JP2014172978A - Copolymerized polyimide precursor and copolymerized polyimide - Google Patents
Copolymerized polyimide precursor and copolymerized polyimide Download PDFInfo
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Abstract
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本発明は、共重合ポリイミド前駆体および共重合ポリイミドに関するものである。 The present invention relates to a copolymerized polyimide precursor and a copolymerized polyimide.
ポリイミド樹脂は、高い機械的強度、耐熱性、絶縁性、耐溶剤性を有しているため、液晶表示素子や半導体における保護材料、絶縁材料、カラーフィルタ等の電子材料用薄膜として広く用いられている。 Polyimide resin has high mechanical strength, heat resistance, insulation, and solvent resistance, so it is widely used as a thin film for electronic materials such as protective materials, insulation materials, and color filters in liquid crystal display elements and semiconductors. Yes.
しかし、従来の全芳香族ポリイミド樹脂は、濃い琥珀色を呈して着色するため、高い透明性が要求される電子デバイス分野の厚膜においては問題が生じる。特許文献１は、ポリイミドフィルムの光透過性を改善し、特許文献２は、レジスト用途においてポリイミドの耐熱性及び低誘電率を改善している。 However, since the conventional wholly aromatic polyimide resin is colored with a deep amber color, there is a problem in the thick film of the electronic device field that requires high transparency. Patent Document 1 improves the light transmittance of a polyimide film, and Patent Document 2 improves the heat resistance and low dielectric constant of polyimide in resist applications.
しかし、さらに液晶ディスプレイやＬＥＤ分野等においては、該用途に適したプロセスが適用でき、優れた光透過性を有し、耐熱性に優れるポリイミドが求められていた。 However, in the field of liquid crystal displays and LEDs, a process suitable for the application can be applied, and polyimide having excellent light transmittance and excellent heat resistance has been demanded.
本発明の目的は、光透過度を維持しつつ、かつ耐熱性に優れるポリイミド樹脂を提供することにある。 The objective of this invention is providing the polyimide resin which is excellent in heat resistance, maintaining light transmittance.
このような目的は、下記（１）〜（７）の本発明により達成される。
（１）式（１）で表される単位構造と、式（２）で表される単位構造とを有する共重合ポリイミド前駆体。
（２）式（１）で表される単位構造と、式（２）で表される単位構造との比率［式（１）の数／式（２）の数］が９０／１０〜９９．９／０．０１であることを特徴とする（１）に記載の共重合ポリイミド前駆体。
（３）溶剤中で、下記式（３）及び式（４）で表されるジアミン化合物、及び式（５）で表されるテトラカルボン酸化合物を重合反応させることにより得られる（１）または（２）に記載の共重合ポリイミド前駆体。
（４）（１）乃至（３）のいずれか１項に記載の共重合ポリイミド前駆体を重合反応させることにより得られる、式（６）で表される単位構造と、式（７）で表される単位構造を有する共重合ポリイミド。
（５）式（６）で表される単位構造と、式（７）で表される単位構造との比率［式（６）の数／式（７）の数］が９０／１０〜９９．９／０．０１であることを特徴とする（４）に記載の共重合ポリイミド。
（６）膜厚１０μｍのフィルムにした時のイエローインデックスが４．０未満であることを特徴とする（４）または（５）のいずれかに記載の共重合ポリイミド。
（７）膜厚１０μｍのフィルムにした時の動的粘弾性測定において、ｔａｎδの極大点から求めたガラス転移温度が４００℃以上であることを特徴とする（４）乃至（６）のいずれか１項に記載の共重合ポリイミド。
Such an object is achieved by the present inventions (1) to (7) below.
(1) A copolymer polyimide precursor having a unit structure represented by the formula (1) and a unit structure represented by the formula (2).
(2) The ratio of the unit structure represented by formula (1) and the unit structure represented by formula (2) [number of formula (1) / number of formula (2)] is 90/10 to 99.99. The copolymer polyimide precursor according to (1), which is 9 / 0.01.
