JP2006199945A - Low water absorbable polyimide resin and process for its production - Google Patents
Low water absorbable polyimide resin and process for its production Download PDFInfo
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本発明は、無色透明性の低吸収性ポリイミド樹脂およびその製造方法、該ポリイミド樹脂からなるフィルムの製造方法、および該ポリイミド樹脂を含有する封止材を提供する。 The present invention provides a colorless and transparent low-absorption polyimide resin and a method for producing the same, a method for producing a film comprising the polyimide resin, and a sealing material containing the polyimide resin.
一般に、ポリイミド樹脂は、芳香族テトラカルボン酸無水物と芳香族ジアミンとの縮合反応により得られたポリアミド酸を脱水閉環反応させて得られる耐熱性の樹脂である。分子鎖の剛直性、共鳴安定化、および強い化学結合により優れた熱分解抵抗性と酸化や加水分解などの化学変化に対する抵抗性を有し、機械的特性、電気的特性および柔軟性に優れているので、電気、電子、自動車および航空宇宙産業などの分野においてフィルム、コーティング剤、成形部品および絶縁材料として幅広く使用されている。 In general, a polyimide resin is a heat-resistant resin obtained by subjecting a polyamic acid obtained by a condensation reaction of an aromatic tetracarboxylic acid anhydride and an aromatic diamine to a dehydration ring-closing reaction. Excellent thermal decomposition resistance due to molecular chain rigidity, resonance stabilization, and strong chemical bonding, and resistance to chemical changes such as oxidation and hydrolysis, and excellent mechanical properties, electrical properties and flexibility Therefore, it is widely used as a film, coating agent, molded part and insulating material in fields such as electrical, electronic, automotive and aerospace industries.
しかし、一般に、芳香族ポリイミド樹脂フィルムは、分子内あるいは分子間電子移動錯体の形成に由来する可視光の吸収により、黄色あるいは褐色に着色しているため、フラットパネルディスプレーや携帯電話機器等の基板材料、光ファイバー、光導波路、光学用接着剤等の光学用途には適さなかった。このような光学用途においては、フレキシブル性、耐熱着色性および機械強度を併せ持つ透明高耐熱性樹脂の技術開発が急務となっている。 However, in general, aromatic polyimide resin films are colored yellow or brown due to absorption of visible light derived from the formation of intramolecular or intermolecular electron transfer complexes, so substrates for flat panel displays, mobile phone devices, etc. It was not suitable for optical applications such as materials, optical fibers, optical waveguides, and optical adhesives. In such an optical application, there is an urgent need for technical development of a transparent high heat resistant resin having both flexibility, heat resistant colorability and mechanical strength.
光学用プラスチックとして用いられてきたポリメタクリル酸メチルは、低複屈折性と無色透明性を有しているが、耐熱性が不足しているため、上記光学用途には使用出来なかった。また、ポリカーボネートは、比較的高いガラス転移温度を有しているが、上記光学用途に必要とされる耐熱着色性を満足できず、複屈折も大きいという欠点のため適応できなかった。 Polymethyl methacrylate, which has been used as an optical plastic, has low birefringence and colorless transparency, but cannot be used in the above optical applications because of insufficient heat resistance. Further, polycarbonate has a relatively high glass transition temperature, but cannot satisfy the heat-resistant coloring property required for the above optical use and cannot be adapted due to the disadvantage that the birefringence is large.
発光ダイオード（ＬＥＤ）、光センサ等の光電変換デバイスの封止材料には、無色透明性、易成形性、耐熱性が必要とされる。特に、ＬＥＤの封止材料としては、これらの性能に優れるエポキシ樹脂が広く用いられてきた（特許文献１参照）。近年、発光材料の開発が進んだことにより、ＬＥＤは高輝度化するとともに青色や紫外光等発光波長の短いものが普及してきた。これに伴い、封止材料はより高温度や高いエネルギーの光にさらされる。既存のエポキシ樹脂は耐熱性、耐光性が不足しており、着色（黄変）が生じるなど長期間の無色透明性の維持は困難であった。また、環境保持の観点からハンダの鉛フリー化が進んでいるが、これに伴いＬＥＤの実装温度も上がる傾向にある。既存のエポキシ樹脂では耐熱性が不足するために、鉛フリー化が困難であるという問題があった。 A sealing material for a photoelectric conversion device such as a light emitting diode (LED) or an optical sensor requires colorless transparency, easy moldability, and heat resistance. In particular, epoxy resins having excellent performance have been widely used as LED sealing materials (see Patent Document 1). In recent years, as the development of light emitting materials has progressed, LEDs have become brighter, and those with short emission wavelengths such as blue and ultraviolet light have become widespread. Accordingly, the sealing material is exposed to light of higher temperature and higher energy. Existing epoxy resins have insufficient heat resistance and light resistance, and it has been difficult to maintain colorless transparency for a long period of time such as coloring (yellowing). Moreover, although lead-free soldering is progressing from the viewpoint of environmental preservation, the LED mounting temperature tends to increase accordingly. There is a problem that it is difficult to make lead-free because existing epoxy resins lack heat resistance.
これに対し、耐熱性、耐光性に優れる封止材料としてシリコーン系樹脂を用いる検討が行なわれている。しかしながら、シリコーン系樹脂は密着性が不充分で脆いという欠点があり、デバイスの信頼性の点で問題がある。さらにシリコーン系樹脂を封止材料に用いると、デバイスの実装時の高温環境下では、樹脂から発生する揮発成分に起因して電気接触不良が発生する場合がある。さらに、スネルの法則によるとＬＥＤの光取り出し効率を上げるためには、発光波長域における封止材料の屈折率は高いことが好ましい。これに対し、既存のエポキシ樹脂やシリコーン系樹脂の屈折率は一般的に１．５５未満であり、さらに高い屈折率を有する封止材料が求められている。 On the other hand, studies have been made to use a silicone resin as a sealing material having excellent heat resistance and light resistance. However, silicone resins have the drawback of insufficient adhesion and are brittle, and there is a problem in terms of device reliability. Further, when a silicone resin is used as a sealing material, an electrical contact failure may occur due to a volatile component generated from the resin under a high temperature environment when the device is mounted. Furthermore, according to Snell's law, in order to increase the light extraction efficiency of the LED, it is preferable that the refractive index of the sealing material in the emission wavelength region is high. On the other hand, the refractive index of the existing epoxy resin or silicone resin is generally less than 1.55, and a sealing material having a higher refractive index is demanded.
また、従来ＬＥＤデバイスの封止に用いられているエポキシ樹脂やシリコーン系樹脂は熱硬化性樹脂であるため、封止時の硬化に時間がかかり、製造時間が長くなるという問題があった。これに対し、熱可塑性樹脂を射出成形することによりＬＥＤデバイスの封止を行なう方法が提案されている（特許文献２参照）。しかし、この方法ではＬＥＤ実装時の高温環境下では封止樹脂が軟化し変形してしまうために、封止が不完全になるという問題があった。 Moreover, since the epoxy resin and silicone resin conventionally used for sealing of LED devices are thermosetting resins, there is a problem that it takes time to cure at the time of sealing and the manufacturing time becomes long. On the other hand, a method for sealing an LED device by injection molding a thermoplastic resin has been proposed (see Patent Document 2). However, this method has a problem that sealing is incomplete because the sealing resin is softened and deformed in a high temperature environment during LED mounting.
そのような問題を解決する材料として、無色透明性ポリイミド樹脂が提案されている。高い耐熱性と透明性を有するポリイミド樹脂として、パーフルオロアルキル基を有する繰り返し構造単位を含むフッ素化ポリイミド樹脂が報告されている（特許文献3および特許文献4参照）。フッ素化ポリイミド樹脂は、溶媒可溶性に乏しいので、保存安定性の悪いポリアミド酸をキャストして膜形成した後、３５０℃の高温で加熱イミド化してフィルムに成形している。フッ素を含むため、塗膜形成やイミド化の際の熱処理により黄色に着色しやすく、表面平滑性が不安定であり、膜厚の制御が難しいといった不具合がある。 As a material for solving such a problem, a colorless and transparent polyimide resin has been proposed. As a polyimide resin having high heat resistance and transparency, a fluorinated polyimide resin containing a repeating structural unit having a perfluoroalkyl group has been reported (see Patent Document 3 and Patent Document 4). Since the fluorinated polyimide resin is poor in solvent solubility, after forming a film by casting a polyamic acid having poor storage stability, the film is formed by heating imidization at a high temperature of 350 ° C. Since it contains fluorine, it tends to be colored yellow by heat treatment during coating film formation or imidization, surface smoothness is unstable, and film thickness control is difficult.
