JP2008056797A - Fluorescence material and optical device using the same - Google Patents
Fluorescence material and optical device using the same Download PDFInfo
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- JP2008056797A JP2008056797A JP2006235133A JP2006235133A JP2008056797A JP 2008056797 A JP2008056797 A JP 2008056797A JP 2006235133 A JP2006235133 A JP 2006235133A JP 2006235133 A JP2006235133 A JP 2006235133A JP 2008056797 A JP2008056797 A JP 2008056797A
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- 125000003118 aryl group Chemical group 0.000 claims abstract description 21
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Abstract
Description
本発明は、蛍光材料、及びそれ用いた光デバイスに関する。本発明の蛍光材料は、優れた蛍光特性、高い耐熱性、及び優れた機械特性を有し高効率の緑色蛍光を有するものであり、発光デバイス用材料として使用可能なものである。また、この蛍光材料を用いて作製された光デバイスは、従来にない優れた特性を有する。 The present invention relates to a fluorescent material and an optical device using the same. The fluorescent material of the present invention has excellent fluorescent properties, high heat resistance, excellent mechanical properties, and high-efficiency green fluorescence, and can be used as a material for a light emitting device. In addition, an optical device produced using this fluorescent material has excellent characteristics that have not been obtained in the past.
近年、有機エレクトロルミネッセンス（ＥＬ）素子や、発光型の空間光変調素子、波長変換素子等に使用される有機発光材料として、種々の低分子化合物や高分子化合物が開発されている。発光デバイス等の製造において、低分子化合物を用いる場合、製造プロセスが蒸着方式に制約されるのに対して、高分子化合物は、溶液にして製膜、又はインクジェットプリント方式等により製造できることから製造コストを安くできるという利点を有している。また、高分子化合物は、微細加工なしに微細な塗り分けができる点、そして膜厚を容易に製膜できる等の優れた特徴を有している。そのため、高効率な蛍光発光を示し、かつ発光波長の制御が容易な高分子系の発光材料の開発が望まれている。 In recent years, various low molecular weight compounds and polymer compounds have been developed as organic light emitting materials used for organic electroluminescence (EL) elements, light emitting spatial light modulation elements, wavelength conversion elements and the like. In the production of light emitting devices, etc., when using low molecular weight compounds, the production process is limited to the vapor deposition method, whereas the polymer compounds can be produced in solution by film formation or ink jet printing, etc. It has the advantage that can be made cheaper. In addition, the polymer compound has excellent features such that fine coating can be performed without fine processing and the film thickness can be easily formed. Therefore, it is desired to develop a high-molecular light-emitting material that exhibits high-efficiency fluorescence and can easily control the emission wavelength.
高分子発光材料としては、従来よりポリ−ｐ−フェニレンやポリフェニレンビニレン等のπ共役型高分子が知られている。しかし、このようなπ共役型高分子は、耐熱性や耐環境性（蛍光強度及び蛍光スペクトル形状の長期安定性）が十分でなく、また、製膜や微細加工が容易ではないという問題があった。一方、代表的な耐熱性高分子であるポリイミドは、優れた耐熱性や電気特性を有しており、前駆体であるポリアミド酸が製膜等の加工性に優れていることから、表示用デバイス材料としての用途が期待されている。例えば、非特許文献１には、主鎖や側鎖に蛍光性のフリル基を導入して青色の蛍光発光を示すポリイミドが開示されており、また、特許文献１及び特許文献２には、発光機能あるいは電荷輸送機能を有するポリイミドを用いた有機ＥＬ素子が開示されている。しかし、上記文献等に開示されたポリイミドの蛍光発光は、ポリイミドの主鎖又は側鎖に導入された蛍光性官能基によるものであり、また、その蛍光強度は、ポリイミド分子間の強い相互作用と、それに伴う濃度消失によって、同一の蛍光性官能基を有する低分子化合物の蛍光強度に比べると、その蛍光強度は非常に低いものである。
As polymer light-emitting materials, π-conjugated polymers such as poly-p-phenylene and polyphenylene vinylene are conventionally known. However, such π-conjugated polymers have problems such as insufficient heat resistance and environmental resistance (long-term stability of fluorescence intensity and fluorescence spectrum shape), and film formation and microfabrication are not easy. It was. On the other hand, polyimide, which is a typical heat-resistant polymer, has excellent heat resistance and electrical properties, and the precursor polyamic acid has excellent processability such as film formation. Use as a material is expected. For example, Non-Patent
また、非特許文献２等に開示されているように、ポリイミド自体が紫外線の照射により、可視光の蛍光発光を示すことは、従来から知られていた。この蛍光は、ポリイミドの分子構造中のジアミン部分（電子供与性）と酸無水物部分（電子吸引性）との間で形成される電荷移動錯体（ＣＴＣ）に起因する蛍光（ＣＴ蛍光）である（例えば、非特許文献３参照）。しかし、芳香族ポリイミドの場合には、ＣＴ相互作用が強く、無輻射失活過程が増加するため、その蛍光強度は弱くなる。代表的な全芳香族ポリイミドフィルムであるピロメリット酸二無水物と４，４’−ジアミノジフェニルエーテルから合成されるポリイミド（ＰＭＤＡ／ＯＤＡ）においては、通常の蛍光分光計では観測が困難なほどの弱い蛍光しか観測されない。また、非特許文献４には、全芳香族ポリイミドでも、ビフェニルテトラカルボン酸二無水物とパラフェニレンジアミンから合成されるポリイミド（ＢＰＤＡ／ＰＤＡ）は相対的に強い蛍光を示すことが報告されている。しかし、既存の蛍光性高分子化合物に比べると、その蛍光強度は非常に弱く、蛍光の量子収率は１％以下と非常に低いと考えられる。
In addition, as disclosed in Non-Patent
また、特許文献３には、三次元的な構造を有し、芳香環に直接フッ素が結合した芳香族酸二無水物と脂環式構造を有するジアミンとからなる構造単位を有するポリイミドを用いることで、優れた蛍光発光特性（蛍光強度の強さ、緑色から赤色領域における蛍光波長の制御性、蛍光強度の長期安定性）を有するとともに、耐熱性、化学安定性、製膜性に優れた単色発光性の蛍光性ポリイミドが得られることが開示されている。また、特許文献4には、三次元的な構造を有し、電子受容性の低い酸二無水物と脂環式構造を有するジアミンとからなる構造単位を有するポリイミドを用いることで、優れた青色蛍光発光特性を有し、耐熱性、化学安定性、製膜製に優れた単色発光性の蛍光性ポリイミドが得られることが開示されている。加えて、非特許文献５には、これらの蛍光性ポリイミドの薄膜を発光層あるいはホール輸送層として用いて有機電界発光（エレクトロルミネッセンス）による発光デバイスを作製した例が報告されている。
上記特許文献３及び４によれば、優れた蛍光特性を有する蛍光性ポリイミドを得られることが開示されている。上記特許文献３及び４に開示された蛍光性ポリイミドは、それぞれ、緑色から赤色領域における蛍光波長の制御性、及び青色蛍光特性を示すものである。
また、一般にポリイミドは、テトラカルボン酸二無水物（以下、酸二無水物）とジアミンとを極性溶媒中で反応させことによりポリアミド酸を得、これを加熱処理あるいは化学的脱水処理によりイミド化することにより得られる。本発明者らの検討により、ポリイミドの蛍光発光波長は、ジアミンに比して酸二無水物の電子構造および立体構造に強く依存することが明らかとなっている。すなわち、電子親和力の弱い非フッ素化酸二無水物から合成されたポリイミド（以下、非フッ素化無水物ポリイミド）は青色蛍光発光を示し、一方、電子親和力が強く、分子間で二量化しやすいフッ素化酸二無水物から合成されたポリイミド（以下、フッ素化無水物ポリイミド）は緑色・赤色発光を呈する。また、非フッ素化酸二無水物に数モル％のフッ素化酸二無水物を添加した混合物を原料として用いて合成したポリイミドは白色の蛍光を示す。しかし、フッ素化酸二無水物は一般に高価であり、またわずかな水分で開環しやすいため保存性に注意を有する。蛍光性ポリイミドの原料の経済性及び操作性を向上させるためには、フッ素化酸二無水物ポリイミドを用いることなく青色以外の蛍光を得ることが求められている。
According to the
In general, polyimide is obtained by reacting tetracarboxylic dianhydride (hereinafter referred to as acid dianhydride) and diamine in a polar solvent to obtain polyamic acid, which is imidized by heat treatment or chemical dehydration treatment. Can be obtained. As a result of studies by the present inventors, it has been clarified that the fluorescence emission wavelength of polyimide strongly depends on the electronic structure and steric structure of acid dianhydride as compared with diamine. That is, a polyimide synthesized from a non-fluorinated acid dianhydride having a low electron affinity (hereinafter referred to as a non-fluorinated anhydride polyimide) exhibits blue fluorescence, while it has a high electron affinity and is easily dimerized between molecules. Polyimide synthesized from hydrofluoric acid dianhydride (hereinafter referred to as fluorinated anhydride polyimide) exhibits green and red light emission. Moreover, the polyimide synthesize | combined using the mixture which added several mol% fluorinated acid dianhydride to the non-fluorinated acid dianhydride as a raw material shows white fluorescence. However, fluorinated dianhydrides are generally expensive, and are apt to be opened with a slight amount of water, so that attention is paid to storage stability. In order to improve the economical efficiency and operability of the raw material of fluorescent polyimide, it is required to obtain fluorescence other than blue without using fluorinated acid dianhydride polyimide.