(3) (1) or (1) obtained by polymerizing a diamine compound represented by the following formula (3) and formula (4) and a tetracarboxylic acid compound represented by formula (5) in a solvent. Copolymer polyimide precursor according to 2).
(4) A unit structure represented by formula (6) obtained by polymerizing the copolymerized polyimide precursor according to any one of (1) to (3), and represented by formula (7) Copolymer polyimide having a unit structure.
(5) The ratio of the unit structure represented by formula (6) and the unit structure represented by formula (7) [number of formula (6) / number of formula (7)] is 90/10 to 99.99. The copolymerized polyimide according to (4), which is 9 / 0.01.
(6) The copolymerized polyimide according to any one of (4) and (5), wherein the yellow index when the film is 10 μm thick is less than 4.0.
(7) Any of (4) to (6), wherein the glass transition temperature obtained from the maximum point of tan δ is 400 ° C. or higher in dynamic viscoelasticity measurement when a film having a thickness of 10 μm is formed. The copolymerized polyimide according to item 1.
本発明によれば、光透過度が高く、かつ耐熱性に優れるポリイミド樹脂を提供することが可能となる。 According to the present invention, it is possible to provide a polyimide resin having high light transmittance and excellent heat resistance.
以下、本発明の光透過度が高く、かつ耐熱性に優れるポリイミド樹脂を提供する共重合ポリイミド前駆体および共重合ポリイミドについて好適実施形態に基づいて詳細に説明するが、これらは本発明の実施形態の一例であり、これらの内容のみに限定されない。 Hereinafter, the copolymer polyimide precursor and the copolymer polyimide that provide a polyimide resin having high light transmittance and excellent heat resistance according to the present invention will be described in detail based on preferred embodiments, which are embodiments of the present invention. It is an example and is not limited only to these contents.
本実施形態によれば、共重合ポリイミド前駆体は、ジアミン化合物とテトラカルボン酸化合物を重合反応して得られる下記の式（１）および式（２）で表わされる単位構造で構成されたものであり、この構成で作製される共重合体ポリイミドワニスは、高い透明性と耐熱性に優れた前駆体を有するためポリイミド共重合体を生成することができる。
このような共重合ポリイミド前駆体の作製方法には２つの方法がある。
According to this embodiment, the copolymer polyimide precursor is composed of a unit structure represented by the following formula (1) and formula (2) obtained by polymerization reaction of a diamine compound and a tetracarboxylic acid compound. In addition, the copolymer polyimide varnish produced with this configuration has a precursor having high transparency and excellent heat resistance, and therefore can produce a polyimide copolymer.
There are two methods for producing such a copolymerized polyimide precursor.
＜共重合ポリイミド前駆体の説明１＞
まず、第１の共重合ポリイミド前駆体の作製方法について述べる。
本発明の共重合ポリイミド前駆体は、溶剤中で、下記式（３）及び式（４）で表されるジアミン化合物、及び式（５）で表されるテトラカルボン酸無水物を重合反応させることにより得られる。
<Description 1 of copolymerized polyimide precursor>
First, a method for producing the first copolymer polyimide precursor will be described.
The copolymerized polyimide precursor of the present invention is obtained by polymerizing a diamine compound represented by the following formulas (3) and (4) and a tetracarboxylic acid anhydride represented by the formula (5) in a solvent. Is obtained.
本発明の共重合ポリイミド前駆体は、式（３）及び式（４）で表されるジアミン化合物、
及び式（５）で表されるテトラカルボン酸無水物を同時に有する溶液を重合反応して得られ、ワニス状で得られるものである。
The copolymer polyimide precursor of the present invention is a diamine compound represented by formula (3) and formula (4),
And a solution having a tetracarboxylic acid anhydride represented by the formula (5) at the same time as a polymerization reaction, and obtained in a varnish form.