１，２，４，５−シクロヘキサンテトラカルボン酸二無水物を用いて熱溶融可能なポリイミド樹脂を得る技術が開示されている(特許文献５参照)。その実施例１では、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物とジアミノジフェニルメタンと反応させてポリアミド酸を得、これを加熱してイミド化し、得られたポリイミドを加熱加圧成形して、ガラス転移温度３０４℃の透明で黄色のポリイミド樹脂フィルムを製造している。また、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物とジアミノジフェニルエーテルから調製したポリイミド樹脂溶液からガラス転移温度３００℃以上で透明で着色の少ないフィルムが得られることが報告されている(特許文献6参照)。特許文献５記載の方法は、従来法と同様に高温のイミド化工程を含むので、着色防止性が不十分であり、また、両特許文献に記載のポリイミド樹脂フィルムは、吸水率が高く、吸湿寸法安定性に劣る欠点を有していた。 A technique for obtaining a heat-meltable polyimide resin using 1,2,4,5-cyclohexanetetracarboxylic dianhydride is disclosed (see Patent Document 5). In Example 1, 1,2,4,5-cyclohexanetetracarboxylic dianhydride and diaminodiphenylmethane are reacted to obtain polyamic acid, which is heated to imidize, and the resulting polyimide is heated and pressed. Thus, a transparent yellow polyimide resin film having a glass transition temperature of 304 ° C. is manufactured. It has also been reported that a transparent and less colored film can be obtained at a glass transition temperature of 300 ° C. or higher from a polyimide resin solution prepared from 1,2,4,5-cyclohexanetetracarboxylic dianhydride and diaminodiphenyl ether ( (See Patent Document 6). Since the method described in Patent Document 5 includes a high-temperature imidization step as in the conventional method, the anti-coloring property is insufficient, and the polyimide resin films described in both Patent Documents have high water absorption and moisture absorption. It had the disadvantage of poor dimensional stability.
本発明の目的は、上述の課題を解決し、フレキシブル性、耐熱性、透明性および寸法安定性に優れ、フラットパネルディスプレーや携帯電話機器等の基板材料、光ファイバー、光導波路、光学用接着剤等の光学用途に好適な低吸水性ポリイミド樹脂を提供することにある。
本発明の他の目的は、鉛フリーハンダを用いる実装を可能にし、かつ、高い光取り出し効率を得ることができる、ＬＥＤ、光センサ等の光電変換デバイスの封止材料として好適な、無色、透明、高耐熱性かつ高屈折率であり、高温での着色が少ない低吸水性ポリイミド樹脂を提供することにある。
本発明の他の目的は、上記ポリイミド樹脂からなるフィルムを製造する方法を提供することにある。
さらに、本発明の目的は、上記ポリイミド樹脂を含有する封止材を提供することにある。
The object of the present invention is to solve the above-mentioned problems, excellent in flexibility, heat resistance, transparency and dimensional stability, substrate materials such as flat panel displays and mobile phone devices, optical fibers, optical waveguides, optical adhesives, etc. Another object of the present invention is to provide a low water-absorbing polyimide resin suitable for optical use.
Another object of the present invention is colorless, transparent, suitable as a sealing material for photoelectric conversion devices such as LEDs and photosensors, which can be mounted using lead-free solder and can obtain high light extraction efficiency. Another object of the present invention is to provide a low water-absorbing polyimide resin that has high heat resistance and high refractive index and is less colored at high temperatures.
Another object of the present invention is to provide a method for producing a film comprising the above polyimide resin.
Furthermore, the objective of this invention is providing the sealing material containing the said polyimide resin.
本発明者らは、上記目的を達成するために鋭意検討を重ねた結果、特定の脂環式テトラカルボン酸、脂環式テトラカルボン酸二無水物およびこれらの反応性誘導体から選ばれる化合物と、特定の構造を有するジアミンおよびジイソシアネートから選ばれる化合物とのイミド化反応により得られるポリイミド樹脂が高い耐熱性と透明性を維持しながら低吸水性を有することを見出し、本発明に至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained a compound selected from a specific alicyclic tetracarboxylic acid, alicyclic tetracarboxylic dianhydride, and a reactive derivative thereof, The present inventors have found that a polyimide resin obtained by an imidation reaction with a compound selected from a diamine having a specific structure and a diisocyanate has low water absorption while maintaining high heat resistance and transparency, and has led to the present invention.
すなわち、本発明は、下記式１:
で表される１，２，４，５−シクロヘキサンテトラカルボン酸、下記式２：
で表される１，２，４，５−シクロヘキサンテトラカルボン酸二無水物およびこれらの反応性誘導体からなる群より選ばれる少なくとも１種のアシル含有化合物と、下記式３：
（式中、Ｘは−ＮＨ２または−Ｎ＝Ｃ＝Ｏであり、ｎは０〜４の整数、ｐは０または１であり、ｎ＋ｐは１〜５の整数である）で表される、少なくとも一つのフェニレン基とイソプロピリデン基を有する化合物から選ばれる少なくとも１種のイミノ形成化合物とを反応させる工程を含むポリイミド樹脂の製造方法を提供する。
That is, the present invention provides the following formula 1:
1,2,4,5-cyclohexanetetracarboxylic acid represented by the following formula 2:
And at least one acyl-containing compound selected from the group consisting of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and their reactive derivatives represented by the following formula 3:
(Wherein, X is —NH 2 or —N═C═O, n is an integer of 0 to 4, p is 0 or 1, and n + p is an integer of 1 to 5). Provided is a method for producing a polyimide resin comprising a step of reacting at least one imino-forming compound selected from compounds having at least one phenylene group and isopropylidene group.
また、本発明は、上記製造方法によって得られた、下記式４：
さらに、本発明は、上記の製造方法で得られたポリイミド樹脂を含む溶液からポリイミドフィルムを製造する方法、および上記ポリイミド樹脂を含む光電変換デバイス用封止材を提供する。
Further, the present invention provides the following formula 4 obtained by the above production method:
Furthermore, this invention provides the method of manufacturing a polyimide film from the solution containing the polyimide resin obtained by said manufacturing method, and the sealing material for photoelectric conversion devices containing the said polyimide resin.
本発明のポリイミド樹脂は、下記式１：
で表される１，２，４，５−シクロヘキサンテトラカルボン酸、下記式２：
で表される１，２，４，５−シクロヘキサンテトラカルボン酸二無水物およびこれらの反応性誘導体からなる群より選ばれる少なくとも１種のアシル含有化合物と、下記式３：
（式中、Ｘは−ＮＨ２または−Ｎ＝Ｃ＝Ｏであり、ｎは０〜４の整数、ｐは０または１であり、ｎ＋ｐは１〜５の整数である）で表される、少なくとも一つのフェニレン基とイソプロピリデン基を有する化合物から選ばれる少なくとも１種のイミノ形成化合物とを、有機極性溶媒中で反応させることにより製造される。
The polyimide resin of the present invention has the following formula 1:
1,2,4,5-cyclohexanetetracarboxylic acid represented by the following formula 2:
And at least one acyl-containing compound selected from the group consisting of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and their reactive derivatives represented by the following formula 3:
(Wherein, X is —NH 2 or —N═C═O, n is an integer of 0 to 4, p is 0 or 1, and n + p is an integer of 1 to 5). It is produced by reacting at least one imino-forming compound selected from compounds having at least one phenylene group and isopropylidene group in an organic polar solvent.