従って、本研究の目的は、優れた蛍光特性（蛍光強度の強さ、蛍光強度の長期安定性）と高い耐熱性（ガラス転移点：２００℃以上、熱分解開始温度：３５０℃以上）に加え、優れた機械的特性（高い弾性率、可撓性、高靱性）を有し、酸二無水物部にフッ素を含有しないポリイミド系の新規の緑色蛍光材料を提供することにある。 Therefore, the purpose of this study is in addition to excellent fluorescence properties (intensity of fluorescence intensity, long-term stability of fluorescence intensity) and high heat resistance (glass transition point: 200 ° C or higher, thermal decomposition start temperature: 350 ° C or higher) Another object of the present invention is to provide a novel green fluorescent material based on polyimide that has excellent mechanical properties (high elastic modulus, flexibility, high toughness) and does not contain fluorine in the acid dianhydride part.
本発明者らは、上記目的を達成するため検討を重ねた結果、特定の酸二無水物構造を有するポリイミドからなる蛍光材料が上記目的を達成し得るという知見を得、その知見を基に鋭意検討を重ねた結果、本発明を完成するに至った。 As a result of repeated studies to achieve the above object, the present inventors have obtained the knowledge that a fluorescent material comprising a polyimide having a specific acid dianhydride structure can achieve the above object, and eagerly based on that knowledge. As a result of repeated studies, the present invention has been completed.
本発明は、上記知見に基づいてなされたものであり、下記一般式（１）で表される繰り返し単位を有するポリイミドを含有する蛍光材料を提供するものである。 This invention is made | formed based on the said knowledge, and provides the fluorescent material containing the polyimide which has a repeating unit represented by following General formula (1).
（式中、Ｒ1は、
脂環式構造又は芳香環を含む２価の有機基を示す）
(Wherein R 1 is
A divalent organic group containing an alicyclic structure or an aromatic ring)
上記一般式（１）において、Ｒ1としては、例えば、２価の脂環式構造（環状アルキル基）を有する有機基が挙げられる。
具体的には、Ｒ1としては、下記式（２）〜（５）で示される有機基が挙げられる。
In the general formula (1), examples of R 1 include an organic group having a divalent alicyclic structure (cyclic alkyl group).
Specifically, examples of R 1 include organic groups represented by the following formulas (2) to (5).
（式中、Ｒ２はアルキル基又はフルオロアルキル基を含む２価の有機基である。） (In the formula, R 2 is a divalent organic group containing an alkyl group or a fluoroalkyl group.)
（式中、Ｒ３はアルキル基又はフルオロアルキル基を含む１価の有機基である。） (In the formula, R 3 is a monovalent organic group containing an alkyl group or a fluoroalkyl group.)
また、本発明は、上記蛍光材料を用いて製造された有機発光デバイスを提供するものである。有機発光デバイスとしては、有機ＥＬ素子や有機レーザーなどの発光素子、波長変換素子及び空間光変調素子などが挙げられる。
また、本発明は、上記蛍光材料を用いて製造された有機光波長変換デバイスを提供するものである。
Moreover, this invention provides the organic light emitting device manufactured using the said fluorescent material. Examples of organic light emitting devices include light emitting elements such as organic EL elements and organic lasers, wavelength conversion elements, and spatial light modulation elements.
Moreover, this invention provides the organic light wavelength conversion device manufactured using the said fluorescent material.
本発明によれば、優れた緑色蛍光発光特性を有すると共に、耐熱性及び機械特性に優れた新規の蛍光材料が提供される。 ADVANTAGE OF THE INVENTION According to this invention, while having the outstanding green fluorescence emission characteristic, the novel fluorescent material excellent in heat resistance and mechanical characteristics is provided.
以下に、本発明を詳細に説明する。
本発明の蛍光材料は、下記一般式（１）で表わされる繰り返し単位を有するポリイミドを含有する。
The present invention is described in detail below.
The fluorescent material of the present invention contains a polyimide having a repeating unit represented by the following general formula (1).
一般式（１）において、Ｒ１は、脂環式構造又は芳香族環を含む２価の有機基を示す。
上記脂環式構造としては、例えばシクロアルカン構造、シクロアルケン構造等が挙げられる。脂環式構造を構成する炭素数に特に制限はないが、通常は４〜３０個程度、好ましくは５〜２０個程度、更に好ましくは５〜１５個程度である。炭素数が上記範囲内であると、耐熱性に優れた蛍光材料を得ることができる。また、上記芳香族環としては、ベンゼン環、ナフタレン環等の芳香環を１個以上含むものが挙げられる。Ｒ１が芳香環である場合、Ｒ１の２個の結合部位は、得られるポリイミドに剛直性を持たせる観点から、芳香環上に直接存在していることが好ましい。
Ｒ１としては、例えば、以下の式（２）〜（５）で示される有機基が挙げられる。
In the general formula (1), R 1 represents a divalent organic group containing an alicyclic structure or an aromatic ring.
Examples of the alicyclic structure include a cycloalkane structure and a cycloalkene structure. Although there is no restriction | limiting in particular in carbon number which comprises an alicyclic structure, Usually, about 4-30 pieces, Preferably it is about 5-20 pieces, More preferably, it is about 5-15 pieces. When the carbon number is within the above range, a fluorescent material having excellent heat resistance can be obtained. Moreover, as said aromatic ring, what contains 1 or more aromatic rings, such as a benzene ring and a naphthalene ring, is mentioned. When R 1 is an aromatic ring, the two bonding sites of R 1 are preferably directly present on the aromatic ring from the viewpoint of imparting rigidity to the resulting polyimide.
