌ／分、送風量２６ｍ３／分、温度３５℃で、噴霧乾燥し、ポリイミド前駆体粉末を得た。
このポリイミド前駆体粉末は、理論上イミド化によって生成する（脱離する）１３．５質量％のアルコ−ルと９質量％の水を含む。
この処理条件で行ったところ、１３ｋｇ／Ｈｒの処理量であり生産性も良好であった。
この粉末は、平均粒径６μｍであり２０μｍを超えるものはなかった。
この粉末を用いて、マイクロ波加熱装置（ＭＯＨ−３０００：ミクロ電子株式会社製）を用い、３ｋＷで６分間発泡成形を行った。次に、この発泡成形品を熱風オ−ブン（ＳＴＰＨ−２０１：タバイエスペック株式会社製）で窒素雰囲気下、段階的に昇温し、最終温度４００℃で１０分間加熱処理を行いポリイミド発泡体を得た。
この発泡体断面を、マイクロスコ−プ（以下ＭＳ）（ＶＨ−５０００Ｃ：株式会社キ−エンス社製）で観察したところ、気泡径のバラツキの少ない良好なポリイミド発泡体であった。
Using the mist dryer (MDP-050: manufactured by Fujisaki Electric Co., Ltd.) (hereinafter referred to as MDP-050) shown in FIG. 1, the polyimide precursor solution obtained in Reference Example 1 was fed at a rate of 0.43 L / min, and the blowing rate. Spray drying was performed at 26 m 3 / min and a temperature of 35 ° C. to obtain a polyimide precursor powder.
This polyimide precursor powder contains 13.5% by mass of alcohol and 9% by mass of water which are theoretically generated (desorbed) by imidization.
When the treatment was performed under these treatment conditions, the treatment amount was 13 kg / Hr and the productivity was good.
This powder had an average particle size of 6 μm and none exceeded 20 μm.
Using this powder, foam molding was performed at 3 kW for 6 minutes using a microwave heating apparatus (MOH-3000: manufactured by Micro Electronics Co., Ltd.). Next, this foamed molded product is heated stepwise in a nitrogen atmosphere with a hot air oven (STPH-201: manufactured by Tabai Espec Co., Ltd.), and heat-treated at a final temperature of 400 ° C. for 10 minutes to obtain a polyimide foam. Obtained.
When the cross section of the foam was observed with a microscope (hereinafter referred to as MS) (VH-5000C: manufactured by Keyence Corporation), it was a good polyimide foam with little variation in bubble diameter.
参考例１で得たポリイミド前駆体溶液を図１に示すＭＤＰ−０５０を用いて、送液量０．４３Ｌ／分、送風量２６ｍ３／分、温度５０℃で噴霧乾燥し、ポリイミド前駆体粉末を得た。
この粉末は、平均粒径６μｍであり、２０μｍを超えるものはなかった。
この処理条件で行ったところ、１２ｋｇ／Ｈｒの処理量であり生産性も良好であった。
この粉末を用いて、実施例１と同様に発泡成形し、ポリイミド発泡体を得た。
この発泡体断面をＭＳで観察したところ、気泡径のバラツキの少ない良好なポリイミド発泡体であった。
The polyimide precursor solution obtained in Reference Example 1 was spray-dried at a temperature of 50 ° C. using a MDP-050 shown in FIG. 1 at a liquid feed rate of 0.43 L / min, a blowing rate of 26 m 3 / min, and a polyimide precursor powder. Got.
This powder had an average particle size of 6 μm and none exceeded 20 μm.
When the treatment was performed under these treatment conditions, the treatment amount was 12 kg / Hr and the productivity was good.
Using this powder, foam molding was carried out in the same manner as in Example 1 to obtain a polyimide foam.
When this foam cross section was observed by MS, it was a good polyimide foam with little variation in cell diameter.
参考例１で得たポリイミド前駆体溶液を図１に示すＭＤＰ−０５０を用いて、送液量０．４３Ｌ／分、送風量３２ｍ３／分、温度３５℃で噴霧乾燥し、ポリイミド前駆体粉末を得た。
この粉末は、平均粒径６μｍであり２０μｍを超えるものはなかった。
この処理条件で行ったところ、１３ｋｇ／Ｈｒの処理量であり生産性も良好であった。
この粉末を用いて、実施例１と同様に発泡成形し、ポリイミド発泡体を得た。
この発泡体断面をＭＳで観察したところ、気泡径のバラツキの少ない良好なポリイミド発泡体であった。
The polyimide precursor solution obtained in Reference Example 1 was spray-dried at a temperature of 35 ° C. using a MDP-050 shown in FIG. 1 at a liquid feed rate of 0.43 L / min, a blowing rate of 32 m 3 / min, and a polyimide precursor powder. Got.
This powder had an average particle size of 6 μm and none exceeded 20 μm.
When the treatment was performed under these treatment conditions, the treatment amount was 13 kg / Hr and the productivity was good.