前記アシル含有化合物としては、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物、１，２，４，５−シクロヘキサンテトラカルボン酸、１，２，４，５−シクロヘキサンテトラカルボン酸モノメチルエステル、１，２，４，５−シクロヘキサンテトラカルボン酸ジメチルエステル、１，２，４，５−シクロヘキサンテトラカルボン酸トリメチルエステル、１，２，４，５−シクロヘキサンテトラカルボン酸テトラメチルエステル、１，２，４，５−シクロヘキサンテトラカルボン酸モノエチルエステル、１，２，４，５−シクロヘキサンテトラカルボン酸ジエチルエステル、１，２，４，５−シクロヘキサンテトラカルボン酸トリエチルエステル、１，２，４，５−シクロヘキサンテトラカルボン酸テトラエチルエステルなどが挙げられ、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物が好ましい。これらは単独であるいは２種以上混合して用いることができる。 Examples of the acyl-containing compound include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid monomethyl ester 1,2,4,5-cyclohexanetetracarboxylic acid dimethyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid trimethyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid tetramethyl ester, 1,2 , 4,5-cyclohexanetetracarboxylic acid monoethyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid diethyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid triethyl ester, 1,2,4,5 -Cyclohexanetetracarboxylic acid tetraethyl ester Gerare, 1,2,4,5-cyclohexane tetracarboxylic dianhydride is preferred. These can be used alone or in admixture of two or more.
前記イミノ形成化合物としては、２，２−ビス（３−アミノフェニル）プロパン、２，２−ビス（４−アミノフェニル）プロパン、１，３−ビス（３−アミノ−α，α−ジメチルベンジル）ベンゼン、１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン、１，４−ビス（３−アミノ−α，α−ジメチルベンジル）ベンゼン、１，４−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン、２，２−ビス［４−（３−アミノ−α，α−ジメチルベンジル）フェニル］プロパン、２，２−ビス［４−（４−アミノ−α，α−ジメチルベンジル）フェニル］プロパン、２，２−ビス（３−イソシアナトフェニル）プロパン、２，２−ビス（４−イソシアナトフェニル）プロパン、１，３−ビス（３−イソシアナト−α，α−ジメチルベンジル）ベンゼン、１，３−ビス（４−イソシアナト−α，α−ジメチルベンジル）ベンゼン、１，４−ビス（３−イソシアナト−α，α−ジメチルベンジル）ベンゼン、１，４−ビス（４−イソシアナト−α，α−ジメチルベンジル）ベンゼン、２，２−ビス［４−（３−イソシアナト−α，α−ジメチルベンジル）フェニル］プロパン、２，２−ビス［４−（４−イソシアナト−α，α−ジメチルベンジル）フェニル］プロパン、ｍ−α，α，α’，α’−テトラメチルキシリレンジアミン、ｍ−α，α，α’，α’−テトラメチルキシリレンジイソシアネート、２，２−ビス−［４−（ジメチルアミノメチル）フェニル］プロパン、２，２−ビス−［４−（ジメチルイソシアナトメチル）フェニル］プロパンなどが挙げられ、ジアミン化合物（式３の２つのＸが−ＮＨ２である化合物）が好ましい。これらは単独あるいは２種以上混合して用いることができる。 Examples of the imino-forming compound include 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) propane, and 1,3-bis (3-amino-α, α-dimethylbenzyl). Benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-) α, α-dimethylbenzyl) benzene, 2,2-bis [4- (3-amino-α, α-dimethylbenzyl) phenyl] propane, 2,2-bis [4- (4-amino-α, α- Dimethylbenzyl) phenyl] propane, 2,2-bis (3-isocyanatophenyl) propane, 2,2-bis (4-isocyanatophenyl) propane, 1,3-bis (3-isocyanato-α, α-dimethyl Benji L) benzene, 1,3-bis (4-isocyanato-α, α-dimethylbenzyl) benzene, 1,4-bis (3-isocyanato-α, α-dimethylbenzyl) benzene, 1,4-bis (4- Isocyanato-α, α-dimethylbenzyl) benzene, 2,2-bis [4- (3-isocyanato-α, α-dimethylbenzyl) phenyl] propane, 2,2-bis [4- (4-isocyanato-α, α-dimethylbenzyl) phenyl] propane, m-α, α, α ′, α′-tetramethylxylylenediamine, m-α, α, α ′, α′-tetramethylxylylene diisocyanate, 2,2-bis -[4- (dimethylaminomethyl) phenyl] propane, 2,2-bis- [4- (dimethylisocyanatomethyl) phenyl] propane and the like, and diamine compounds (two X's of formula 3 Is a compound in which —NH 2 is preferred. These may be used alone or in combination of two or more.
前記イミノ形成化合物の他にも、ポリイミド樹脂の良好な低吸水性を損なわない範囲で他のジアミンを、各種物性、例えば耐熱性、熱膨張係数、誘電率、屈折率または複屈折などを制御するために、必要に応じてイミノ形成化合物の１〜４９モル％併用することもできる。 In addition to the imino-forming compound, other diamines are controlled within a range that does not impair good low water absorption of the polyimide resin, and various physical properties such as heat resistance, thermal expansion coefficient, dielectric constant, refractive index, or birefringence are controlled. Therefore, 1 to 49 mol% of the imino forming compound can be used together as necessary.
併用できるジアミンは限定されるわけではないが、例えば、ｍ−フェニレンジアミン、ｐ−フェニレンジアミン、４，４’−ジアミノジフェニルエーテル、３，３’−ジアミノジフェニルエーテル、４，４’−ジアミノジフェニルメタン、３，３’−ジアミノジフェニルメタン、４，４’−ジアミノジフェニルスルホン、３，３’−ジアミノジフェニルスルホン、４，４’−ジアミノベンゾフェノン、３，３’−ジアミノベンゾフェノン、１，３−ビス（３−アミノフェノキシ）ベンゼン、１，３−ビス（４−アミノフェノキシ）ベンゼン、１，４−ビス（４−アミノフェノキシ）ベンゼン、４，４’−ビス（３−アミノフェノキシ）ビフェニル、４，４’−ビス（４−アミノフェノキシ）ビフェニル、ビス［４−（３−アミノフェノキシ）フェニル］スルホン、ビス［４−（４−アミノフェノキシ）フェニル］スルホン、ビス［４−（３−アミノフェノキシ）フェニル］エーテル、ビス［４−（４−アミノフェノキシ）フェニル］エーテル、ビス［４−（３−アミノフェノキシ）フェニル］プロパン、ビス［４−（４−アミノフェノキシ）フェニル］プロパン、ビス（４−アミノシクロヘキシル）メタン、ｍ−キシリレンジアミン、ｐ−キシリレンジアミン、イソフォロンジアミンなどが挙げられる。 The diamine that can be used in combination is not limited. For example, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenylmethane, 3, 3'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 1,3-bis (3-aminophenoxy ) Benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis ( 4-Aminophenoxy) biphenyl, bis [4- (3-aminophenoxy) Enyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-aminophenoxy) phenyl] ether, bis [4- (3-aminophenoxy) phenyl] propane, bis [4- (4-aminophenoxy) phenyl] propane, bis (4-aminocyclohexyl) methane, m-xylylenediamine, p-xylylenediamine, isophoronediamine and the like Can be mentioned.
本発明の製造方法に用いる有機極性溶媒は特に限定されないが、非プロトン性有機極性溶媒であることが望ましい。例えば、γ−ブチロラクトン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルフォルムアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド、ｐ−クロロフェノール、ｍ−クレゾール、テトラヒドロフランなどが挙げられる。上記の中でも特にγ−ブチロラクトンおよびＮ，Ｎ−ジメチルアセトアミドを用いることにより無色・透明性が向上する。これらの溶媒は単独あるいは２種以上混合して使用することができる。 Although the organic polar solvent used for the manufacturing method of this invention is not specifically limited, It is desirable that it is an aprotic organic polar solvent. Examples include γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, p-chlorophenol, m-cresol, tetrahydrofuran and the like. Among these, colorlessness and transparency are improved by using γ-butyrolactone and N, N-dimethylacetamide. These solvents can be used alone or in admixture of two or more.
本発明のポリイミド樹脂の製造方法および得られたポリイミド樹脂の有機極性溶媒溶液を用いるポリイミドフィルムの製造方法について、以下に説明する。 The manufacturing method of the polyimide resin of this invention and the manufacturing method of the polyimide film using the organic polar solvent solution of the obtained polyimide resin are demonstrated below.