共重合ポリイミド前駆体の重合反応は、まず反応温度は、通常−２０〜１５０℃、好ましくは−５〜１００℃の任意の温度を選択することができる。 As for the polymerization reaction of the copolymerized polyimide precursor, first, the reaction temperature can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
また、共重合ポリイミド前駆体の合成に用いられる溶媒としては、例えば、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ｍ−クレゾール、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルホスホルアミド、γ−ブチロラクトン等が挙げられ、特にＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）を好適に用いことができる。これらは、単独で使用しても、混合して使用してもよい。さらに、共重合ポリイミド前駆体を溶解しない溶媒であっても、均一な溶液が得られる範囲内で上記溶媒に加えて使用してもよい。 Examples of the solvent used for the synthesis of the copolymerized polyimide precursor include N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), m-cresol, N, N-dimethylformamide ( DMF), N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylphosphoramide, γ-butyrolactone, etc., and particularly preferably N, N-dimethylacetamide (DMAc) is used. it can. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve a copolymer polyimide precursor, you may use it in addition to the said solvent within the range in which a uniform solution is obtained.
その混合割合は式（１）で表される単位構造と、式（２）で表される単位構造との比率［式（１）の数／式（２）の数］が９０／１０〜９９．９／０．０１であることが好ましい。この比率の共重合ポリイミド前駆体を用いることで、光透過度が高く、かつ耐熱性に優れるという二つの特性を併せ持つ共重合ポリイミドを簡便に作成することが可能となる。具体的には前記比率［式（１）の数／式（２）の数］は、式（３）及び式（４）の仕込み比率から算出することができる。 The mixing ratio of the unit structure represented by formula (1) and the unit structure represented by formula (2) [number of formula (1) / number of formula (2)] is 90/10 to 99. .9 / 0.01 is preferable. By using a copolymerized polyimide precursor of this ratio, it is possible to easily prepare a copolymerized polyimide having both the characteristics of high light transmittance and excellent heat resistance. Specifically, the ratio [number of formulas (1) / number of formulas (2)] can be calculated from the charging ratios of formulas (3) and (4).
＜共重合ポリイミド前駆体の説明２＞
次に、もう一つの共重合ポリイミド前駆体の作製方法としては、下記の式（１）および式（２）で表わされる単位構造を別々に合成した後、混合させることで共重合体ポリイミドワニスを作製することができる
前記二種の単位構造の作製について述べる。
まず、式（１）で表わされる単位構造は、下記の式（５）であらわされるテトラカルボン酸と、式（３）であらわされるジアミン化合物を用い共重合させたポリイミド前駆体である。
Next, as another method for preparing a copolymerized polyimide precursor, unit structures represented by the following formulas (1) and (2) are separately synthesized, and then mixed to obtain a copolymer polyimide varnish. Can be made
The production of the two types of unit structures will be described.
First, the unit structure represented by the formula (1) is a polyimide precursor copolymerized using a tetracarboxylic acid represented by the following formula (5) and a diamine compound represented by the formula (3).
もう一方の式（２）であらわされる単位構造は、下記の式（５）であらわされるテトラカルボン酸無水物と、式（４）であらわされるジアミン化合物を用い共重合させたポリイミド前駆体である。
＜重合方法＞
前記二種のポリイミド前駆体の重合反応は、まず反応温度は、通常−２０〜１５０℃、好ましくは−５〜１００℃の任意の温度を選択することができる。
また、ポリイミド前駆体の合成に用いられる溶媒としては、例えば、Ｎ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）、Ｎ−メチル−２−ピロリドン（ＮＭＰ）、ｍ−クレゾール、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルカプロラクタム、ジメチルスルホキシド、テトラメチル尿素、ピリジン、ジメチルスルホン、ヘキサメチルホスホルアミド、
γ−ブチロラクトン等が挙げられ、特にＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ）を好適に用いことができる。これらは、単独で使用しても、混合して使用してもよい。さらに、ポリイミド前駆体を溶解しない溶媒であっても、均一な溶液が得られる範囲内で上記溶媒に加えて使用してもよい。
<Polymerization method>
In the polymerization reaction of the two kinds of polyimide precursors, first, the reaction temperature can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
Examples of the solvent used for the synthesis of the polyimide precursor include N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), m-cresol, N, N-dimethylformamide (DMF). N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethylphosphoramide,
Examples thereof include γ-butyrolactone, and N, N-dimethylacetamide (DMAc) can be particularly preferably used. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt | dissolve a polyimide precursor, you may use it in addition to the said solvent within the range in which a uniform solution is obtained.