Examples of R 1 include organic groups represented by the following formulas (2) to (5).
式（３）中、Ｒ２はアルキル基又はフルオロアルキル基を含む２価の有機基である。上記
アルキル基としては、例えばメチレン基、エチレン基、イソプロピリデン基、ヘキサメチレン基等の長鎖アルキル基等が挙げられる。また、フルオロアルキル基としては、ジフルオロメチレン基、ヘキサフルオロイソプロピリデン基等が挙げられる。
In formula (3), R 2 is a divalent organic group containing an alkyl group or a fluoroalkyl group. Examples of the alkyl group include long-chain alkyl groups such as a methylene group, an ethylene group, an isopropylidene group, and a hexamethylene group. Examples of the fluoroalkyl group include a difluoromethylene group and a hexafluoroisopropylidene group.
式（４）中、Ｒ３はアルキル基又はフルオロアルキル基を含む１価の有機基である。
上記アルキル基としては、例えばメチル基、エチル基、イソプロピル基、ヘキサメチル基等の長鎖アルキル基等が挙げられる。また、フルオロアルキル基としてはトリフルオロメチル基、ペンタフルオロエチル基等が挙げられる。また、Ｒ３としては、アルコキシ基、又はフルオロアルコキシ基であってもよい。
In Formula (4), R 3 is a monovalent organic group containing an alkyl group or a fluoroalkyl group.
Examples of the alkyl group include long-chain alkyl groups such as a methyl group, an ethyl group, an isopropyl group, and a hexamethyl group. Examples of the fluoroalkyl group include a trifluoromethyl group and a pentafluoroethyl group. R 3 may be an alkoxy group or a fluoroalkoxy group.
式（５）中、Ｒ４はフルオロアルキル基を含む１価有機基である。フルオロアルキル基としてはトリフルオロメチル基、ペンタフルオロエチル基等が挙げられる。 In formula (5), R 4 is a monovalent organic group containing a fluoroalkyl group. Examples of the fluoroalkyl group include a trifluoromethyl group and a pentafluoroethyl group.
より具体的には、式（１）中、Ｒ１の２価の有機基としては、例えば、下記式（６）〜（１０）で表されるものが挙げられる。 More specifically, in the formula (1), examples of the divalent organic group represented by R 1 include those represented by the following formulas (6) to (10).
上記式（１）で表わされるポリイミドにおいて特筆すべきことは、原料である２,２’,３,３’−ジフェニルエーテルテトラカルボン酸二無水物（ｉ-ＯＤＰＡ）にフッ素を含まないにもかかわらず、波長４８９〜４９８ｎｍを中心とした緑色領域に強い蛍光発光を示すことである。前述したように、これまで非フッ素化酸二無水物から合成されたポリイミドにおいては、紫〜青色領域の蛍光発光しか観測されていない。例えばｉ-ＯＤＰＡの構造異性体である３,３’,４,４’−ジフェニルエーテルテトラカルボン酸二無水物（ｓ-ＯＤＰＡ）と脂環式ジアミンの組み合わせから合成されたポリイミドの蛍光発光は、ジアミンの化学構造によらず３９０〜４１０ｎｍの紫色領域であった。本発明によるポリイミドが緑色領域の蛍光発光を示す理由はまだ明らかでないが、ｉ-ＯＤＰＡの骨格構造は強く屈曲しており、隣り合う２つのベンゼン環が分子内で近接することがその特異な蛍光波長に関係していると考えられる。
What should be noted in the polyimide represented by the above formula (1) is that the
加えて、本発明の蛍光材料に含まれる、上記式（１）で表わされるポリイミドは、脂環式構造又は芳香環を含む２価の有機基を有することから耐熱性が高く、しかも低い吸水性及び優れた機械的特性を有することから蛍光性光学デバイス用材料として好適に用いることができる。特に、式（１）中のＲ１が式（２）〜（４）の脂環式構造を有する場合は、ポリイミドの分子内および分子間の電荷移動相互作用が抑制されるため、本発明の蛍光材料は高い蛍光強度（量子収率は最高で３８％）を発現できる。これは、特開平０４−３０７８５７号公報に開示されているフッ素化酸二無水物ポリイミドと同等の蛍光発光能である。また、式（１）中のＲ１が式（５）のフルオロアルキル基を有する芳香環（例えば、ベンゼン環）の場合、フルオロアルキル基の強い電子吸引性効果によりジアミンの電子供与性が低下し、ポリイミド分子内および分子間の電荷移動相互作用が抑制される。このため、蛍光強度の低下が少なく、一般的な全芳香族ポリイミドに比べて蛍光強度が飛躍的に向上する。結果として、全芳香族ポリイミドとしては高蛍光であることが報告されているビフェニルテトラカルボン酸二無水物とパラフェニレンジアミンから合成されるポリイミド（ＢＰＤＡ／ＰＤＡ）（量子収率１％未満）に比べて高い蛍光強度（量子収率約４％）を示す。さらに、本発明の蛍光材料に含まれるポリイミドは、特開平０４−３０７８５７号公報に開示されている赤色発光ポリイミドよりも高い蛍光強度を示す。
結果として、上記一般式（１）で表されるポリイミドは、Ｒ１の構造が脂環式構造又は芳香を含むか、あるいはフルオロアルキル基を含有する芳香環の場合に、特に強い緑色発光を有する。
In addition, since the polyimide represented by the above formula (1) contained in the fluorescent material of the present invention has a divalent organic group containing an alicyclic structure or an aromatic ring, it has high heat resistance and low water absorption. In addition, since it has excellent mechanical properties, it can be suitably used as a material for fluorescent optical devices. In particular, when R 1 in the formula (1) has the alicyclic structure of the formulas (2) to (4), the charge transfer interaction within and between the molecules of the polyimide is suppressed. Fluorescent materials can exhibit high fluorescence intensity (quantum yield up to 38%). This is a fluorescence emission ability equivalent to that of the fluorinated dianhydride polyimide disclosed in Japanese Patent Laid-Open No. 04-307857. In addition, when R 1 in the formula (1) is an aromatic ring having a fluoroalkyl group of the formula (5) (for example, a benzene ring), the electron donating property of the diamine is reduced due to the strong electron withdrawing effect of the fluoroalkyl group. In addition, the charge transfer interaction within and between the polyimide molecules is suppressed. For this reason, there is little fall of fluorescence intensity and fluorescence intensity improves remarkably compared with a general wholly aromatic polyimide. As a result, compared to polyimide (BPDA / PDA) (quantum yield less than 1%) synthesized from biphenyltetracarboxylic dianhydride and paraphenylenediamine, which are reported to be highly fluorescent as fully aromatic polyimide High fluorescence intensity (quantum yield of about 4%). Furthermore, the polyimide contained in the fluorescent material of the present invention exhibits higher fluorescence intensity than the red light emitting polyimide disclosed in Japanese Patent Application Laid-Open No. 04-307857.
As a result, the polyimide represented by the general formula (1) has particularly strong green light emission when the structure of R 1 includes an alicyclic structure or an aromatic or an aromatic ring containing a fluoroalkyl group. .