ポリイミド樹脂溶液の製造
少なくとも１種のイミノ形成化合物を有機極性溶媒に溶解する。有機極性溶媒１００重量部に対してイミノ形成化合物を１０〜３０重量部溶解するのが好ましい。得られた溶液に、少なくとも１種のアシル含有化合物を−５℃〜室温付近で添加後、室温付近〜１００℃の温度に３０〜６０分間保ってポリアミド酸溶液を製造する。
Preparation of polyimide resin solution At least one imino-forming compound is dissolved in an organic polar solvent. It is preferable to dissolve 10 to 30 parts by weight of the imino-forming compound with respect to 100 parts by weight of the organic polar solvent. At least one acyl-containing compound is added to the obtained solution at −5 ° C. to about room temperature, and then kept at a temperature of about room temperature to 100 ° C. for 30 to 60 minutes to produce a polyamic acid solution.
反応液中の１種以上のイミノ形成化合物と１種以上のアシル含有化合物の合計量は、反応液全量の２０〜５０重量％が好ましく、３０〜４０重量％がより好ましい。２０重量％以上であると、適切な固有粘度のポリイミド樹脂が得られる。５０重量％以下であると、ポリイミド樹脂の固有粘度が過剰に増大することを防ぐことができ、ポリイミド樹脂溶液の粘度が高くなり過ぎて、均一撹拌が困難になり、樹脂が焦げ付く問題を避けることができる。 The total amount of one or more imino-forming compounds and one or more acyl-containing compounds in the reaction solution is preferably 20 to 50% by weight, more preferably 30 to 40% by weight, based on the total amount of the reaction solution. When it is 20% by weight or more, a polyimide resin having an appropriate intrinsic viscosity can be obtained. If it is 50% by weight or less, the intrinsic viscosity of the polyimide resin can be prevented from excessively increasing, and the viscosity of the polyimide resin solution becomes too high, making it difficult to uniformly stir and avoiding the problem of the resin scorching. Can do.
ついで、必要に応じてイミド化触媒を添加し、加熱還流下、生成水を系外に留出しつつ脱水反応を生成水の留出がなくなるまで行い、ポリイミド樹脂溶液を得る。イミド化触媒は、トリメチルアミン、トリエチルアミン、トリ−ｎ−プロピルアミン、トリ−ｎ−ブチルアミン、ピリジン、β−ピコリンなどの３級アミン；亜燐酸、燐酸、塩酸、過塩素酸などの無機酸類；クロトン酸、安息香酸などの有機酸類から選択される。これらの中で、特に３級アミンを使用することが好ましい。イミド化触媒の添加量は、アシル含有化合物の１〜１０モル％が好ましい。 Then, if necessary, an imidation catalyst is added, and while heating and refluxing, the dehydrated reaction is performed while distilling out the generated water out of the system until the distilling of the generated water ceases to obtain a polyimide resin solution. Imidation catalysts include tertiary amines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, and β-picoline; inorganic acids such as phosphorous acid, phosphoric acid, hydrochloric acid, perchloric acid; crotonic acid Selected from organic acids such as benzoic acid. Among these, it is particularly preferable to use a tertiary amine. The amount of the imidation catalyst added is preferably 1 to 10 mol% of the acyl-containing compound.
上記方法の代わりに、アシル含有化合物、イミノ形成化合物、有機極性溶媒および必要に応じてイミド化触媒を一括に仕込んだ後加熱を開始し、直ちに脱水イミド化を行うことも好ましい。 Instead of the above-described method, it is also preferable to start dehydration and imidization immediately after charging the acyl-containing compound, the imino-forming compound, the organic polar solvent and, if necessary, the imidization catalyst all at once.
イミノ形成化合物とアシル含有化合物とのモル比は、好ましくは０．９５〜１．０５、より好ましくは０．９９〜１．０１である。上記範囲内であると、適切な対数粘度（０．５〜２．０）の無色透明性ポリイミド樹脂が得られ、十分な強度のポリイミドフィルムが得られる。 The molar ratio between the imino-forming compound and the acyl-containing compound is preferably 0.95 to 1.05, more preferably 0.99 to 1.01. Within the above range, a colorless transparent polyimide resin having an appropriate logarithmic viscosity (0.5 to 2.0) is obtained, and a polyimide film having sufficient strength is obtained.
脱水イミド化の反応温度は好ましくは１６０〜２００℃、より好ましくは１７０〜１９０℃、さらに好ましくは１８０〜１９０℃である。上記範囲内であると、高分子量化が十分に進行し、また、溶液粘度が著しく増加し樹脂が反応容器の壁面に焦げ付くなどの不具合を避けることができる。また、場合によってはトルエン、キシレンなどの共沸脱水剤を用いても良い。脱水イミド化時間は、イミノ形成化合物の反応性に依存するが、３〜１２時間が好ましく、６〜８時間がより好ましい。 The reaction temperature of dehydration imidation is preferably 160 to 200 ° C, more preferably 170 to 190 ° C, and further preferably 180 to 190 ° C. Within the above range, high molecular weight can be sufficiently increased, and the viscosity of the solution can be remarkably increased so that problems such as the resin scorching on the wall surface of the reaction vessel can be avoided. In some cases, an azeotropic dehydrating agent such as toluene or xylene may be used. The dehydration imidation time depends on the reactivity of the imino forming compound, but is preferably 3 to 12 hours, more preferably 6 to 8 hours.
通常は、上記方法によりポリイミド樹脂溶液を製造するが、第３の製造方法として、ポリアミド酸溶液を製造し、これに無水酢酸などの脱水剤および公知の３級アミンを添加し、１００〜１２０℃で３〜６時間イミド化を行い、メタノールなどのポリイミドに対する貧溶媒を添加してポリイミド樹脂を沈殿させ、ろ過・洗浄・乾燥によりポリイミド樹脂を固体として分離し、有機極性溶媒に溶解させてポリイミド樹脂溶液を得ることもできる。 Usually, a polyimide resin solution is produced by the above-mentioned method. As a third production method, a polyamic acid solution is produced, and a dehydrating agent such as acetic anhydride and a known tertiary amine are added thereto, and a temperature of 100 to 120 ° C. In 3 to 6 hours, imidization is performed, a poor solvent for polyimide such as methanol is added to precipitate the polyimide resin, the polyimide resin is separated as a solid by filtration, washing and drying, and dissolved in an organic polar solvent to obtain a polyimide resin. A solution can also be obtained.
ポリイミド樹脂を溶解する有機極性溶媒としては、γ−ブチロラクトン、Ｎ，Ｎ−ジメチルアセトアミド、Ｎ，Ｎ−ジメチルフォルムアミド、Ｎ−メチル−２−ピロリドン、ジメチルスルホキシド、ヘキサメチルホスホルアミド、ｐ−クロロフェノール、ｍ−クレゾール、テトラメチレンスルホン、プロピレンカーボネート等が挙げられる。これらの溶媒は２種以上混合して使用することもできる。さらに、樹脂の溶解度が低くならない範囲で、テトラヒドロフラン、１，４−ジオキサン、１，３−ジオキソランなどの環状エーテル類およびシクロヘキサノン、シクロペンタノン等の環状ケトン類を併用することもできる。 Examples of the organic polar solvent for dissolving the polyimide resin include γ-butyrolactone, N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, hexamethylphosphoramide, p-chloro. Phenol, m-cresol, tetramethylene sulfone, propylene carbonate and the like can be mentioned. These solvents can be used in combination of two or more. Furthermore, cyclic ethers such as tetrahydrofuran, 1,4-dioxane and 1,3-dioxolane and cyclic ketones such as cyclohexanone and cyclopentanone can be used in combination as long as the solubility of the resin does not decrease.
上記各製造方法で得られたポリイミド樹脂は下記式４：
５１モル％以上（１００％を含む）有する。他の繰り返し単位は、上記した任意に使用されるジアミンに由来する。また、上記各製造方法で得られたポリイミド樹脂溶液中のポリイミド樹脂濃度は１０〜５０重量％であるのが好ましく、２０〜３０重量％であるのがより好ましい。
The polyimide resin obtained by each of the above production methods is represented by the following formula 4:
ポリイミドフィルムの製造
上記方法により製造したポリイミド樹脂溶液を、離型性を付与したガラス基板あるいはステンレス製基板などにキャストして膜状とし、ホットプレート上あるいは乾燥炉中で、その膜が自己支持性を有するまで８０〜１２０℃の温度で約３０〜６０分予備乾燥する。ついで、膜を基板から引き剥がし、両端部を固定した後、膜の収縮を制限しながら残留溶媒の突沸が起こらないように少なくとも使用溶媒の沸点か、好ましくは沸点よりも５〜１０℃高い温度まで１時間かけて昇温し、該温度において真空乾燥し、ポリイミド樹脂フィルムを得る。
Manufacture of polyimide film The polyimide resin solution manufactured by the above method is cast on a glass substrate or stainless steel substrate to which release properties are imparted to form a film, and the film is self-supporting on a hot plate or in a drying furnace. Is pre-dried at a temperature of 80 to 120 ° C. for about 30 to 60 minutes. Next, after peeling off the film from the substrate and fixing both ends, at least the boiling point of the solvent used, preferably 5 to 10 ° C. higher than the boiling point so that the residual solvent does not bump while limiting the shrinkage of the film The temperature is raised over 1 hour and vacuum dried at the temperature to obtain a polyimide resin film.