本発明の共重合ポリイミド前駆体前記は、前述のポリイミド前駆体式（１）と式（２）で表される単位構造とを比率［式（１）の数／式（２）の数］が９０／１０〜９９．９／０．０１で混合したものであることが好ましく、この比率の共重合ポリイミド前駆体を用いることで、光透過度が高く、かつ耐熱性に優れる共重合ポリイミドを簡便に作成することが可能となる。 Copolymerized polyimide precursor of the present invention The ratio of the above-mentioned polyimide precursor formula (1) and unit structure represented by formula (2) is 90 [number of formula (1) / number of formula (2)]. / 10 to 99.9 / 0.01 is preferable. By using a copolymer polyimide precursor of this ratio, a copolymer polyimide having high light transmittance and excellent heat resistance can be easily obtained. It becomes possible to create.
＜共重合ポリイミド＞
本発明の共重合体ポリイミドは、上記の共重合ポリイミド前駆体をさらに重合反応させることにより得られる、式（６）で表される単位構造と、式（７）で表される単位構造を有する共重合ポリイミドである。
<Copolymerized polyimide>
The copolymer polyimide of the present invention has a unit structure represented by the formula (6) and a unit structure represented by the formula (7), which are obtained by further polymerizing the copolymer polyimide precursor. It is a copolymerized polyimide.
本発明のポリイミド共重合体は、共重合ポリイミド前駆体、式（１）で表される単位構造と、式（２）で表される単位構造との比率が［式（１）の数／式（２）の数］が９０／１０〜９９．９／０．０１であったことから、その比率がそのまま保存され［式（６）の数／式（７）の数］とすることができる。 In the polyimide copolymer of the present invention, the ratio of the copolymer polyimide precursor, the unit structure represented by the formula (1) and the unit structure represented by the formula (2) is [number of formulas (1) / formula Since the number of (2)] was 90/10 to 99.9 / 0.01, the ratio was preserved as it was and could be [number of formula (6) / number of formula (7)]. .
＜共重合ポリイミドの作製＞
具体的な共重合体ポリイミドは、以下の方法で作製することができる。
すなわち、先に作製した共重合ポリイミド前駆体ワニスを、基板上に塗布する工程、乾燥し溶媒を除去する工程、さらに昇温して熱イミド化する工程を経ることによって得ることができる。
<Preparation of copolymerized polyimide>
A specific copolymer polyimide can be produced by the following method.
That is, it can be obtained by applying the previously prepared copolymerized polyimide precursor varnish on the substrate, drying and removing the solvent, and further heating and imidizing.
共重合ポリイミド前駆体ワニスを、基板上に塗布する工程で用いる基板は特に限定するものではないが、ワニスに含まれる溶媒に侵されることがないように、例えば、ガラス基板
、シリコン基板（シリコンウェハ等）、または金属基板等が適しており、特にガラス基板が好適に使用される。
The substrate used in the step of applying the copolymerized polyimide precursor varnish on the substrate is not particularly limited. For example, a glass substrate or a silicon substrate (silicon wafer) is used so as not to be affected by the solvent contained in the varnish. Etc.), or a metal substrate is suitable, and a glass substrate is particularly preferably used.
さらに、共重合ポリイミド前駆体ワニスを塗布する前に、減圧化で脱泡させて用いることで気泡による欠損が生じることを抑制することができる。 Furthermore, before applying the copolymerized polyimide precursor varnish, it is possible to suppress the occurrence of defects due to bubbles by degassing under reduced pressure.