なお、上記一般式（１）で表される緑色発光を示すポリイミド構造の繰り返し単位と、一般式（１）の構造異性体である下記一般式（１１）で表される青色発光を有するポリイミド構造の繰り返し単位とからなる共重合体を製造することにより、種々の蛍光発光波長を有するポリイミドを得ることができる。すなわち、上記一般式（１）で表される緑色発光を示すポリイミド構造の繰り返し単位と、一般式（１１）で表される青色発光を有するポリイミド構造の繰り返し単位からなるポリイミドの共重合体は、その共重合比が１００：０〜６５：３５（モル比）の範囲では緑色発光、２０：８０〜５：９５（モル比）の範囲では蛍光発光のスペクトルが青色から緑色領域に広がるため水色（シアン）発光、０：１００（モル比）では青色発光を示した。従って、共重合比を制御することにより、蛍光発光の波長域を青色〜緑色において制御することが可能である。 In addition, the polyimide structure which has the blue light emission represented by the following general formula (11) which is the repeating unit of the polyimide structure which shows the green light emission represented by the said General formula (1), and the structural isomer of General formula (1). Polyimides having various fluorescence emission wavelengths can be obtained by producing a copolymer composed of the above repeating units. That is, a polyimide copolymer comprising a repeating unit of a polyimide structure showing green light emission represented by the general formula (1) and a repeating unit of a polyimide structure having blue light emission represented by the general formula (11), When the copolymerization ratio is in the range of 100: 0 to 65:35 (molar ratio), green light emission, and in the range of 20:80 to 5:95 (molar ratio), the fluorescence emission spectrum spreads from the blue to the green region. Cyan) emission, and 0: 100 (molar ratio) showed blue emission. Therefore, by controlling the copolymerization ratio, it is possible to control the wavelength range of fluorescence emission from blue to green.
本発明の蛍光材料に含有される、一般式（１）で表わされるポリイミドとしては、例えば、下記式（１２）、（１３）、（１４）、（１５）及び（１６）で表わされる繰り返し単位を有するポリイミドが挙げられる。 Examples of the polyimide represented by the general formula (1) contained in the fluorescent material of the present invention include repeating units represented by the following formulas (12), (13), (14), (15) and (16). The polyimide which has is mentioned.
本発明の蛍光材料に含有されるポリイミドの分子量は、その蛍光特性が発揮される範囲であれば特に限定されないが、その前駆体（ポリアミド酸あるいはポリアミド酸エステル）の分子量として対数粘度換算で０.０５〜５.０(ｄｌ／ｇ)（温度３０℃の有機溶媒中、濃度０.５ｇ／ｄｌ）の範囲であることが好ましい。 The molecular weight of the polyimide contained in the fluorescent material of the present invention is not particularly limited as long as the fluorescence characteristics are exhibited, but the molecular weight of the precursor (polyamic acid or polyamic acid ester) is 0. It is preferably in the range of 05 to 5.0 (dl / g) (concentration 0.5 g / dl in an organic solvent at a temperature of 30 ° C.).
本発明の蛍光材料に含有されるポリイミドの製造方法に特に制限はないが、例えば、３,３’,４,４’−ジフェニルエーテルテトラカルボン酸二無水物（ｉ−ＯＤＰＡ）と前記Ｒ1のジアミン化合物とを重縮合して得られるポリアミド酸を２００℃以上の温度で加熱閉環することによって製造することができる。加熱閉環する方法に特に制限はなく、従来公知の方法が用いられる。 There is no particular limitation on the production method of the polyimide contained in the fluorescent material of the present invention, for example, 3,3 ', 4,4'-diphenyl ether tetracarboxylic acid dianhydride (i-ODPA) with a diamine of the R 1 The polyamic acid obtained by polycondensation with a compound can be produced by heat-cycling at a temperature of 200 ° C. or higher. There is no restriction | limiting in particular in the method of carrying out heat ring closure, A conventionally well-known method is used.
用いられるジアミン化合物としては、例えば、１，４−ジアミノシクロヘキサン、４，４’−ジアミノジシクロヘキシルメタン、２，２’−ビス（トリフルオロメチル）−４，４’−ジアミノビシクロヘキサン、２，２’−ビス（４−アミノシクロヘキシル）−ヘキサフルオロプロパン等やこれらの構造異性体等が挙げられる。 Examples of the diamine compound to be used include 1,4-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 2,2′-bis (trifluoromethyl) -4,4′-diaminobicyclohexane, 2,2 ′. -Bis (4-aminocyclohexyl) -hexafluoropropane and the like, and structural isomers thereof and the like can be mentioned.
以下に、本発明の蛍光材料を用いたフィルムの製造方法の一例を示す。
まず、極性有機溶媒中で、等モル量の２,２’,３,３’−ジフェニルエーテルテトラカルボン酸二無水物と４，４’−ジアミノジシクロヘキシルメタンとを重縮合し、ポリアミド酸溶液を得る。この時、Ｎ，Ｏ−ビス（トリメチルシリル）アセトアミドやＮ，Ｏ−ビス（トリメチルシリル）トリフルオロアセトアミドのようなシリルエステル化物を混合すると、原料の会合体や生成物の不溶化（ゲル化）が起こりにくくなる。用いる極性有機溶媒としては、例えば、Ｎ−メチル−４−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等が挙げられる。重合溶液中の原料化合物の濃度は、好ましくは５〜４０重量％であり、更に好ましくは１０〜２５重量％である。この反応を下記式に示す。
Below, an example of the manufacturing method of the film using the fluorescent material of this invention is shown.
First, an equimolar amount of 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride and 4,4′-diaminodicyclohexylmethane are polycondensed in a polar organic solvent to obtain a polyamic acid solution. At this time, when a silyl esterified product such as N, O-bis (trimethylsilyl) acetamide or N, O-bis (trimethylsilyl) trifluoroacetamide is mixed, insolubilization (gelation) of the raw material aggregates and products hardly occurs. Become. Examples of the polar organic solvent to be used include N-methyl-4-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide and the like. The concentration of the raw material compound in the polymerization solution is preferably 5 to 40% by weight, more preferably 10 to 25% by weight. This reaction is shown in the following formula.
上述のようにして得られたポリアミド酸の溶液を、溶融石英板等の基板上に回転塗布し、不活性気体（例えば窒素）雰囲気下で、例えば７０℃程度の温度から３００℃程度の温度まで段階的あるいは連続的に加熱し、脱水閉環（イミド化）する。この反応を下記式に示す。段階的加熱の例としては、例えば、７０℃で２時間、１６０℃で１時間、２５０℃で３０分、３００℃で２時間のように行ってもよく、また毎分５℃での連続的な昇温によっても良い。イミド化後、空気中あるいは水中で基板から剥離することによりポリイミドフィルムを得る。基板からの剥離が困難な場合は、ポリアミド酸溶液をアルミ板上に回転塗布し、熱イミド化後、基板ごと１０％塩酸に浸しアルミ板を溶解することにより、ポリイミドフィルムを得る。また、基板材料としては溶融石英や単結晶シリコン等の無機系のみならず、ポリイミド成型体等の有機高分子を用いても良い。 The polyamic acid solution obtained as described above is spin-coated on a substrate such as a fused quartz plate, and the temperature is about 70 ° C. to about 300 ° C. in an inert gas (eg, nitrogen) atmosphere. Heating stepwise or continuously to dehydrate ring closure (imidization). This reaction is shown in the following formula. Examples of stepwise heating may be, for example, 70 ° C for 2 hours, 160 ° C for 1 hour, 250 ° C for 30 minutes, 300 ° C for 2 hours, or continuous at 5 ° C per minute. It is also possible to increase the temperature. After imidation, a polyimide film is obtained by peeling from the substrate in air or water. When peeling from the substrate is difficult, the polyimide film is obtained by spin-coating the polyamic acid solution on the aluminum plate, thermal imidization, and then immersing the substrate together with 10% hydrochloric acid to dissolve the aluminum plate. Further, as a substrate material, not only an inorganic material such as fused quartz or single crystal silicon but also an organic polymer such as a polyimide molded body may be used.