真空乾燥を行う時間はフィルムの膜厚にも依存するが、例えば、１５０〜２００μｍのフレキシブルディスプレー用プラスチック基板用フィルムの場合、残留溶媒を１％未満にするには、５〜４８時間が好ましく、より好ましくは８〜２４時間である。 The time for performing vacuum drying depends on the film thickness of the film. For example, in the case of a film for a plastic substrate for flexible display having a thickness of 150 to 200 μm, 5 to 48 hours are preferable to reduce the residual solvent to less than 1%. More preferably, it is 8 to 24 hours.
ポリイミド樹脂溶液をガラス基板あるいはステンレス製の基板にキャストするには、公知の乾式ならびに乾湿式成形方法等のいかなる製膜方法を用いてもよい。例えば、ダイ押し出しによる流延法、アプリケーター、コーター等を用いる方法が挙げられる。また、ポリエチレンテレフタレートやポリエチレンナフタレートのような有機高分子のフィルム上にキャストすることもできる。 In order to cast the polyimide resin solution onto a glass substrate or a stainless steel substrate, any film forming method such as a known dry type or dry wet type method may be used. Examples thereof include a casting method using die extrusion, a method using an applicator, a coater, and the like. It can also be cast on an organic polymer film such as polyethylene terephthalate or polyethylene naphthalate.
ポリイミド樹脂フィルムの表面平滑性や、離型性などの特性を向上させることを目的に、製造の任意の段階で、各種界面活性剤や内部離型剤などを加えることができる。 Various surfactants and internal mold release agents can be added at any stage of production for the purpose of improving the properties such as surface smoothness and releasability of the polyimide resin film.
上記方法により得たポリイミド樹脂溶液を光電変換素子の上に塗布した後、有機溶媒を揮発させることにより、耐熱性に優れ、高い屈折率を有する樹脂封止部を形成し、優れた光電変換デバイスを得ることができる。また、ＬＥＤ用封止樹脂には発光波長を可視領域に変換する等の目的で蛍光材料等が混合される場合がある。本発明のポリイミド樹脂は各種蛍光材料と混合した場合に混合性、分散性、安定性に優れているので、ＬＥＤ用の封止材料として好ましい。さらに、樹脂封止部の表面に、発光方向の制御の目的で、任意の透明樹脂製のレンズを形成する事も可能である。この樹脂製レンズに導入される光は、樹脂封止部で低エネルギーの可視光に変換されているので、汎用エポキシ樹脂等のレンズでも充分な耐久性を示す。本発明のポリイミド樹脂はエポキシ樹脂等のレンズと良好な密着性を有するので、LEDの封止材料として特に好ましい。 After applying the polyimide resin solution obtained by the above method onto a photoelectric conversion element, the organic solvent is volatilized to form a resin-sealed portion having excellent heat resistance and a high refractive index, and an excellent photoelectric conversion device Can be obtained. In addition, a fluorescent material or the like may be mixed in the LED sealing resin for the purpose of converting the emission wavelength into the visible region. Since the polyimide resin of the present invention is excellent in mixing property, dispersibility, and stability when mixed with various fluorescent materials, it is preferable as a sealing material for LED. Furthermore, any transparent resin lens can be formed on the surface of the resin sealing portion for the purpose of controlling the light emission direction. Since the light introduced into the resin lens is converted into low energy visible light at the resin sealing portion, a lens such as a general-purpose epoxy resin exhibits sufficient durability. The polyimide resin of the present invention is particularly preferable as an LED sealing material because it has good adhesion to a lens such as an epoxy resin.
以下、実施例により本発明を具体的に説明する。但し、本発明はこれら実施例になんら制限されるものではない。
なお、実施例および比較例で得られたポリイミド樹脂、ポリイミドフィルムの物性は、以下に示す方法で測定した。
Hereinafter, the present invention will be described specifically by way of examples. However, the present invention is not limited to these examples.
In addition, the physical property of the polyimide resin and polyimide film obtained by the Example and the comparative example was measured by the method shown below.
（１）対数粘度
ポリイミド樹脂溶液の一部を無水メタノールに投入してポリイミド樹脂を析出させ、ろ過して未反応単量体から分離した。８０℃で１２時間真空乾燥して得られたポリイミド０．１ｇをＮ−メチル−２−ピロリドン２０ｍＬに溶解し、キャノン−フェンスケ粘度計を使用して３０℃における対数粘度（μ）を下記式により求めた。
μ＝｛ｌｎ（ｔｓ／ｔ０）｝／Ｃ
ｔ０：溶媒の流下時間
ｔｓ：希薄高分子溶液の流下時間
Ｃ：０．５ｇ／ｄＬ
(1) Logarithmic viscosity A part of the polyimide resin solution was put into anhydrous methanol to precipitate the polyimide resin, and filtered to separate from the unreacted monomer. 0.1 g of polyimide obtained by vacuum drying at 80 ° C. for 12 hours is dissolved in 20 mL of N-methyl-2-pyrrolidone, and the logarithmic viscosity (μ) at 30 ° C. is obtained by the following formula using a Canon-Fenske viscometer. Asked.
μ = {ln (t s / t 0)} / C
t 0 : Flowing time of solvent t s : Flowing time of dilute polymer solution C: 0.5 g / dL
（２）ガラス転移温度（Ｔｇ）
島津製作所（株）製ＤＳＣ−４０Ｍ型示差熱分析装置を用いて、ポリイミドフィルムを窒素雰囲気下において１０℃／分で４００℃まで昇温し、ガラス転移温度を測定した。
(2) Glass transition temperature (Tg)
Using a DSC-40M differential thermal analyzer manufactured by Shimadzu Corporation, the polyimide film was heated to 400 ° C. at 10 ° C./min in a nitrogen atmosphere, and the glass transition temperature was measured.
（３）吸水率測定
約２５μｍの厚さのポリイミドフィルムを１５０℃で１時間乾燥した。デシケーター中に１時間保持した後の重量をＷ１とし、２３℃の蒸留水に２４時間浸漬し、表面の水滴を拭き取った後の重量をＷ２とし、下記式より算出した。
吸水率（％）＝（Ｗ２−Ｗ１）÷Ｗ１×１００
(3) Measurement of water absorption rate A polyimide film having a thickness of about 25 μm was dried at 150 ° C. for 1 hour. The weight after holding in a desiccator for 1 hour was defined as W1, and the weight after immersing in distilled water at 23 ° C. for 24 hours and wiping off the water droplets on the surface was defined as W2.
Water absorption rate (%) = (W2−W1) ÷ W1 × 100
（４）全光線透過率およびＹＩ値
「ＪＩＳ Ｋ７１０５透明度試験法」に準ずる無色性、透明性を評価する指標としてポリイミドフィルムの全光線透過率およびＹＩ値を、日本電色工業株式会社製色差・濁度測定器ＣＯＩ−３００Ａを用いて測定した。
(4) Total light transmittance and YI value As an index for evaluating the colorlessness and transparency according to “JIS K7105 Transparency Test Method”, the total light transmittance and YI value of the polyimide film were used. It measured using turbidity measuring device COI-300A.
（５）屈折率
（株）アタゴ社製屈折率測定装置（ＤＲ−Ｍ２）を用い、５８９ｎｍの干渉フィルターをセットし、２３℃で屈折率を測定した。
(5) Refractive index Using a refractive index measuring apparatus (DR-M2) manufactured by Atago Co., Ltd., a 589 nm interference filter was set, and the refractive index was measured at 23 ° C.