塗布作業の方法は、特に限定しない。基板上に共重合ポリイミド前駆体ワニスが塗布されればそれで良い The method of application | coating operation | work is not specifically limited. If the copolymerized polyimide precursor varnish is coated on the substrate, that's fine.
次に、乾燥し溶媒を除去する工程であるが、これに続く昇温して熱イミド化する工程を併せて行うことも可能である。
例として、真空下又は不活性ガス存在下で、開始時は室温以上で１時間以上加温、途中１５０℃〜２００℃で１時間以上加温し、最終的に２５０℃以上で１時間以上することで、乾燥、および熱イミド化ができる。
使用する不活性ガスは、例えば、窒素、アルゴン等を使用することができる。
具体的には、真空下で、８０℃で１時間、１５０℃で１時間、２００℃で１時間、次いで最終的に３００℃で１時間と段階的に昇温することで溶媒除去と熱イミド化を併せて行うことができる。
Next, although it is the process of drying and removing a solvent, it is also possible to perform the process which heats up and heat imidizes subsequent to this.
For example, in a vacuum or in the presence of an inert gas, at the beginning, warm at room temperature or higher for 1 hour or longer, heat at 150 ° C to 200 ° C for 1 hour or longer, and finally at 250 ° C or higher for 1 hour or longer. Thus, drying and thermal imidization can be performed.
As the inert gas used, for example, nitrogen, argon, or the like can be used.
Specifically, under vacuum, solvent removal and thermal imide are carried out by raising the temperature stepwise at 80 ° C. for 1 hour, 150 ° C. for 1 hour, 200 ° C. for 1 hour, and finally 300 ° C. for 1 hour. Can also be performed.
上記の様にして、得られたポリイミド共重合体は、以下に示す特性を有することを確認した。 As described above, it was confirmed that the obtained polyimide copolymer had the following characteristics.
本発明の実施形態において、透明性を有する事が必要であり、前記ポリイミド重合体は、光線透過率、ヘイズ、および黄色度（イエローインデックス、ＹＩ）において良好な測定値であることが重要である。特にポリイミド樹脂は黄色に着色する傾向が高く、そのため、ＹＩが低ければ低いほど良好である。具体的には、膜厚１０μｍのフィルムにした時のＹＩが４．０未満であることが好ましい。
本実施形態において、前記条件でＹＩが４．０未満となることを確認した。
In an embodiment of the present invention, it is necessary to have transparency, and it is important that the polyimide polymer has good measured values in light transmittance, haze, and yellowness (yellow index, YI). . In particular, the polyimide resin has a high tendency to be colored yellow. Therefore, the lower the YI, the better. Specifically, it is preferable that YI when the film is 10 μm thick is less than 4.0.
In the present embodiment, it was confirmed that YI was less than 4.0 under the above conditions.
本発明のポリイミド共重合体は、耐熱性に優れることが重要であり、本発明の実施形態において、ガラス転移温度が４００℃以上であることが確認できた。４００℃未満においては、ガラス転移温度の測定は、膜厚１０μｍのフィルムにした時の動的粘弾性測定において、ｔａｎδの極大点から求めた。 It is important for the polyimide copolymer of the present invention to be excellent in heat resistance. In the embodiment of the present invention, it was confirmed that the glass transition temperature was 400 ° C. or higher. Below 400 ° C., the glass transition temperature was determined from the maximum point of tan δ in the dynamic viscoelasticity measurement when a film having a thickness of 10 μm was formed.
以下に記載のポリイミドフィルムの評価方法を具体的に記載した。 The evaluation method of the polyimide film described below was specifically described.
＜光線透過率、ヘイズ、黄色度（ＹＩ）＞
日本分光社製紫外可視分光光度計（Ｖ−６５０）を用い、フィルム（１０μｍ厚）の４００ｎｍの波長の全光線透過率、ヘイズ、ＸＹＺ三刺激値を測定した。
ＹＩの算出はＸＹＺ三刺激値と、ＪＩＳ Ｋ ７３７３の「標準イルミナントＤ６５を使用しＸＹＺ表色系を用いる場合」の式により行った。
<Light transmittance, haze, yellowness (YI)>
Using a UV-visible spectrophotometer (V-650) manufactured by JASCO Corporation, the total light transmittance, haze, and XYZ tristimulus values at a wavelength of 400 nm of the film (10 μm thick) were measured.