ポリアミド酸の合成方法としては、上記のように極性有機溶媒を用いて合成する方法の他、原料である酸二無水物とジアミン化合物の昇華性を利用して、真空蒸着重合法により基板上で合成する方法が挙げられる。この場合のポリイミドフィルムの合成方法としては、具体的には、酸二無水物モノマーとジアミンモノマーを、真空槽内でそれぞれの蒸着源を加熱して蒸発させ、基板上でポリアミド酸を合成し、さらにこれを不活性気体中で加熱して、脱水閉環することによりポリイミド薄膜を得ることができる。また、必要に応じてピリジン／無水酢酸などの閉環触媒と脱水剤の組み合わせによる化学処理を行ってイミド化してもよい。 As a method for synthesizing the polyamic acid, in addition to the method of synthesizing using a polar organic solvent as described above, the sublimation property of the acid dianhydride and the diamine compound as raw materials is used to form a polyamic acid on a substrate by a vacuum deposition polymerization method. The method of synthesizing is mentioned. As a method for synthesizing the polyimide film in this case, specifically, an acid dianhydride monomer and a diamine monomer are evaporated by heating respective vapor deposition sources in a vacuum chamber, and a polyamic acid is synthesized on the substrate. Furthermore, a polyimide thin film can be obtained by heating this in inert gas and carrying out dehydration ring closure. Further, if necessary, imidization may be performed by chemical treatment with a combination of a ring-closing catalyst such as pyridine / acetic anhydride and a dehydrating agent.
次に、本発明の有機発光デバイス、有機光波長変換デバイスについて説明する。本発明の有機発光デバイス、及び有機光波長変換デバイスは、上述した本発明の蛍光材料を用いて製造されたものである。
本発明の蛍光材料は、有機ＥＬ素子、有機レーザー、波長変換素子、空間光変調素子等の有機発光デバイス、又は有機光波長変換デバイスの材料として用いることができる。例えば、本発明の蛍光材料のフィルムを発光層／受光層として用いて、透明基板／透明電極／電荷輸送層／発光層／受光層／電極の積層体を形成することにより有機ＥＬ素子にすることができる。
その他、通信用の光導波路や光源、光ファイバー増幅器、蛍光増白剤、塗料、インク、蛍光コレクタ、シンチレータ、植物育成用フィルム等に利用することができる。
Next, the organic light emitting device and the organic light wavelength conversion device of the present invention will be described. The organic light emitting device and the organic light wavelength conversion device of the present invention are manufactured using the fluorescent material of the present invention described above.
The fluorescent material of the present invention can be used as a material for organic light-emitting devices such as organic EL elements, organic lasers, wavelength conversion elements, and spatial light modulation elements, or organic light wavelength conversion devices. For example, using the film of the fluorescent material of the present invention as a light emitting layer / light receiving layer, an organic EL device is formed by forming a laminate of transparent substrate / transparent electrode / charge transport layer / light emitting layer / light receiving layer / electrode. Can do.
In addition, it can be used for optical waveguides and light sources for communication, optical fiber amplifiers, optical brighteners, paints, inks, fluorescent collectors, scintillators, plant growth films, and the like.
以下に、実施例を示して本発明を具体的に説明するが、これらにより本発明は何ら制限を受けるものではない。
実施例１
三角フラスコに、２,２’,３,３’−ジフェニルエーテルテトラカルボン酸二無水物（ｉ-ＯＤＰＡ）０．９８５３ｇ（３．１７６ｍｍｏｌ）と４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．６６８１ｇ（３．１７６ｍｍｏｌ）を加え、溶液の原材料の濃度が１５重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）９．３７ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で４８時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３００℃で１．５時間、２段階で昇温して加熱イミド化を行った。
Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these examples.
Example 1
Into an Erlenmeyer flask, 0.9853 g (3.176 mmol) of 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride (i-ODPA) and 0.6681 g of 4,4′-diaminodicyclohexylmethane (DCHM) ( 3.176 mmol) was added, and 9.37 g of N, N-dimethylacetamide (DMAc) was added so that the concentration of the raw material of the solution was 15% by weight. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 48 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 300 ° C. for 1.5 hours, and heated in two steps for imidization. It was.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ−１及び１７１９ｃｍ−１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ−１、１６３７ｃｍ−１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を蝕針式膜厚計で測定したところ、１．０３μｍであった。また、熱重量分析装置（ＴＧＡ）により熱分解開始温度（５％重量減少温度）を測定したところ、４１５℃であった。得られたポリイミド薄膜の蛍光発光スペクトルを励起波長４１４ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、波長４８９ｎｍを中心に、非常に強い蛍光が観測された。この結果を図１に示した。図１は、蛍光発光強度を測定した結果を示すグラフである。図１には、後述する実施例２、及び比較例１,２のポリイミドにおけるそれぞれの蛍光スペクトルの波長依存性を併せて示す。図１において縦軸は蛍光強度（対数表示）、横軸は波長（ｎｍ）を示している。図１に示すように、実施例１で得られた蛍光材料は、後述する比較例１のポリイミドとは蛍光の発光中心波長（ピーク波長）が異なるが、発光中心波長における蛍光強度は比較例１のポリイミドに比して約３６倍であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 1.03 micrometer when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. Moreover, it was 415 degreeC when the thermal decomposition start temperature (5% weight reduction | decrease temperature) was measured with the thermogravimetric analyzer (TGA). When the fluorescence emission spectrum of the obtained polyimide thin film was measured at an excitation wavelength of 414 nm and a fluorescence observation wavelength of 330 to 800 nm, very strong fluorescence was observed centering on the wavelength of 489 nm. The results are shown in FIG. FIG. 1 is a graph showing the results of measuring fluorescence emission intensity. In FIG. 1, the wavelength dependence of each fluorescence spectrum in the polyimide of Example 2 mentioned later and Comparative Examples 1 and 2 is shown collectively. In FIG. 1, the vertical axis represents fluorescence intensity (logarithmic display), and the horizontal axis represents wavelength (nm). As shown in FIG. 1, the fluorescent material obtained in Example 1 is different from the polyimide of Comparative Example 1 described later in the emission center wavelength (peak wavelength) of fluorescence, but the fluorescence intensity at the emission center wavelength is Comparative Example 1. It was about 36 times that of polyimide.