（６）耐熱加速試験
１５０℃に保持した熱風乾燥機中に５０×５０ｍｍの試験フィルムを入れ、４００ｎｍにおける光線透過率およびＹＩ値の変化を追跡した。
(6) Heat resistance acceleration test A 50 × 50 mm test film was placed in a hot air dryer maintained at 150 ° C., and changes in light transmittance and YI value at 400 nm were followed.
参考例１〈１，２，４，５−シクロヘキサンテトラカルボン酸二無水物の合成〉
内容積５リットルのハステロイ製（ＨＣ２２）オートクレーブに、ピロメリット酸５５２ｇ、活性炭にＲｈを担持させた触媒（エヌ・イーケムキャット（株）製）２００ｇ、水１６５６ｇを仕込み、撹拌しながらオートクレーブ内を水素ガスで置換し、水素圧を５．０ＭＰａとして６０℃まで昇温した。水素圧を５．０ＭＰａに保ちながら２時間反応させた。オートクレーブ内の水素ガスを窒素ガスで置換し、反応液をオートクレーブから抜き出した。この反応液を熱時濾過して触媒を分離した。ロータリーエバポレーターを用い、減圧下で濾過液から水を留去して濃縮し、結晶を析出させた。析出した結晶を室温で固液分離し、乾燥して１，２，４，５−シクロヘキサンテトラカルボン酸４８１ｇ（収率８５．０％）を得た。
Reference Example 1 <Synthesis of 1,2,4,5-cyclohexanetetracarboxylic dianhydride>
A 5 liter Hastelloy (HC22) autoclave is charged with 552 g of pyromellitic acid, 200 g of a catalyst with Rh supported on activated carbon (manufactured by NP Chemcat Co., Ltd.), and 1656 g of water. The gas was replaced with gas, and the temperature was raised to 60 ° C. with a hydrogen pressure of 5.0 MPa. The reaction was carried out for 2 hours while maintaining the hydrogen pressure at 5.0 MPa. The hydrogen gas in the autoclave was replaced with nitrogen gas, and the reaction solution was extracted from the autoclave. The reaction solution was filtered while hot to separate the catalyst. Using a rotary evaporator, water was distilled off from the filtrate under reduced pressure and concentrated to precipitate crystals. The precipitated crystals were separated into solid and liquid at room temperature and dried to obtain 481, g (yield: 85.0%) of 1,2,4,5-cyclohexanetetracarboxylic acid.
続いて、得られた１，２，４，５−シクロヘキサンテトラカルボン酸４８１ｇと無水酢酸４０００ｇとを、５リットルのガラス製セパラブルフラスコに仕込み、撹拌しながら反フラスコ内を窒素ガスで置換した。窒素ガス雰囲気下に溶媒の還流温度まで昇温し、１０分間溶媒を還流させた。撹拌しながら室温まで冷却し、結晶を析出させた。析出した結晶を固液分離し、乾燥して一次結晶を得た。さらに分離母液をロータリーエバポレーターにて減圧下に濃縮し、結晶を析出させた。この結晶を固液分離し、乾燥して二次結晶を得た。一次結晶、二次結晶を合わせて１，２，４，５−シクロヘキサンテトラカルボン酸二無水物３７５ｇが得られた（無水化の収率９６．６％）。 Subsequently, 481 g of the obtained 1,2,4,5-cyclohexanetetracarboxylic acid and 4000 g of acetic anhydride were charged into a 5-liter separable flask made of glass, and the inside of the anti-flask was replaced with nitrogen gas while stirring. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. While stirring, the mixture was cooled to room temperature to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain primary crystals. Further, the separated mother liquor was concentrated under reduced pressure using a rotary evaporator to precipitate crystals. The crystals were separated into solid and liquid and dried to obtain secondary crystals. The primary crystal and the secondary crystal were combined to obtain 375 g of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (anhydrous yield of 96.6%).
実施例１
温度計、撹拌器、窒素導入管、分留器付き冷却管を備えた５００ｍＬの５つ口フラスコ中で、窒素雰囲気下、１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン（ＢｉｓＡ−Ｍ、別称：４，４’−（ｍ−フェニレンジイソプロピリデン）ジアニリン）３４．５８ｇ（０．１モル）を溶媒（γ−ブチロラクトン６８．６５ｇ及びＮ，Ｎ−ジメチルアセトアミド１７．１６ｇ）に溶解した。得られた溶液を氷水バスを用いて５℃に冷却した。同温に保ちながら、１，２，４，５−シクロヘキサンテトラカルボン酸二無水物２２．６２（０．１モル）およびイミド化触媒としてトリエチルアミン０．５０ｇ（０．００５モル）を一括添加した。添加終了後、１８０℃に昇温し、随時留出液を留去させながら８時間還流させた。反応終了後、内温が１００℃になるまで空冷した後、Ｎ，Ｎ−ジメチルアセトアミド１４３．６ｇを加えて希釈し、撹拌しながら冷却し、固形分濃度２０重量％のポリイミド樹脂溶液を得た。このポリイミド樹脂溶液の重量は２６２．４７ｇ、また、留出液総重量は４．８６ｇであった。ポリイミド樹脂溶液の一部を１Ｌのメタノールに注ぎいれてポリイミドを沈殿させた。濾別したポリイミドをメタノールで洗浄した後、１００℃の真空乾燥機中で２４時間乾燥して白色粉末を得た。この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１７０２ｃｍ−１、１７７２ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、０．９４であった。
上記で得たポリイミド樹脂溶液を、１０００μｍのドクターブレードを用いて、プラスチック用離型剤（中京化成工業（株）製“ペリコート”）が均一に塗布されたステンレス基板上にキャストした。これをホットプレートで１００℃、６０分間保持し、溶媒を揮発させて自己支持性を有する無色透明な一次乾燥フィルムを得た。このフィルムをステンレス枠に固定し、２００℃で８時間真空乾燥して残留溶媒を除去し、膜厚１１７μｍの無色透明なポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値、吸水率およびガラス転移温度を測定した。結果を第１表に示した。
Example 1
1,3-bis (4-amino-α, α-dimethylbenzyl) benzene in a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a condenser tube with a fractionator under a nitrogen atmosphere (BisA-M, also known as 4,4 ′-(m-phenylenediisopropylidene) dianiline) 34.58 g (0.1 mol) was dissolved in solvents (68.65 g of γ-butyrolactone and 17.16 g of N, N-dimethylacetamide). ). The resulting solution was cooled to 5 ° C. using an ice water bath. While maintaining the same temperature, 22.62 (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and 0.50 g (0.005 mol) of triethylamine as an imidization catalyst were added all at once. After completion of the addition, the temperature was raised to 180 ° C., and the mixture was refluxed for 8 hours while distilling off the distillate as needed. After completion of the reaction, the mixture was air-cooled until the internal temperature reached 100 ° C., diluted by adding 143.6 g of N, N-dimethylacetamide, and cooled with stirring to obtain a polyimide resin solution having a solid content concentration of 20% by weight. . The weight of this polyimide resin solution was 262.47 g, and the total weight of the distillate was 4.86 g. A part of the polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide. The polyimide separated by filtration was washed with methanol, and then dried in a vacuum dryer at 100 ° C. for 24 hours to obtain a white powder. The IR spectrum of the powder was measured, 1702Cm -1 characteristic of imido group, absorption of 1772 cm -1 were observed. The logarithmic viscosity of the polyimide was measured and found to be 0.94.
The polyimide resin solution obtained above was cast on a stainless steel substrate uniformly coated with a mold release agent for plastic (“Pericoat” manufactured by Chukyo Chemical Co., Ltd.) using a 1000 μm doctor blade. This was kept on a hot plate at 100 ° C. for 60 minutes, and the solvent was volatilized to obtain a colorless and transparent primary dry film having self-supporting property. This film was fixed to a stainless steel frame and vacuum-dried at 200 ° C. for 8 hours to remove the residual solvent, thereby obtaining a colorless and transparent polyimide film having a film thickness of 117 μm. The total light transmittance, YI value, water absorption and glass transition temperature of this film were measured. The results are shown in Table 1.