YI was calculated according to the XYZ tristimulus value and the formula of “when using standard illuminant D65 and XYZ color system” of JIS K 7373.
＜弾性率＞
エスアイアイ・ナノテクノロジー社製動的粘弾性測定装置（ＤＭＳ６０００）を用いて、動的粘弾性測定により、周波数１Ｈｚ、昇温速度５℃／分における貯蔵弾性率を求めた。
<Elastic modulus>
The storage elastic modulus at a frequency of 1 Hz and a heating rate of 5 ° C./min was determined by dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (DMS6000) manufactured by SII Nanotechnology.
＜ガラス転移温度の算出＞
オリエンテック社製動的粘弾性測定装置（レオバイブロンＤＤＶ０１ＦＰ型）を用いて、動的粘弾性測定により、周波数１Ｈｚ、昇温速度５℃／分におけるｔａｎδピークからポリイミドフィルム（１０μｍ厚）のガラス転移温度を求めた。
<Calculation of glass transition temperature>
Glass transition temperature of polyimide film (10 μm thickness) from tan δ peak at a frequency of 1 Hz and a heating rate of 5 ° C./min by dynamic viscoelasticity measurement using a dynamic viscoelasticity measuring device (Leovibron DDV01FP type) manufactured by Orientec. Asked.
＜線膨張係数（ＣＴＥ）＞
エスアイアイ・ナノテクノロジー社製熱機械的分析装置（ＴＭＡ／ＳＳ１２０Ｃ）を用いて、熱機械分析により、荷重１５．６８ｍＮ、昇温速度５℃／分における試験片の伸びより、３０℃〜２００℃の範囲での平均値としてポリイミドフィルム（１０μｍ厚）の線膨張係数を求めた。
<Linear expansion coefficient (CTE)>
Using a thermomechanical analyzer (TMA / SS120C) manufactured by SII NanoTechnology Co., Ltd., the elongation of the test piece at a load of 15.68 mN and a heating rate of 5 ° C./min is 30 ° C. to 200 ° C. The linear expansion coefficient of the polyimide film (10 μm thickness) was determined as an average value in the range of
以下に本発明を実施例に続いて詳細に説明するが、本発明はこれに限定するものではない。 Hereinafter, the present invention will be described in detail following examples, but the present invention is not limited thereto.
（実施例１）
５０ｍＬ三ツ口フラスコに窒素雰囲気下で２，２‘−ビス（トリフルオロメチル）ベンジジン（以下、ＴＦＤＢと略記することがある）０．７４９９ｇと９，９−ビス（４−アミノフェニル）フルオレン（以下、ＦＤＡと略記することがある）０．０９１０ｇを入れ、ジメチルアセトアミド（以下、ＤＭＡｃと略記することがある）５．１ｍＬを加えて撹拌することにより溶解させた。
この三ツ口フラスコを室温のウォーターバス中で、撹拌しながら３，３，４，４−テトラカルボン酸二無水物（以下、ＢＰＤＡと略記することがある）０．７６６４ｇを添加し、ＤＭＡｃ１．７ｍＬでフラスコ内壁に付着したＢＰＤＡを洗い落とし、そのまま室温で１４時間撹拌した。その後、ＤＭＡｃ１．０ｍＬを追加してＢＰＤＡの溶け残りを溶解させ、室温で２４時間撹拌し、均一で粘稠な共重合ポリイミド前駆体溶液組成物を得た。
Example 1
In a 50 mL three-necked flask, 0.7499 g of 2,2′-bis (trifluoromethyl) benzidine (hereinafter sometimes abbreviated as TFDB) and 9,9-bis (4-aminophenyl) fluorene (hereinafter, 0.0910 g (sometimes abbreviated as FDA) was added, and 5.1 mL of dimethylacetamide (hereinafter sometimes abbreviated as DMAc) was added and dissolved by stirring.