比較例１
実施例１におけるｉ-ＯＤＰＡに代えて、３，３’，４，４’−ビフェニルテトラカルボン酸二無水物（s-ＢＰＤＡ）１．４７ｇ（４．９９６ｍｍｏｌ）を、またＤＣＨＭに代えて１，４−ジアミノベンゼン（ＰＤＡ）０．５４ｇ（４．９９４ｍｍｏｌ）を用いて、実施例１と同様の方法でポリアミド酸のＤＭＡｃ溶液（１５重量％）を調製し、ポリイミド薄膜を作製した。得られた薄膜の膜厚を蝕針式膜厚計で測定したところ、４.０μｍであった。また、５％重量減少温度を測定したところ、４８０℃であった。この非フッ素化全芳香族ポリイミド薄膜の蛍光発光スペクトルを励起波長３６３ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、中心波長５１４ｎｍに蛍光が観測された。結果を図１に示す。このポリイミドはこれまで報告されている全芳香族ポリイミドの中では強い蛍光を出すことから、この試料の蛍光強度を比較のための基準とした。
Comparative Example 1
Instead of i-ODPA in Example 1, 1.47 g (4.996 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (s-BPDA) and 1, A DMAc solution (15% by weight) of polyamic acid was prepared in the same manner as in Example 1 using 0.54 g (4.994 mmol) of 4-diaminobenzene (PDA) to prepare a polyimide thin film. It was 4.0 micrometers when the film thickness of the obtained thin film was measured with the stylus-type film thickness meter. The 5% weight loss temperature was measured and found to be 480 ° C. When the fluorescence emission spectrum of this non-fluorinated wholly aromatic polyimide thin film was measured at an excitation wavelength of 363 nm and a fluorescence observation wavelength of 330 to 800 nm, fluorescence was observed at a central wavelength of 514 nm. The results are shown in FIG. Since this polyimide emits strong fluorescence among all aromatic polyimides reported so far, the fluorescence intensity of this sample was used as a reference for comparison.
比較例２
実施例１におけるｉ-ＯＤＰＡに代えて、１，４−ビス（３，４−ジカルボキシトリフルオロフェノキシ）テトラフルオロベンゼン二無水物（１０ＦＥＤＡ）２．９１ｇ（５．０ｍｍｏｌ）、ＤＣＨＭ１．０５ｇ（５．０ｍｍｏｌ）を用いて、実施例１と同様の方法でポリアミド酸のＤＭＡｃ溶液（１０重量％）を調製し、ポリイミド薄膜を作製した。得られた薄膜の膜厚は１．０μｍ、５％重量減少温度は４０５℃であった。このポリイミド薄膜の蛍光発光スペクトルを励起波長４０９ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、中心波長４８３ｎｍに蛍光が観測された。結果を図１に示した。比較例２で得られた蛍光材料の発光中心波長における蛍光強度は、比較例１のポリイミドに比して約４６倍であった。
Comparative Example 2
Instead of i-ODPA in Example 1, 1.91 g (5.0 mmol) of 1,4-bis (3,4-dicarboxytrifluorophenoxy) tetrafluorobenzene dianhydride (10FEDA), 1.05 g of DCHM (5 0.0 mmol), a DMAc solution (10 wt%) of polyamic acid was prepared in the same manner as in Example 1 to prepare a polyimide thin film. The obtained thin film had a thickness of 1.0 μm and a 5% weight loss temperature of 405 ° C. When the fluorescence emission spectrum of the polyimide thin film was measured at an excitation wavelength of 409 nm and a fluorescence observation wavelength of 330 to 800 nm, fluorescence was observed at a central wavelength of 483 nm. The results are shown in FIG. The fluorescence intensity at the emission center wavelength of the fluorescent material obtained in Comparative Example 2 was about 46 times that of the polyimide in Comparative Example 1.
比較例３
実施例１におけるｉ-ＯＤＰＡに代えて、１，４−ジフルオロピロメリト酸二無水物（Ｐ２ＦＤＡ）１．２７ｇ（５．０ｍｍｏｌ）、ＤＣＨＭ１．０５ｇ（５．０ｍｍｏｌ）を用いて、実施例１と同様の方法でポリアミド酸のＤＭＡｃ溶液（１０重量％）を調製し、ポリイミド薄膜を作製した。得られた薄膜の膜厚は７．７μｍ、５％重量減少温度は３９４℃であった。このポリイミド薄膜の蛍光発光スペクトルを励起波長５３７ｎｍで測定したところ、中心波長５８８ｎｍ及び７１３ｎｍに蛍光が観測された。結果を図１に示した。比較例３で得られた蛍光材料の発光中心波長における蛍光強度は、比較例１のポリイミドに比して約３倍であった。
Comparative Example 3
Instead of i-ODPA in Example 1, 1.27 g (5.0 mmol) of 1,4-difluoropyromellitic dianhydride (P2FDA) and 1.05 g (5.0 mmol) of DCHM were used. A DMAc solution (10% by weight) of polyamic acid was prepared in the same manner to produce a polyimide thin film. The obtained thin film had a thickness of 7.7 μm and a 5% weight loss temperature of 394 ° C. When the fluorescence emission spectrum of this polyimide thin film was measured at an excitation wavelength of 537 nm, fluorescence was observed at center wavelengths of 588 nm and 713 nm. The results are shown in FIG. The fluorescence intensity at the emission center wavelength of the fluorescent material obtained in Comparative Example 3 was about 3 times that of the polyimide in Comparative Example 1.
実施例２
三角フラスコに、２,２’,３,３’−ジフェニルエーテルテトラカルボン酸二無水物（ｉ-ＯＤＰＡ）０．６９７１ｇ（２．２４７ｍｍｏｌ）と２,２‘−ビストリフルオロメチル−４,４’−ジアミノビフェニル（ＴＦＤＢ）０．７１９６ｇ（２．２４７ｍｍｏｌ）を用いて、溶液の原材料の濃度が２５重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）４．２５ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で４８時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３５０℃で１．５時間、２段階で昇温して加熱イミド化を行った。
Example 2
Into an Erlenmeyer flask, 0.6971 g (2.247 mmol) of 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride (i-ODPA) and 2,2′-bistrifluoromethyl-4,4′-diamino Using 0.7196 g (2.247 mmol) of biphenyl (TFDB), 4.25 g of N, N-dimethylacetamide (DMAc) was added so that the concentration of the raw material of the solution was 25% by weight. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 48 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 350 ° C. for 1.5 hours, and heated in two steps for imidization. It was.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ−１及び１７１９ｃｍ−１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ−１、１６３７ｃｍ−１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を蝕針式膜厚計で測定したところ、８．８μｍであった。このポリイミド薄膜の蛍光発光スペクトルを励起波長４３０ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、中心波長４９８ｎｍに蛍光が観測された。結果を図１に示した。図１に示すように、実施例２で得られた蛍光材料の発光中心波長における蛍光強度は、比較例１のポリイミドに比して約１２倍であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 8.8 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. When the fluorescence emission spectrum of this polyimide thin film was measured at an excitation wavelength of 430 nm and a fluorescence observation wavelength of 330 to 800 nm, fluorescence was observed at a central wavelength of 498 nm. The results are shown in FIG. As shown in FIG. 1, the fluorescence intensity at the emission center wavelength of the fluorescent material obtained in Example 2 was about 12 times that of the polyimide of Comparative Example 1.