実施例２
１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン３４．５８ｇ（０．１モル）のかわりに１，４−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン（ＢｉｓＡ−Ｐ）２７．６６ｇ（０．０８モル）およびｍ−フェニレンジアミン（ＭＰＤ）２．１６ｇ（０．０２モル）を用い、還流時間を６時間に変更した以外は実施例１と同様にして２４２．３３ｇのポリイミド樹脂溶液を得た。実施例１と同様にして白色粉末を得、この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１７０４ｃｍ−１、１７７０ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、１．０１であった。
上記で製造したポリイミド樹脂溶液を用い、実施例１と同様にして膜厚１２２μｍのポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値、吸水率およびガラス転移温度を測定した。結果を第１表に示した。
Example 2
1,4-bis (4-amino-α, α-dimethylbenzyl) benzene (BisA) instead of 34.58 g (0.1 mol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene -P) 242 in the same manner as in Example 1 except that 27.66 g (0.08 mol) and m-phenylenediamine (MPD) 2.16 g (0.02 mol) were used and the reflux time was changed to 6 hours. .33 g of polyimide resin solution was obtained. To give a white powder in the same manner as in Example 1, the IR spectrum of the powder was measured, 1704 cm -1 characteristic of imido group, absorption of 1770 cm -1 were observed. It was 1.01 when the logarithmic viscosity of the polyimide was measured.
Using the polyimide resin solution produced above, a polyimide film having a thickness of 122 μm was obtained in the same manner as in Example 1. The total light transmittance, YI value, water absorption and glass transition temperature of this film were measured. The results are shown in Table 1.
実施例３
１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン３４．５８ｇ（０．１モル）のかわりに１，４−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン（ＢｉｓＡ−Ｐ）２７．６６ｇ（０．０８モル）および４，４’−ビス（４−アミノフェノキシ）ビフェニル（ＢＡＰＢ）７．３８ｇ（０．０２モル）を用い、還流時間を６時間に変更した以外は実施例１と同様にして２６４．１６ｇのポリイミド樹脂溶液を得た。実施例１と同様にして白色粉末を得、この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１７０４ｃｍ−１、１７７０ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、０．８７であった。
上記で製造したポリイミド樹脂溶液を用い、実施例１と同様にして膜厚１１２μｍの無色透明なポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値、吸水率およびガラス転移温度を測定した。結果を第１表に示した。
Example 3
Instead of 34.58 g (0.1 mol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene (BisA -P) 27.66 g (0.08 mol) and 4,4'-bis (4-aminophenoxy) biphenyl (BAPB) 7.38 g (0.02 mol) were used, except that the reflux time was changed to 6 hours. Was the same as in Example 1 to obtain 264.16 g of a polyimide resin solution. To give a white powder in the same manner as in Example 1, the IR spectrum of the powder was measured, 1704 cm -1 characteristic of imido group, absorption of 1770 cm -1 were observed. It was 0.87 when the logarithmic viscosity of the polyimide was measured.
Using the polyimide resin solution produced above, a colorless and transparent polyimide film having a thickness of 112 μm was obtained in the same manner as in Example 1. The total light transmittance, YI value, water absorption, and glass transition temperature of this film were measured. The results are shown in Table 1.
実施例４
１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン３４．５８ｇ（０．１モル）のかわりにｍ−α，α，α’，α’−テトラメチルキシリレンジイソシアネート（ｍ−ＴＭＤＩ）２４．５２ｇ（０．１モル）を用いた以外は実施例１と同様にして２１４．１６ｇのポリイミド樹脂溶液を得た。実施例１と同様にして白色粉末を得、この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１６９８ｃｍ−１、１７７６ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、０．７２であった。
上記で製造したポリイミド樹脂溶液を用い、実施例１と同様にして膜厚１１２μｍの無色透明なポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値、吸水率およびガラス転移温度を測定した。結果を第１表に示した。
Example 4
Instead of 34.58 g (0.1 mol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, m-α, α, α ′, α′-tetramethylxylylene diisocyanate (m- TMDI) 24.52 g (0.1 mol) was used in the same manner as in Example 1 to obtain 214.16 g of a polyimide resin solution. To give a white powder in the same manner as in Example 1, the IR spectrum of the powder was measured, 1698 cm -1 characteristic of imido group, absorption of 1776 cm -1 were observed. The logarithmic viscosity of the polyimide was measured and found to be 0.72.
Using the polyimide resin solution produced above, a colorless and transparent polyimide film having a thickness of 112 μm was obtained in the same manner as in Example 1. The total light transmittance, YI value, water absorption and glass transition temperature of this film were measured. The results are shown in Table 1.
比較例１
１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン３４．５８ｇ（０．１モル）のかわりにビス（４−アミノフェニル）メタン（ＤＤＭ）１９．８３ｇ（０．１モル）を用い、還流時間を６時間に変更した以外は実施例１と同様にして２１０．５０ｇのポリイミド樹脂溶液を得た。実施例１と同様にして白色粉末を得、この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１７００ｃｍ−１、１７６８ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、１．０４であった。
上記で製造したポリイミド樹脂溶液を用い、実施例１と同様にして膜厚１０８μｍの無色透明なポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値およびガラス転移温度を測定した。結果を第１表に示した。
Comparative Example 1
19.83 g (0.1 mol) of bis (4-aminophenyl) methane (DDM) instead of 34.58 g (0.1 mol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene 210.50 g of polyimide resin solution was obtained in the same manner as in Example 1 except that the reflux time was changed to 6 hours. To give a white powder in the same manner as in Example 1, the IR spectrum of the powder was measured, 1700 cm -1 characteristic of imido group, absorption of 1768 cm -1 were observed. The logarithmic viscosity of the polyimide was measured and found to be 1.04.
Using the polyimide resin solution produced above, a colorless and transparent polyimide film having a thickness of 108 μm was obtained in the same manner as in Example 1. The total light transmittance, YI value and glass transition temperature of this film were measured. The results are shown in Table 1.
比較例２
１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン３４．５８ｇ（０．１モル）のかわりにビス（４−アミノフェニル）メタン１０．１１ｇ（０．０５モル）およびｍ−フェニレンジアミン（ＭＰＤ）５．４２ｇ（０．０５モル）を用い、還流時間を６時間に変更した以外は実施例１と同様にして２１０．５０ｇのポリイミド樹脂溶液を得た。実施例１と同様にして白色粉末を得、この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１７０１ｃｍ−１、１７６９ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、０．６７であった。
上記で製造したポリイミド樹脂溶液を用い、実施例１と同様にして膜厚１０６μｍの無色透明なポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値およびガラス転移温度を測定した。結果を第１表に示した。
Comparative Example 2
Instead of 34.58 g (0.1 mol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 10.11 g (0.05 mol) of bis (4-aminophenyl) methane and m- 210.50 g of a polyimide resin solution was obtained in the same manner as in Example 1 except that 5.42 g (0.05 mol) of phenylenediamine (MPD) was used and the reflux time was changed to 6 hours. To give a white powder in the same manner as in Example 1, the IR spectrum of the powder was measured, 1701Cm -1 characteristic of imido group, absorption of 1769cm -1 were observed. It was 0.67 when the logarithmic viscosity of the polyimide was measured.
Using the polyimide resin solution produced above, a colorless and transparent polyimide film having a thickness of 106 μm was obtained in the same manner as in Example 1. The total light transmittance, YI value and glass transition temperature of this film were measured. The results are shown in Table 1.
比較例３
１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン３４．５８ｇ（０．１モル）のかわりにビス（４−アミノフェニル）エーテル（オキシジアニリン、ＯＤＡ）２０．１０ｇ（０．１モル）を用い、還流時間を３時間に変更した以外は実施例１と同様にして２０５．０５ｇのポリイミド樹脂溶液を得た。実施例１と同様にして白色粉末を得、この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１６９１ｃｍ−１、１７６４ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、１．２１であった。
上記で製造したポリイミド樹脂溶液を用い、実施例１と同様にして膜厚１１５μｍの無色透明なポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値およびガラス転移温度を測定した。結果を第１表に示した。
Comparative Example 3
Instead of 34.58 g (0.1 mol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 20.10 g of bis (4-aminophenyl) ether (oxydianiline, ODA) (0 0.1 mol), and 205.05 g of a polyimide resin solution was obtained in the same manner as in Example 1 except that the reflux time was changed to 3 hours. To give a white powder in the same manner as in Example 1, the IR spectrum of the powder was measured, 1691Cm -1 characteristic of imido group, absorption of 1764cm -1 were observed. The logarithmic viscosity of the polyimide was measured and found to be 1.21.