Using this powder, foam molding was carried out in the same manner as in Example 1 to obtain a polyimide foam.
When this foam cross section was observed by MS, it was a good polyimide foam with little variation in cell diameter.
比較例１
参考例１で得たポリイミド前駆体溶液をスプレ−ドライヤ−（ＧＳ３１０：ヤマト科学株式会社製）を用い、噴霧乾燥を行ったが、８０℃以下では粉末を得ることが出来なかった。
そこで、粉末が出来る条件、送液量０．０２Ｌ／分、送風量０．５ｍ／分、温度１２０℃でポリイミド前駆体粉末を得た。
この粉末は、平均粒径１３μｍであり、４０μｍを超えるものもあった。
この処理条件で行ったところ、０．６ｋｇ／Ｈｒの処理量であり、生産性に問題があった。
この粉末を用いて、実施例１と同様に発泡成形したが、発泡体を形成することが出来なかった。
Comparative Example 1
The polyimide precursor solution obtained in Reference Example 1 was spray dried using a spray dryer (GS310: manufactured by Yamato Scientific Co., Ltd.), but no powder could be obtained at 80 ° C. or lower.
Therefore, a polyimide precursor powder was obtained under conditions where powder can be produced, a liquid feeding amount of 0.02 L / min, a blowing rate of 0.5 m / min, and a temperature of 120 ° C.
This powder had an average particle size of 13 μm, and some exceeded 40 μm.
When the treatment was performed under these treatment conditions, the treatment amount was 0.6 kg / Hr, and there was a problem in productivity.
Using this powder, foam molding was performed in the same manner as in Example 1, but a foam could not be formed.
比較例２
参考例１で得たポリイミド前駆体溶液を混合乾燥機（タナベウィルテック株式会社製）を用い、温度３５℃、５０ｒｐｍで攪拌しながら減圧して乾燥を行ってポリイミド前駆体粉末を得た。
この粉末は、平均粒径１８μｍであったが、２５０μｍを超えるものも存在し、分布の広いものであった。
この処理条件では、バッチ式の処理になるため、１０ｋｇ処理するのに６Ｈｒを要し、生産性に問題があった。
この粉末を用いて、実施例１と同様に発泡成形し、ポリイミド発泡体を得た。
この発泡体断面をＭＳ（マイクロスコ−プ）で観察したところ、気泡径のバラツキが多いポリイミド発泡体であった。
ＭＳの測定法：５〜４０倍の倍率ズ−ムレンズで観察
Comparative Example 2
The polyimide precursor solution obtained in Reference Example 1 was dried using a mixing dryer (manufactured by Tanabe Wiltech Co., Ltd.) while stirring at a temperature of 35 ° C. and 50 rpm to obtain a polyimide precursor powder.
Although this powder had an average particle size of 18 μm, some of the powder exceeded 250 μm and had a wide distribution.
Under this processing condition, since it is a batch-type processing, 6 Hr was required to process 10 kg, and there was a problem in productivity.
Using this powder, foam molding was carried out in the same manner as in Example 1 to obtain a polyimide foam.
When the cross section of the foam was observed with MS (microscope), it was a polyimide foam with a large variation in bubble diameter.
MS measurement method: Observation with 5 to 40 times magnification zoom lens
１ ノズル
２ 処理液
３ 吐出Ａｉｒ
４ 乾燥用Ａｉｒ
５ フィルタ−
６ 取り出し口
７ 排気ライン
１０ ポリイミド前駆体溶液の噴霧物
1 Nozzle 2
4 Air for drying
5 Filter
6
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005250280A JP2007063380A (en) | 2005-08-30 | 2005-08-30 | Method for producing polyimide precursor powder for expansion molding use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005250280A JP2007063380A (en) | 2005-08-30 | 2005-08-30 | Method for producing polyimide precursor powder for expansion molding use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2007063380A true JP2007063380A (en) | 2007-03-15 |
Family
ID=37925944
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005250280A Pending JP2007063380A (en) | 2005-08-30 | 2005-08-30 | Method for producing polyimide precursor powder for expansion molding use |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2007063380A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009008499A1 (en) * | 2007-07-11 | 2009-01-15 | Ube Industries, Ltd. | Method for production of polyimide foam, and polyimide foam |
| JP2009019107A (en) * | 2007-07-11 | 2009-01-29 | Ube Ind Ltd | Polyimide foam comprising 3,3',4,4'-biphenyltetracarboxylic acid component and method for producing the same |
| JP2009108243A (en) * | 2007-10-31 | 2009-05-21 | Ube Ind Ltd | New polyimide foam and method for producing the same |
| KR100963647B1 (en) | 2008-08-28 | 2010-06-15 | 한국화학연구원 | Polyimide particle and its process for producing |
| US10844173B2 (en) | 2016-08-03 | 2020-11-24 | Sabic Global Technologies B.V. | Method for the manufacture of a poly(imide) prepolymer powder and varnish, poly(imide) prepolymer powder and varnish prepared thereby, and poly(imide) prepared therefrom |
| CN117304562A (en) * | 2023-11-27 | 2023-12-29 | 宁波市嘉化新材料科技有限公司 | Synthetic resin layered material and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004515897A (en) * | 2000-12-14 | 2004-05-27 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | High density polyimide foam insulator |
| JP2004323715A (en) * | 2003-04-25 | 2004-11-18 | Ube Ind Ltd | Foamed polyimide molded product and method for producing the same |