実施例３
三角フラスコに、２,２’,３,３’−ジフェニルエーテルテトラカルボン酸二無水物（ｉ-ＯＤＰＡ）０．２３６５ｇ（０．７６２ｍｍｏｌ）、３,３’,４,４’−ジフェニルエーテルテトラカルボン酸二無水物（s-ＯＤＰＡ）０．０５９１g（０．１９１ｍｍｏｌ）、及び４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．２００５ｇ（０．９５３ｍｍｏｌ）を加え、溶液の原材料の濃度が１５重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）２．８１１ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で４８時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３００℃で１．５時間、２段階で昇温して加熱イミド化を行った。
Example 3
To an Erlenmeyer flask, 0.2365 g (0.762 mmol) of 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride (i-ODPA), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dicarboxylic acid Add 0.0591 g (0.191 mmol) of anhydride (s-ODPA) and 0.2005 g (0.953 mmol) of 4,4′-diaminodicyclohexylmethane (DCHM) to bring the concentration of the raw materials in the solution to 15% by weight. As such, 2.811 g of N, N-dimethylacetamide (DMAc) was added. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 48 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 300 ° C. for 1.5 hours, and heated in two steps for imidization. It was.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ−１及び１７１９ｃｍ−１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ−１、１６３７ｃｍ−１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を蝕針式膜厚計で測定したところ、０．９μｍであった。このポリイミド薄膜の蛍光発光スペクトルを励起波長３２２ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、波長４８９ｎｍを中心に、強い緑色蛍光が観測された。結果を図２に示した。図２には、後述する実施例４，５及び比較例１,４のポリイミドにおけるそれぞれの蛍光スペクトルの波長依存性を併せて示す。図２において縦軸は蛍光強度（対数表示）、横軸は波長（nm）を示している。実施例３で得られた蛍光材料の発光中心波長における蛍光強度は、比較例１のポリイミドに比して約３２倍であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 0.9 micrometer when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. When the fluorescence emission spectrum of the polyimide thin film was measured at an excitation wavelength of 322 nm and a fluorescence observation wavelength of 330 to 800 nm, strong green fluorescence was observed centering on the wavelength of 489 nm. The results are shown in FIG. In FIG. 2, the wavelength dependence of each fluorescence spectrum in the polyimide of Examples 4 and 5 mentioned later and Comparative Examples 1 and 4 is shown collectively. In FIG. 2, the vertical axis represents fluorescence intensity (logarithmic display), and the horizontal axis represents wavelength (nm). The fluorescence intensity at the emission center wavelength of the fluorescent material obtained in Example 3 was about 32 times that of the polyimide of Comparative Example 1.
実施例４
三角フラスコに、２,２’,３,３’−ジフェニルエーテルテトラカルボン酸二無水物（ｉ-ＯＤＰＡ）０．０２９６ｇ（０．０９５３ｍｍｏｌ）、３,３’,４,４’−ジフェニルエーテルテトラカルボン酸二無水物（s-ＯＤＰＡ）０．２６６０g（０．８５８ｍｍｏｌ）、及び４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．２００５ｇ（０．９５３ｍｍｏｌ）を加え、溶液の原材料の濃度が１５重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）２．８１１ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で４８時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３００℃で１．５時間、２段階で昇温して加熱イミド化を行った。
Example 4
To an Erlenmeyer flask, 0.0296 g (0.0953 mmol) of 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride (i-ODPA), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dicarboxylic acid Add 0.2660 g (0.858 mmol) of anhydride (s-ODPA) and 0.2005 g (0.953 mmol) of 4,4′-diaminodicyclohexylmethane (DCHM) to bring the concentration of raw materials in the solution to 15% by weight. As such, 2.811 g of N, N-dimethylacetamide (DMAc) was added. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 48 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 300 ° C. for 1.5 hours, and heated in two steps for imidization. It was.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ−１及び１７１９ｃｍ−１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ−１、１６３７ｃｍ−１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を蝕針式膜厚計で測定したところ、３．５μｍであった。このポリイミド薄膜の蛍光発光スペクトルを励起波長３３９ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、３５０ｎｍ〜６００ｎｍにおいて強い蛍光が観測された。結果を図２に示した。図２に示すように、実施例４で得られた蛍光材料は、蛍光波長が青色〜緑色領域全体に広がっており、蛍光色は水色を示す。実施例４で得られた蛍光材料の発光中心波長における蛍光強度は、比較例１のポリイミドに比して約１７倍であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 3.5 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. When the fluorescence emission spectrum of this polyimide thin film was measured at an excitation wavelength of 339 nm and a fluorescence observation wavelength of 330 to 800 nm, strong fluorescence was observed at 350 nm to 600 nm. The results are shown in FIG. As shown in FIG. 2, the fluorescent material obtained in Example 4 has a fluorescent wavelength that extends over the entire blue to green region, and the fluorescent color is light blue. The fluorescence intensity at the emission center wavelength of the fluorescent material obtained in Example 4 was about 17 times that of the polyimide of Comparative Example 1.
実施例５
三角フラスコに、２,２’,３,３’−ジフェニルエーテルテトラカルボン酸二無水物（ｉ-ＯＤＰＡ）０．０１４８ｇ（０．０４７６ｍｍｏｌ）、３,３’,４,４’−ジフェニルエーテルテトラカルボン酸二無水物（s-ＯＤＰＡ）０．２８０８g（０．９０５ｍｍｏｌ）、及び４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．２００５ｇ（０．９５３ｍｍｏｌ）を加え、溶液の原材料の濃度が１５重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）２．８１１ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で４８時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３００℃で１．５時間、２段階で昇温して加熱イミド化を行った。
Example 5
To an Erlenmeyer flask, 0.0148 g (0.0476 mmol) of 2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride (i-ODPA), 3,3 ′, 4,4′-diphenyl ether tetracarboxylic acid dicarboxylic acid Anhydrous (s-ODPA) 0.2808 g (0.905 mmol) and 4,4′-diaminodicyclohexylmethane (DCHM) 0.2005 g (0.953 mmol) are added to bring the concentration of the raw materials in the solution to 15% by weight. As such, 2.811 g of N, N-dimethylacetamide (DMAc) was added. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 48 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 300 ° C. for 1.5 hours, and heated in two steps for imidization. It was.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ−１及び１７１９ｃｍ−１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ−１、１６３７ｃｍ−１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を蝕針式膜厚計で測定したところ、３．６μｍであった。このポリイミド薄膜の蛍光発光スペクトルを励起波長３４３ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、３５０ｎｍ〜６００ｎｍにおいて強い蛍光が観測された。結果を図２に示した。図２に示すように、実施例５で得られた蛍光材料は、蛍光波長が青色〜緑色領域全体に広がっており、蛍光色は水色を示す。実施例５で得られた蛍光材料の発光中心波長における蛍光強度は、比較例１のポリイミドに比して約１３倍であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 3.6 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. When the fluorescence emission spectrum of this polyimide thin film was measured at an excitation wavelength of 343 nm and a fluorescence observation wavelength of 330 to 800 nm, strong fluorescence was observed at 350 nm to 600 nm. The results are shown in FIG. As shown in FIG. 2, the fluorescent material obtained in Example 5 has a fluorescent wavelength extending over the entire blue to green region, and the fluorescent color is light blue. The fluorescence intensity at the emission center wavelength of the fluorescent material obtained in Example 5 was about 13 times that of the polyimide of Comparative Example 1.