Using the polyimide resin solution produced above, a colorless and transparent polyimide film having a film thickness of 115 μm was obtained in the same manner as in Example 1. The total light transmittance, YI value and glass transition temperature of this film were measured. The results are shown in Table 1.
比較例４
１，３−ビス（４−アミノ−α，α−ジメチルベンジル）ベンゼン３４．５８ｇ（０．１モル）のかわりにビス［４−（４−アミノフェノキシ）フェニル］スルホン（ＢＡＰＳ）４３．２５ｇ（０．１モル）を用い、還流時間を６時間に変更した以外は実施例１と同様にして３１１．９２ｇのポリイミド樹脂溶液を得た。実施例１と同様にして白色粉末を得、この粉末のＩＲスペクトルを測定したところ、イミド基に特有の１７０４ｃｍ−１、１７７２ｃｍ−１の吸収が見られた。ポリイミドの対数粘度を測定したところ、０．９０であった。
上記で製造したポリイミド樹脂溶液を用い、実施例１と同様にして膜厚１１６μｍの無色透明なポリイミドフィルムを得た。このフィルムの全光線透過率、ＹＩ値およびガラス転移温度を測定した。結果を第１表に示した。
Comparative Example 4
Instead of 34.58 g (0.1 mol) of 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 43.25 g of bis [4- (4-aminophenoxy) phenyl] sulfone (BAPS) ( 0.1 mol), and 31.92 g of a polyimide resin solution was obtained in the same manner as in Example 1 except that the reflux time was changed to 6 hours. To give a white powder in the same manner as in Example 1, the IR spectrum of the powder was measured, 1704 cm -1 characteristic of imido group, absorption of 1772 cm -1 were observed. The logarithmic viscosity of the polyimide was measured and found to be 0.90.
Using the polyimide resin solution produced above, a colorless and transparent polyimide film having a thickness of 116 μm was obtained in the same manner as in Example 1. The total light transmittance, YI value and glass transition temperature of this film were measured. The results are shown in Table 1.
実施例５
実施例２と同様にして得たポリイミド樹脂粉末を１，３−ジオキソラン（沸点７８℃）に溶解し、固形分濃度２０重量％のポリイミド樹脂溶液を調整した。この溶液を、２０００μｍのドクターブレードを用いて、プラスチック用離型剤が均一に塗布されたガラス基板上にキャストした。次にこの基板をホットプレート上で６０℃に１時間、さらに９０℃に１時間保持して溶媒を揮発させた後、熱風乾燥機内で１５０℃で３時間乾燥した。冷却後基板上に形成されたフィルムを剥がし、無色透明な乾燥ポリイミドフィルムを得た。このフィルムの膜厚、屈折率、耐熱加速試験の結果を第２表に示した。
Example 5
A polyimide resin powder obtained in the same manner as in Example 2 was dissolved in 1,3-dioxolane (boiling point 78 ° C.) to prepare a polyimide resin solution having a solid concentration of 20% by weight. This solution was cast on a glass substrate on which a plastic release agent was uniformly applied using a 2000 μm doctor blade. Next, the substrate was kept on a hot plate at 60 ° C. for 1 hour and further at 90 ° C. for 1 hour to volatilize the solvent, and then dried at 150 ° C. for 3 hours in a hot air dryer. After cooling, the film formed on the substrate was peeled off to obtain a colorless and transparent dry polyimide film. Table 2 shows the film thickness, refractive index, and heat acceleration test results of this film.
比較例５
ビスフェノールＡ型液状エポキシ樹脂（ジャパンエポキシレジン（株）、エピコート８２８ＵＳ、エポキシ当量１９０）３８ｇ、メチルヘキサヒドロ無水フタル酸（新日本理化（株）、リカシッドＭＨ−７００Ｇ、１．０当量）３２．８ｇおよび硬化促進剤として２−エチル−４−メチルイミダゾール０．３５ｇを１００ｍｌビーカーに量り取り、撹拌棒で良く混合してエポキシ樹脂混合液を調製した。縦×横×高さの寸法が６０×６０×１０ｍｍのシリコン製樹脂型にエポキシ樹脂混合液３ｇを流し込んだ。樹脂型をガラス基板上に載せて熱風乾燥機中に水平に設置し、９０℃で１時間、１２０℃で３時間、更に１５０℃で３時間硬化反応を行った。冷却後、樹脂型から無色透明なシート状硬化物を得た。このシート状硬化物の厚さ、屈折率、耐熱加速試験の結果を第２表に示した。
Comparative Example 5
38 g of bisphenol A type liquid epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 828US, epoxy equivalent 190), methylhexahydrophthalic anhydride (Shin Nihon Rika Co., Ltd., Ricacid MH-700G, 1.0 equivalent) 32.8 g Then, 0.35 g of 2-ethyl-4-methylimidazole as a curing accelerator was weighed into a 100 ml beaker and mixed well with a stir bar to prepare an epoxy resin mixture. 3 g of the epoxy resin mixture was poured into a silicon resin mold having dimensions of length × width × height of 60 × 60 × 10 mm. The resin mold was placed on a glass substrate and placed horizontally in a hot air dryer, and a curing reaction was performed at 90 ° C. for 1 hour, 120 ° C. for 3 hours, and further at 150 ° C. for 3 hours. After cooling, a colorless and transparent sheet-like cured product was obtained from the resin mold. Table 2 shows the thickness, refractive index, and thermal acceleration test results of the cured sheet.
実施例１〜４と比較例１〜４との比較から明らかなように、本発明によるポリイミド樹脂は、高耐熱性、高透明性および低吸水性なので、フラットパネルディスプレーや携帯電話機器等の基板材料、光ファイバー、光導波路、光学用接着剤等の光学用途に好適である。さらに実施例５と比較例５との比較から明らかなように、本発明のポリイミドフィルムは、高温暴露時の光線透過率の低下およびＹＩ値の上昇が小さく、高い屈折率を有しているので、発光ダイオード（ＬＥＤ）、光センサ等の光電変換デバイスの封止材料として好適である。 As is clear from the comparison between Examples 1 to 4 and Comparative Examples 1 to 4, the polyimide resin according to the present invention has high heat resistance, high transparency, and low water absorption, so that it is a substrate for flat panel displays, mobile phone devices and the like. It is suitable for optical applications such as materials, optical fibers, optical waveguides, and optical adhesives. Furthermore, as is clear from the comparison between Example 5 and Comparative Example 5, the polyimide film of the present invention has a high refractive index because the decrease in light transmittance and the increase in YI value during exposure to high temperatures are small. It is suitable as a sealing material for photoelectric conversion devices such as light emitting diodes (LEDs) and optical sensors.
Claims (8)
で表される１，２，４，５−シクロヘキサンテトラカルボン酸、下記式２：
で表される１，２，４，５−シクロヘキサンテトラカルボン酸二無水物およびこれらの反応性誘導体からなる群より選ばれる少なくとも１種のアシル含有化合物と、下記式３：
（式中、Ｘは−ＮＨ２または−Ｎ＝Ｃ＝Ｏであり、ｎは０〜４の整数、ｐは０または１であり、ｎ＋ｐは１〜５の整数である）で表される、少なくとも一つのフェニレン基とイソプロピリデン基を有する化合物から選ばれる少なくとも１種のイミノ形成化合物とを反応させる工程を含むポリイミド樹脂の製造方法。 Formula 1:
1,2,4,5-cyclohexanetetracarboxylic acid represented by the following formula 2:
And at least one acyl-containing compound selected from the group consisting of 1,2,4,5-cyclohexanetetracarboxylic dianhydride and their reactive derivatives represented by the following formula 3:
(Wherein, X is —NH 2 or —N═C═O, n is an integer of 0 to 4, p is 0 or 1, and n + p is an integer of 1 to 5). A method for producing a polyimide resin, comprising a step of reacting at least one imino-forming compound selected from compounds having at least one phenylene group and an isopropylidene group.
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| KR20120033867A (en) * | 2010-09-30 | 2012-04-09 | 코오롱인더스트리 주식회사 | Polyimide resin and film, alignment layer, substrate for display |
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| JP2012251080A (en) * | 2011-06-03 | 2012-12-20 | Mitsui Chemicals Inc | Novel polyimide and its use |
| JP2017025204A (en) * | 2015-07-22 | 2017-02-02 | 住友化学株式会社 | Polyimide film, and method for producing polyimide film |
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