-
2005
- 2005-08-30 JP JP2005250280A patent/JP2007063380A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004515897A (en) * | 2000-12-14 | 2004-05-27 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | High density polyimide foam insulator |
| JP2004323715A (en) * | 2003-04-25 | 2004-11-18 | Ube Ind Ltd | Foamed polyimide molded product and method for producing the same |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009008499A1 (en) * | 2007-07-11 | 2009-01-15 | Ube Industries, Ltd. | Method for production of polyimide foam, and polyimide foam |
| JP2009019107A (en) * | 2007-07-11 | 2009-01-29 | Ube Ind Ltd | Polyimide foam comprising 3,3',4,4'-biphenyltetracarboxylic acid component and method for producing the same |
| JP2009108243A (en) * | 2007-10-31 | 2009-05-21 | Ube Ind Ltd | New polyimide foam and method for producing the same |
| KR100963647B1 (en) | 2008-08-28 | 2010-06-15 | 한국화학연구원 | Polyimide particle and its process for producing |
| US10844173B2 (en) | 2016-08-03 | 2020-11-24 | Sabic Global Technologies B.V. | Method for the manufacture of a poly(imide) prepolymer powder and varnish, poly(imide) prepolymer powder and varnish prepared thereby, and poly(imide) prepared therefrom |
| CN117304562A (en) * | 2023-11-27 | 2023-12-29 | 宁波市嘉化新材料科技有限公司 | Synthetic resin layered material and preparation method thereof |
| CN117304562B (en) * | 2023-11-27 | 2024-02-20 | 宁波市嘉化新材料科技有限公司 | Synthetic resin layered material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3687496B2 (en) | Foamed polyimide and process for producing the same | |
| CN105778130B (en) | A kind of high-intensity high heat-resistance polyimides microporous membrane and preparation method thereof | |
| TWI714944B (en) | Polyamic acid composition with improved storage stability, method for preparing polyimide film by using the same, polyimide film prepared by the same and electronic device | |
| JP2007063380A (en) | Method for producing polyimide precursor powder for expansion molding use | |
| TW201313783A (en) | Black polyimide film and method for preparing the same | |
| JP5928705B2 (en) | Method for producing polyimide precursor solution, polyimide precursor solution using the same, and porous polyimide | |
| JP2002146085A (en) | Method for producing porous polyimide and porous polyimide | |
| KR101338328B1 (en) | Manufacturing Method Of Polyamic acid Composition, Polyamic acid Composition, Polyimide Film And Substrateused For Display Device Using The Same | |
| CN113795537A (en) | Preparation method of polyimide film and polyimide film prepared by same | |
| TWI723360B (en) | Polyimide precursor composition comprising crosslinkable dianhydride compound and antioxidant, polyimide film prepared therefrom and preparation method thereof, and electronic device comprising the same | |
| KR101332627B1 (en) | Polyamic acid Composition, Polyimide Film And Substrateused For Display Device Using The Same | |
| KR102500606B1 (en) | Manufacturing method of polyimide powder and polyimide powder manufactured by the same | |
| JP2009091457A (en) | New polyimide foam and method for producing the same | |
| CN102850569A (en) | Preparation method of polyimide foam | |
| JP4192451B2 (en) | Foamed polyimide and process for producing the same | |
| JP4428034B2 (en) | Foamed polyimide structure and manufacturing method thereof | |
| JP2024512437A (en) | Polyimide film for graphite sheet and graphite sheet manufactured from it | |
| JP4096798B2 (en) | Foamed polyimide molding and its production method | |
| JP4557376B2 (en) | Method for producing porous body and porous body | |
| KR20160077479A (en) | Manufacturing method of polyimide precursor solution, polyimide film manufactured using the same | |
| JP2005042055A (en) | Foam-polyimide-composite, polyimide porous material and method for producing them | |
| JP2004143378A (en) | Foamed polyimide structure and method for producing the same | |
| JP7245504B2 (en) | Method for producing polyimide precursor solution | |
| JP2001270955A (en) | Foamed polyimide | |
| JP4449612B2 (en) | Composition for forming porous carbon film and method for forming porous carbon film |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20080519 |
|
| A977 | Report on retrieval |
Effective date: 20110228 Free format text: JAPANESE INTERMEDIATE CODE: A971007 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20110405 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20110802 |