比較例４
実施例１におけるｉ-ＯＰＤＡに代えて、３,３’,４,４’−ジフェニルエーテルテトラカルボン酸二無水物（s-ＯＤＰＡ）０．９８５３ｇ（３．１７６ｍｍｏｌ）と４，４’−ジアミノジシクロヘキシルメタン（ＤＣＨＭ）０．６６８１ｇ（３．１７６ｍｍｏｌ）を加え、溶液の原材料の濃度が１５重量％になるようにＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）９．３７ｇを加えた。三角フラスコ中の溶液を窒素雰囲気中、室温で４８時間攪拌し、ポリアミド酸のＤＭＡｃ溶液を得た。得られたポリアミド酸のＤＭＡｃ溶液を直径７５ｍｍの石英板上に回転塗布し、窒素雰囲気下、７０℃で１時間、３００℃で１．５時間、２段階で昇温して加熱イミド化を行った。
Comparative Example 4
Instead of i-OPDA in Example 1, 0.9853 g (3.176 mmol) of 3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride (s-ODPA) and 4,4′-diaminodicyclohexylmethane 0.6681 g (3.176 mmol) of (DCHM) was added, and 9.37 g of N, N-dimethylacetamide (DMAc) was added so that the concentration of the raw material of the solution was 15% by weight. The solution in the Erlenmeyer flask was stirred in a nitrogen atmosphere at room temperature for 48 hours to obtain a DMAc solution of polyamic acid. The obtained DMAc solution of polyamic acid was spin-coated on a quartz plate having a diameter of 75 mm, and heated in a nitrogen atmosphere at 70 ° C. for 1 hour, at 300 ° C. for 1.5 hours, and heated in two steps for imidization. It was.
得られたポリイミド薄膜の赤外吸収スペクトルを減衰全反射（ＡＴＲ）法により測定したところ、１７７７ｃｍ−１及び１７１９ｃｍ−１にイミド基のカルボニルに特有の吸収が観察され、またポリアミド酸において観測される１６７７ｃｍ−１、１６３７ｃｍ−１のアミド結合特有の吸収が消失しており、イミド化が完全に進行したことが確認できた。得られた薄膜の膜厚を蝕針式膜厚計で測定したところ、８．９μｍであった。このポリイミド薄膜の蛍光発光スペクトルを励起波長３４７ｎｍ、蛍光観測波長３３０〜８００ｎｍで測定したところ、中心波長３９６ｎｍに強い青色蛍光が観測された。結果を図２に示した。比較例４で得られた蛍光材料の発光中心波長における蛍光強度は、比較例１のポリイミドに比して約２７倍であった。 The infrared absorption spectrum of the obtained polyimide thin film was measured by attenuated total reflection (ATR) method, the absorption specific to carbonyl of the imide group to 1777cm -1 and 1719 cm -1 was observed, also observed in the polyamic acid Absorption peculiar to the amide bond at 1677 cm −1 and 1637 cm −1 disappeared, and it was confirmed that imidization proceeded completely. It was 8.9 micrometers when the film thickness of the obtained thin film was measured with the stylus type film thickness meter. When the fluorescence emission spectrum of this polyimide thin film was measured at an excitation wavelength of 347 nm and a fluorescence observation wavelength of 330 to 800 nm, strong blue fluorescence was observed at a central wavelength of 396 nm. The results are shown in FIG. The fluorescence intensity at the emission center wavelength of the fluorescent material obtained in Comparative Example 4 was about 27 times that of the polyimide of Comparative Example 1.
実施例６
酸二無水物とジアミンの合計（固形分）の濃度を３５％とし、実施例１と同様の方法でｉ-ＯＤＰＡとＤＣＨＭからポリアミド酸のＤＭＡｃ溶液を調製した。この溶液を厚さ１ｍｍの石英板上に塗布し、最高温度３００℃で熱イミド化したところ、膜厚１８μｍのフィルムが得られた。ポリアミド酸溶液の塗布、乾燥、熱イミド化の処理をさらに２度繰り返したところ、膜厚約５０μｍのポリイミドが得られた。ダイシングソーを用いて基板ごと５×５ｍｍの大きさに切り出し、ポリイミドフィルム側に紫外線シャープカットフィルタ（ガラス基板）をアクリル系光学接着剤により貼り付けた。石英基板の裏面から紫外発光ダイオード（発光波長３８６ｎｍ、電流２０ｍＡ、光出力７０ｍｃｄ）を照射したところ、ポリイミドの表面から波長４９０ｎｍを中心とする緑色の明るい蛍光発光が観測された。本発明によるポリイミドが、紫外光→可視光の有機光波長変換デバイスにおける波長変換材料として機能することが明らかとなった。
Example 6
A DMAc solution of polyamic acid was prepared from i-ODPA and DCHM in the same manner as in Example 1, with the total concentration of dianhydride and diamine (solid content) being 35%. When this solution was applied onto a quartz plate having a thickness of 1 mm and thermally imidized at a maximum temperature of 300 ° C., a film having a thickness of 18 μm was obtained. When the polyamic acid solution coating, drying, and thermal imidization were repeated twice, a polyimide film having a thickness of about 50 μm was obtained. The whole substrate was cut into a size of 5 × 5 mm using a dicing saw, and an ultraviolet sharp cut filter (glass substrate) was attached to the polyimide film side with an acrylic optical adhesive. When an ultraviolet light emitting diode (emission wavelength: 386 nm, current: 20 mA, light output: 70 mcd) was irradiated from the back surface of the quartz substrate, bright green fluorescent light centered on a wavelength of 490 nm was observed from the polyimide surface. It has been clarified that the polyimide according to the present invention functions as a wavelength conversion material in an organic light wavelength conversion device of ultraviolet light → visible light.
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| WO2010084587A1 (en) * | 2009-01-21 | 2010-07-29 | 富士電機ホールディングス株式会社 | Color conversion film and multicolor emission organic el device including color conversion film |
| JP2022500216A (en) * | 2018-09-14 | 2022-01-04 | ニューラリンク コーポレーションNeuralink Corp. | Computer visual technology |
| US11925800B2 (en) | 2018-09-14 | 2024-03-12 | Neuralink, Inc. | Device implantation using a cartridge |
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| WO2006120954A1 (en) * | 2005-05-09 | 2006-11-16 | Tokyo Institute Of Technology | Fluorescent material |
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| JP2004161979A (en) * | 2002-09-18 | 2004-06-10 | Manac Inc | New thermoplastic polyimide and imide oligomer |
| JP2004307857A (en) * | 2003-03-26 | 2004-11-04 | Rikogaku Shinkokai | Fluorescent polyimide |
| JP2005320393A (en) * | 2004-05-07 | 2005-11-17 | Rikogaku Shinkokai | Fluorescent material |
| WO2006120954A1 (en) * | 2005-05-09 | 2006-11-16 | Tokyo Institute Of Technology | Fluorescent material |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2010084587A1 (en) * | 2009-01-21 | 2010-07-29 | 富士電機ホールディングス株式会社 | Color conversion film and multicolor emission organic el device including color conversion film |
| JP5236732B2 (en) * | 2009-01-21 | 2013-07-17 | シャープ株式会社 | Color conversion film and multicolor light emitting organic EL device including the color conversion film |
| US8541777B2 (en) | 2009-01-21 | 2013-09-24 | Sharp Kabushiki Kaisha | Color conversion film and multicolor-emitting, organic electroluminescent device comprising the color conversion film |
| US8847219B2 (en) | 2009-01-21 | 2014-09-30 | Sharp Kabushiki Kaisha | Color conversion film and multicolor-emitting, organic electroluminescent device comprising the color conversion film |
| JP2022500216A (en) * | 2018-09-14 | 2022-01-04 | ニューラリンク コーポレーションNeuralink Corp. | Computer visual technology |
| US11925800B2 (en) | 2018-09-14 | 2024-03-12 | Neuralink, Inc. | Device implantation using a cartridge |
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