While stirring this three-necked flask in a water bath at room temperature, 0.7664 g of 3,3,4,4-tetracarboxylic dianhydride (hereinafter sometimes abbreviated as BPDA) was added, and the DMAc was 1.7 mL. BPDA adhering to the inner wall of the flask was washed off and stirred as it was at room temperature for 14 hours. Thereafter, 1.0 mL of DMAc was added to dissolve the undissolved residue of BPDA, and the mixture was stirred at room temperature for 24 hours to obtain a uniform and viscous copolymerized polyimide precursor solution composition.
得られた共重合ポリイミド前駆体溶液組成物を真空脱泡したのちガラス基板上に塗布、そのまま基板上で、真空下、８０℃で１時間、１５０℃で１時間、２００℃で１時間、次いで最終的に３００℃で１時間と段階的に昇温して熱イミド化を行い、無色透明な共重合ポリイミド／ガラス積層体を得た。次いで、得られたポリイミド／ガラス積層体からカッターナイフを用いて剥離し、膜厚が約１０マイクロメートルのポリイミドフィルムを得た。このフィルムの特性を測定した結果を表１に示す。 The resulting copolymerized polyimide precursor solution composition was vacuum degassed and then applied onto a glass substrate, as it was on the substrate, under vacuum, at 80 ° C. for 1 hour, 150 ° C. for 1 hour, 200 ° C. for 1 hour, then Finally, the temperature was raised stepwise at 300 ° C. for 1 hour to carry out thermal imidization to obtain a colorless and transparent copolymer polyimide / glass laminate. Subsequently, it peeled from the obtained polyimide / glass laminated body using the cutter knife, and obtained the polyimide film whose film thickness is about 10 micrometers. The results of measuring the properties of this film are shown in Table 1.
（比較例１）
ＦＤＡを投入しなかったこと以外は、実施例１と同じ。
結果を表1に示す。
(Comparative Example 1)
Same as Example 1 except that no FDA was introduced.
The results are shown in Table 1.
本発明により、光透過度を維持しつつ、かつ耐熱性に優れるポリイミドフィルムを得ることができた。このフィルムは、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として幅広く使用することが可能である。
According to the present invention, a polyimide film having excellent heat resistance while maintaining light transmittance could be obtained. This film can be widely used as a film, a coating agent, a molded part and an insulating material in fields such as the electric, electronic, automobile and aerospace industries.
Claims (7)
A copolymer polyimide precursor having a unit structure represented by the following formula (1) and a unit structure represented by the formula (2).
The solvent according to claim 1 or 2, which is obtained by polymerizing a diamine compound represented by the following formula (3) and formula (4) and a tetracarboxylic acid compound represented by formula (5) in a solvent. Copolymer polyimide precursor.
7. The glass transition temperature obtained from the maximum point of tan δ in a dynamic viscoelasticity measurement when a film having a thickness of 10 μm is formed is 400 ° C. or higher. 7. Copolyimide.
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| JP2018190787A (en) * | 2017-04-28 | 2018-11-29 | 日東電工株式会社 | Flexible wiring circuit board, manufacturing method thereof, and imaging device |
| WO2022118794A1 (en) * | 2020-12-03 | 2022-06-09 | 三井化学株式会社 | Polyamic acid, varnish including same, method for producing polyamic acid, polyimide, film including same, and display panel substrate |
| WO2023013453A1 (en) * | 2021-08-02 | 2023-02-09 | 東洋紡株式会社 | Electronic display apparatus |
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| WO2022118794A1 (en) * | 2020-12-03 | 2022-06-09 | 三井化学株式会社 | Polyamic acid, varnish including same, method for producing polyamic acid, polyimide, film including same, and display panel substrate |
| WO2023013453A1 (en) * | 2021-08-02 | 2023-02-09 | 東洋紡株式会社 | Electronic display apparatus |
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